Stability of thermally hypersensitised

phosphosilicate waveguides and the

characteristic growth curve

J. Canning and P-F. Hu

Optical Fibre Technology Centre & Australian Photonics Cooperative Research Centre,
University of Sydney, 206 National Innovation Centre, ATP, Eveleigh,
Sydney, NSW, 1430, Australia
Tel: 61-2-9351 1934, fax: 61-2-9351 1911, j.canning@oftc.usyd.edu.au

Abstract: Low temperature (800C) hypersensitised hydrogen-loaded

phosphosilicate optical fibre is found to be unstable, decaying progressively
at room temperature. However, the hypersensitisation process linearises the
grating growth characteristic curve. Further, a negative index contribution is
inferred at low fluence in the presence of hydrogen.
2001 Optical Society of America
OCIS codes: (160.4670) Optical materials; (260.5130) Photochemistry; (230.1150) All-optical
devices (999.9999) Hypersensitisation

References and links

1. J. Canning, “Photosensitisation and photostabilisation of laser induced index changes in optical fibres,”
Opt. Fibre. Tech., 6 275-289, (2000)
2. J. Canning, “Contemporary Thoughts on Glass Photosensitivity and their Practical Application,” Materials
Forum, 25 101-128, (2001)
3. J. Canning, M. Åslund and P-F. Hu, “UV-induced absorption losses in hydrogen-loaded optical fibres and
in pre-sensitised optical fibres,” Opt. Lett., 25 1621-1623, (2000)
4. M. Åslund, J. Canning and G. Yoffe, “Locking in photosensitivity in optical fibres and waveguides,” Opt.
Lett., 24 1826-1828, (1999)
5. M. Åslund and J. Canning, “Annealing properties of gratings written into UV-presensitised hydrogen out-
diffused optical fibre,” Opt. Lett., 25 692-694, (2000)
6. J. Canning, “Improving the manufacture of fibre Bragg gratings,” SPIE Vol. 3896 769-778, (1999)
7. J. Canning and P-F. Hu, “Eliminating UV-induced losses during UV-exposure of photo-hypersensitised
optical fibres,” Proceedings of Bragg Gratings, Photosensitivity, and Poling In Glass Waveguides, Stresa,
Italy, paper BthA6-1, (2001)
8. K.P. Chen, P.R. Hermann and R. Tam, “157nm F2 laser photosensitivity and photosensitisation in optical
fibres,” Proceedings of Bragg Gratings, Photosensitivity, and Poling In Glass Waveguides, Stresa, Italy,
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9. K.P. Chen, P.R. Hermann and R. Tam, “Trimming phase and birefringence errors in photosensitivity-
locked planar optical circuits,” Accepted for IEEE Phot. Tech. Lett., (2001)
10. J. Canning and K. Sommer, “Hypersensitisation of Rare-Earth Doped Waveguides for DFB Amplifier and
Laser Applications,” Accepted to Opt Lett. (2001)
11. J. Canning, K. Sommer, M. Englund and S. Huntington, “Direct evidence of two types of UV-induced
glass changes in silicate-based optical fibres,” Adv. Mater., 13 970-973, (2001)
12. J. Canning and P-F. Hu, “Low temperature hypersensitisation of phosphosilicate waveguides in
hydrogen,” Opt. Lett., 26 1230-1232, (2001)
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Sci. Technol., 12 824-828, (2001)
14. P. Hu, J. Canning, K. Sommer and M. Englund, “Phosphosilicate optical fibres: a grating host for all
windows?” Proceedings of Optoelectronics and Optical Communications Conference (OECC/IOOC
2001), Sydney, Australia, pp.24-25, (2001)
15. J. Canning, M.G. Sceats, H.G. Inglis and P.Hill, “Transient and permanent gratings in phosphosilicate
optical fibres produced by the flash condensation technique,” Opt. Lett., 20 2189-2191, (1995)
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Verlag, Berlin, (1995)

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 18. L. Dong, J. L. Archambault, L. Reekie, P. St. J. Russell and D. N. Payne, “Photoinduced absorption
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Theoretical Chemistry Department, University of Sydney, (1997)

1. Introduction
Hypersensitisation is a process recently developed where the intrinsic glass photosensitivity of
waveguides is permanently enhanced with hydrogen and a preliminary pre-exposure [1,2].
Subsequent out-diffusion of the hydrogen leaves behind an optical waveguide with an
enhanced photosensitive response more suited for component fabrication for a number of
reasons. Issues such as unwanted absorption bands, hydrogen out-diffusion and an unstable
index change contribution are removed by this technique [3-5]. Most of the means of
hypersensitisation have involved photolytic irradiation with UV light from various laser
sources, including pulsed exciplex (ArF - 193nm, KrF - 248nm), pulsed excimer (F2 -
157nm), and CW frequency doubled Ar+ lasers (244nm) [1-10]. The waveguide material
analysed to date and found to be responsive to the treatment includes pure silica,
germanosilicate with and without boron and phosphosilicate, emphasising the generality of
the hypersensitisation process. The underlying benefit of this process is to remove the
undesirable component to index change that is present under conventional exposure of UV
irradiation of optical waveguides loaded with hydrogen. This additional index change arises
from stresses at the core/cladding interface that increase as densification takes place at the
core [11].
More recently, low temperature hypersensitisation of phosphosilicate waveguides has
been demonstrated and shown to offer similar advantages to photo-hypersensitisation in most
of these areas [12]. In this process, the initial sensitisation step ordinarily carried out with
irradiation, is instead, carried out by heating during the hydrogen loading phase at moderately
low temperatures, typically 800C. However, low temperature thermal hypersensitisation is a
very low energy process and there are questions regarding its intrinsic stability compared to
photolytic treatment where bonds are broken as well as local heating arising. In this paper we
show that in phosphosilicate optical fibres low temperature hypersensitisation is not stable
over time and decays gradually, increasing the total fluence required to write similar strength
Bragg gratings. Nevertheless, the advantages of low loss and stability reported earlier for
photo-hypersensitised phosphosilicate optical fibres [12-14] remain. Further, another
important reason for still using thermal hypersensitisation is the linearised grating growth
characteristic curve, which simplifies the reproducibility of UV writing or processing of
optical components. In addition, it is found that over short exposure fluence, the grating
strength achievable is found to be larger for the hypersensitised fibre than for fully-hydrogen
loaded fibre. This indicates that the subsequent contribution of hydrogen in conventional
photosensitivity work through OH formation has a negative index contribution.
2. Hypersensitisation and Grating Writing

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Thermal sensitisation of a fibre during hydrogen loading is predicated on the basis that the
grating strength in phosphosilicate fibre did not correlate with the in-diffusion rate of
molecular hydrogen [15]. In order to investigate a similar correlation between out-diffusion
and grating strength, we measured the grating growth curve for hydrogen loaded
phosphosilicate optical fibre at various stages of out-diffusion, including time well outside
complete out-diffusion: i.e. in the hypersensitisation domain. In this way characteristic growth
curves were obtained for fully hydrogen loaded fibre and for fibre at different stages after out-
diffusion.
The phosphosilicate optical fibre is fabricated by modified MCVD where the phosphate is
introduced by flash condensation using phosphoric acid [16]. Up to 17mol% of P2O5 is readily
incorporated into the silica core. The V-parameter is matched to standard telecommunications
grade fibre.

) -5
B
d
(
n
io
s
is -10
m
s
n
a
r
t

-15

-20
1539.0 1539.5 1540.0 1540.5 1541.0
Wavelength (nm)
Figure 1. Typical transmission spectrum of a grating written into hypersensitised
phosphosilicate optical fibre. The resolution is 0.1nm.

Hydrogen loading of the phosphosilicate fibres was carried out at 200atm pressure and
800C for 14 days, well beyond the diffusion saturation time of less than a day at the conditions
employed. This ensured that low energy thermal hypersensitisation has occurred. As soon as
the loading was complete, gratings were written into various samples of the fibre at different
times using 193nm direct grating writing through an optical phase mask. 193nm from an ArF
laser is chosen since longer wavelengths do not produce strong gratings in reasonable time
within phosphorus doped fibres [15]. Figure 1 shows a typical transmission spectrum of such
a grating written into a fibre 14 days after hydrogen begins out-diffusing. The spectrum is
resolution limited by the resolution of the optical spectrum analyser used, ~0.1nm. In previous
work, it was shown that once these gratings are written they have excellent thermal stability
making these gratings suitable for operation within high temperature (upwards of 7000C)
environments [13]. This compares dramatically when no hypersensitisation is used and the
gratings decay within minutes [15]. It is therefore of interest to see whether the thermal
hypersensitisation process itself is of similar stability.
3. Characteristic Curves
Figure 2a and b is a plot of the average induced index change with UV light during writing of
several gratings, which is begun at increasing time away from the loading phase. The average
index is determined from the shift in Bragg wavelength. This index profile describes the
characteristic photosensitive response of the waveguide and the plot is therefore defined to be
the characteristic curve of the material, consistent with the terminology used for photochromic
materials generally [17]. Figure 2b is an expanded version of figure 2a so that the

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(C) 2001 OSA 5 November 2001 / Vol. 9, No. 10 / OPTICS EXPRESS 478
characteristic response at low fluence can be analysed. What is immediately noticeable is that
whilst hydrogen remains present during irradiation, the characteristic growth curve is not
linear. However, the curvature decreases until close to 14 days, whereupon most of the
hydrogen has out-diffused, and the curve is linearised. This in itself is of interest since it
implies that some slow thermally driven, chemical sensitisation has indeed taken place during
loading as previously proposed [15]. Further, it can be observed generally that at low fluence
the index change grows as hydrogen out-diffuses (shown clearly in figure 2b) whilst at larger
fluence the reverse is true.
4. Discussion
∆navex10
-3

2.2
0.06
2.0
1.08
1.8
1.6
1.4
6.00
1.2
1.0
13.2
0.8
0.6
17.3
0.4
0.2
21
0.0
0 1 2 3 4 5 6 7 8 9 10
2
Fluence (kJ/cm )

∆navex10
-3

0.4

0.2

0.0
0 1 2 3
2
Fluence (kJ/cm )
Figure 2 a - top) Photosensitive response curve of phosphosilicate optical fibre at various times
after hydrogen loading (Time is indicated on days on the right).
b - bottom) Expanded version of a) to highlight response at lower fluence.
The solid lines are the initial profiles, which show an increase at low fluence. The dashed lines are the
growth curves after the increase has stopped at low fluence. At high fluence there is a general
decrease in the achieved index change with hydrogen out-diffusion. The arrows indicate the relative
direction of index modulation as it grows at low fluence and then drops at high fluence.

#35645 - $15.00 US Received October 02, 2001; Revised October 30, 2001
(C) 2001 OSA 5 November 2001 / Vol. 9, No. 10 / OPTICS EXPRESS 479
 0.4

yit 0.3
vti
ce
lf
eR
de 0.2
re
vo
ce
R
0.1

0.0
400 500 600 700
Temperature ( C)0

Figure 3. Plot of recovered fraction of normalised reflectivity after 3mins cooling inbetween
temperatures during isochronal annealing for a grating written into fully-hydrogen loaded (open
squares) and hypersensitised (filled squares) phosphosilicate optical fibres. Details of the isochronal
annealing experiments can be found in [13].

The observation of lower index change at low fluence within the hydrogenated samples is
consistent with a negative index contribution arising when hydrogen is present, indicating that
there is an initial growth in a negative index change as a result of continued formation of
hydrogen species. The timescales can only be explained if these species are forming as a
result of the initial index change at the core. Hence they must be related to the growing tensile
stress at the core/cladding interface, which is entirely consistent with previous work showing
that there is a spatially distinct index contribution arising at the core/cladding interface [11].
Since this negative index contribution eventually is overridden by further positive index
growth within the fully hydrogen loaded sample, its magnitude can be approximately
determined by taking the difference at low fluence between the fully hydrogen loaded case
(time zero after loading) and that where the characteristic curve with the largest index
modulation value at the same fluence. From figure 2b this is found to be ~10-4 – the
magnitude is consistent with that expected from polarisability changes when hydrogen species
are formed [18]. It cannot arise from a stress contribution since this contribution is passivated
by the formation of such species.
From previous isochronal annealing data [13], hypersensitised fibre had a
significantly enhanced elastic relaxation at higher temperatures than fibre irradiated fully
when hydrogen is present. Figure 3 summarises this data for comparison. It can be observed
that the grating written into a fully hydrogen-loaded phosphosilicate optical fibre has
significantly reduced recovery of reflectivity after heating, indicating that the elastic
component to the index change generated by core/cladding stresses whilst heating has been
passivated. It also indicates that a stress grating must be present since the reflectivity monitors
an index modulation with a period of ~0.5µm, consistent with that directly observed for
gratings written into pristine germanosilicate optical fibre [19]. It can therefore be concluded
that such a stress grating is negligible in the fully hydrogen loaded case and has been
passivated by hydrogen reactions at the core/cladding interface [11]. Consequently, the stress
contribution will be higher in the hypersensitised sample, supporting a previous argument that
the role of hydrogen in the hypersensitised fibre is to drive the core index change that occurs
in irradiated pristine fibre further [11]. The predominant species involved with UV irradiation
of hydrogen loaded optical fibres are the hydroxyl groups [4,20,21] and it can be concluded
that these are the source of negative index change. However, it has been recently proposed
that densification of silica with 193nm arises because there is rapid local cooling analogous to

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fast quenches used to form high density forms of silica [22]. If this cooling is slow then the
relaxation results in dilation of the network – conceivably, the presence of both stress and
passivating OH at the core/cladding interface can lead to a slowdown in thermal quenching at
the interface. In any case, the final positive index change is likely to arise from densification
at the core.
Figure 4 illustrates the behaviour in more detail. The normalised index change
obtained as a function of post-hydrogen loading time is shown at both low and high fixed
fluence. For comparison, the expected out-diffusion normalised to the initial hydrogen
concentration, is also displayed. The out-diffusion calculation follows that used in [15],
derived from classical diffusion solutions for a cylinder [23]:

Ct ∞
exp(− j n2 Dt m / b 2 )
= −2 ∑ (1)
C∞ n =1 j n J 1 ( jn )
where

w2
tm = t + (2)
8D
and [24]

 − 40.19 kJ / mol 
D = (2.83 x10 4 ) exp  cm 2 / s (3)
 RT 

Neither case follows the diffusion profile indicating that thermal sensitisation as
predicted in [15] is present. Further, at low fluence the contribution from a sizeable negative
component is maximum when the hydrogen concentration is maximum, again, indicating that
hydrogen interactions are the source of component. In line with previous work on
hypersensitisation where the index change arising from hydrogen contributions appears
localised to the diffuse core/cladding boundary as a result of tensile stress increase [11], it
may be concluded that this negative contribution arises around the core/cladding interface.

1.0
2
Fluence 10kJ/cm
Normalised index change and

2
0.8 Fluence 1kJ/cm
Hydrogen out-diffusion
normalised [H2]

0.6

0.4

0.2

0.0
0 5 10 15 20
time (days)

Figure 4 Normalised index change at fixed low and high fluence both as a function of out-diffusion time
are shown. The normalised out-diffusion profile is also superimposed to illustrate the deviation from a
simple linear proportionality between index change and hydrogen.

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(C) 2001 OSA 5 November 2001 / Vol. 9, No. 10 / OPTICS EXPRESS 481
Hence, the overall positive index change is less than expected until at greater fluence the
positive index change due to densification at the core dominates strongly. In the
hypersensitised case, where hydrogen is removed before significant reactions take place, the
absence of a negative contribution to index change results in a larger positive index change at
lower fluence despite the overall positive index change due to changes in the core being less.
This is why as the hydrogen out-diffuses from the core there is a noticeable increase in
positive index change at low fluence compared to the decrease observed at large fluence. As a
result there is a linearisation of the characteristic curve. Combined with the results presented
in figure 2, it can be concluded that the negative index contribution does not arise directly
from tensile stress growth at the interface since this remains present and is unpassivated in the
hypersensitised fibre. After the hydrogen has sufficiently out-diffused the decay profiles are
the same, within experimental error, for both low and high fluence, indicating no additional
phenomena in the hypersensitised fibre.
As mentioned, the elimination of hydrogen in the hypersensitised fibre results in a
linearised characteristic curve as shown in figure 2. This indicates the contribution from a
negative index change plays a role in generating the non-linear response in the characteristic
curve of fully hydrogen-loaded fibre. Hence, the second mechanism describing hydrogen
interactions which leads to increased positive index change with continued irradiation [1,11],
is convoluted with the presence of the negative index change. One can make preliminary
conclusions that the presence of hydrogen increases the total densification possible at the core.
This is consistent with the previous observations of hydrogen hopping in irradiated
hypersensitised fibre where the OH peak characterising Ge or P sites shifts towards the shorter
wavelength associated with SiOH [3,7,14]. It too indicates that the hydrogen plays a catalytic-
like role in aiding structural change such as densification. However, this positive index change
itself has two components in the fully H2-loaded case since annealing removes one over the
other [25]. The reduced positive index change at larger fluence adds further support that the
second positive component is also related to hydrogen reactions, possibly as a result of the
additional contribution from passivation of the tensile stress [1,2,11].
Despite the instability of the low temperature thermal hypersensitisation process, it is
clearly of benefit to allow hydrogen to out-diffuse from the fibre prior to grating writing. A
linearised photosensitive response curve has advantages in a fabrication environment since it
allows improved reliability and reproducibility in component manufacture and removes the
high tolerance demanded on predicting grating device performance. Further, the variation in
annealing decay found in fully hydrogen-loaded samples where two index contributions are
present is removed. This means the uncertainty associated with the different decay rates
between localised regions of high and low index change [25] is removed. The ability to
extract a higher positive refractive index at lower fluence can also lead to more efficient
processing times when the index change required is not large.
7. Conclusion
In conclusion, low temperature hypersensitisation of phosphosilicate optical fibres is found to
be relatively unstable. However, hypersensitisation leads to a linearised photosensitive
response curve and higher refractive index change at lower fluence than a fully hydrogen
loaded optical fibre. There is an optimal value of sensitisation fluence to enjoy the benefits of
a linearised grating growth curve balanced against the increase in writing fluence the further
away from this optimal value. Together with the improved thermal stability of gratings
subsequently written into such fibre and reduced OH formation, these are important
advantages that can allow improved production efficiency in a manufacturing environment.

Acknowledgments:
J. Canning acknowledges an Australian Research Council Large Grant and a QEII Fellowship.

#35645 - $15.00 US Received October 02, 2001; Revised October 30, 2001
(C) 2001 OSA 5 November 2001 / Vol. 9, No. 10 / OPTICS EXPRESS 482