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The application of the mid-infrared spectral region in medical surgery:

Chalcogenide glass optical fibre for 10.6 μm laser transmission

Article  in  Proceedings of SPIE - The International Society for Optical Engineering · March 2008
DOI: 10.1117/12.760882

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 The application of the mid-infrared spectral region in medical surgery:
chalcogenide glass optical fibre for 10.6 µm laser transmission.
1
HL Rowe, 3JD Shephard, 1D Furniss, 1aCA Miller, 1bS Savage, 2TM Benson, 3DP Hand
and 1AB Seddon
1
Novel Photonic Glasses Research Group, 2George Green Institute for Electromagnetic Research,
University of Nottingham, Nottingham NG7 2RD, UK.
3
School of Engineering and Physical Sciences, Heriot-Watt University, Edinburgh EH14 4AS,
Scotland.
a
Now at: Oral and Maxillofacial Medicine and Surgery, School of Clinical Dentistry, University of
Sheffield, UK.
b
Now at: School of Mechanical, Aerospace and Civil Engineering, University of Manchester, UK

ABSTRACT
Infrared-transmitting glass optical fibres are being developed for intended applications in medicine and industry as part
of a laser delivery system, giving more flexibility and accuracy of positioning of the laser beam for the User.
Chalcogenide glass optical fibre is being designed to transmit light at 10.6 µm, to coincide with the wavelength of the
output light from the CO2 laser. In medicine, ablative surgery performed using the CO2 laser causes less damage to
surrounding tissue than when using shorter wavelength laser sources. The effect of composition of chalcogenide glasses
on optical absorption, across the wavelength range 3 µm to > 15 µm, has been investigated using Fourier transform
infrared (FTIR) spectroscopy, for a range of binary, ternary and quaternary glasses, in the form of small bulk glass
specimens. Glasses containing germanium tended to exhibit higher glass transformation temperatures but a shorter
wavelength multiphonon edge. The optical loss of fibre samples has been measured at 10.6 µm using a high power CO2
laser source and employing the fibre cut-back method. As2Se and Te30As20Se50 fibres (both unclad) exhibited 7.2, and
2.3, dBm-1, respectively. Ge17As18Se65 / Ge17As18Se62S3 core/clad. fibre exhibited an optical loss of 10.3 dBm-1. After the
optical loss measurements, fibres were imaged using scanning electron microscopy and it was found that the high power
CO2 laser caused damage to the launch end of some fibres. In particular, at the launch-end of Te-As-Se fibres the glass
appeared to have undergone partial melting and possibly also suffered some vaporisation.

Keywords: chalcogenide glasses, optical fibres, infrared, CO2 laser power delivery.

1. Introduction
Infrared-transmitting glass optical fibres are being developed as a ‘light pipe’ for flexible 10.6 µm laser power delivery
to facilitate medical laser surgery and also industrial cutting and welding. The 10.6 µm laser for medical surgery is used
for cauterisation and causes less collateral tissue damage than does shorter wavelength laser radiation.

Chalcogenide glasses generally exhibit transparent windows in the near- and mid- infrared region of the electromagnetic
spectrum. Chalcogenide glass optical fibres are being developed for laser power delivery1-4. Glass compositions are
based on the chalcogen elements of Group 16 of the Periodic Table, i.e. sulfur, selenium and tellurium in combination,
commonly, with germanium, and arsenic. Their optical, thermal and mechanical properties must all be optimised towards
making robust fibre for 10.6 µm power delivery.

The factors generally limiting the useful transparent window of the chalcogenide glasses for instance for laser power
delivery are: (i) extrinsic absorption caused by oxide, hydride, hydroxide and molecular water impurities and (ii)

Optical Fibers and Sensors for Medical Diagnostics and Treatment Applications VIII,
edited by Israel Gannot, Proc. of SPIE Vol. 6852, 685208, (2008) · 1605-7422/08/$18
doi: 10.1117/12.760882

Proc. of SPIE Vol. 6852 685208-1

2008 SPIE Digital Library -- Subscriber Archive Copy
extrinsic scattering by discrete submicron inclusions of differing refractive index from the glass matrix. Thus purification
procedures are being developed in an effort to reduce this extrinsic absorption and scattering.

Our aim is to design glass fibres capable of delivering 50 W (single-mode) and 100 W (multimode) with good beam
quality (M2 < 10).The properties required for a fibre to transmit such power at 10.6 µm are: (i) low absorption loss at
least 0.1 dB m-1 to avoid unwanted over-heating of the fibre; (ii) inclusion-free glass to avoid unwanted optical loss due
to light scattering and potential localised heating by absorption and (iii) sufficient glass thermal stability, thus high Tg
and large Hruby5 parameter: Tx – Tg, where Tx is the crystallisation-onset temperature, in order to resist thermal
degradation of the chalcogenide glass fibre particularly at the launch face where the incident power is greatest. The
mechanical strength of the fibre should be sufficient to withstand a small bend radius of a few cm.

Here, we discuss the nature of, and measure, the optical loss limiting transparency at 10.6 µm for a range of chalcogenide
glasses and show early results of attempting to transmit high power CO2 laser radiation through optical fibres of differing
chalcogenide glass composition and hence differing physical properties.

2. Experimental
Chalcogenide glasses were synthesised from arsenic (Furukawa, 7n5, 4-20 mm pieces), germanium (Cerac, 5n, 1-6 mm
pieces), selenium (Cerac, 5n, 1-6 mm pieces) and tellurium (Cerac, 6n, 1-6 mm pieces). All chemicals except arsenic
were batched as-received. Arsenic was purified by heat treating to volatilise the surface oxide layer. To achieve this,
about 7 g of arsenic was placed inside a purified silica glass ampoule and heated in vacuo (~ 5 x 10-3 Pa) to 300°C and
held isothermally. Arsenic oxides volatilised and condensed as a white film in the cold zone, away from the batched
arsenic, on the inside surface of the silica ampoule. The heat treatment was stopped when the deposits became silvery in
appearance, probably due to condensation of volatilised arsenic towards the end of the run. The purified arsenic was
stored for no longer than 48 hours inside a glovebox (mBraun) under < 0.1 ppm O2 and < 0.1 ppm H2O before being
used.

Chalcogenide glass rods (diameter, ϕ = 10 mm, length ~ 800 mm) were prepared. Thus, the precursor elements were
batched inside the mBraun glovebox (< 0.1 ppm O2 and < 0.1 ppm H2O) into a silica glass ampoule that had been
previously: (i) rinsed in de-ionised H2O and oven-dried (~100°C); (ii) baked in air (1000°C, 105 Pa); (iii) baked in vacuo
(1000°C, 10-2 Pa)) and (iv) cooled under vacuum, in an effort to remove carbonaceous material and physi- and chemi-
sorbed water. The ampoule, containing the batch, was sealed under vacuum (~ 5 x 10-3 Pa) and the elemental precursors
melted and homogenised for 12 h in a rocking furnace at 800°C to 930°C, depending on glass composition. The glass
melt above the liquidus inside the melting ampoule was quenched in air, or in water, annealed for 1 h close to the glass
transformation temperature (Tg) and cooled to ambient. The chalcogenide glass rod was then removed from the silica
glass ampoule. A disc was sliced from the rod and the two opposite faces were ground (using Buehler, SiC 1000grit) and
polished to a 1 µm finish (using Buehler 6, 3, then 1 µm diamond polish under non-aqueous conditions). The discs were
then examined optically by means of Fourier transform infrared (FTIR) spectroscopy using a glow-bar source, KBr
beam-splitter and DTGS detector for the wavelength (λ) region 3 ≤ λ ≤ 20 µm.

Unstructured chalcogenide glass rods were stored inside the unopened melting silica ampoule until required. Hydrogen
and/or oxygen gettering and distillation were carried out on the As40Se60, Ge17As18Se65 and Ge17As18Se62S3 glasses to
remove impurities and these processes will be described in more detail in a future paper. The Ge17As18Se65 /
Ge17As18Se62S3 (atomic %) core / clad., step-index preform was fabricated using an in-house designed and built extruder
described by Furniss et al.6.

The as-annealed unstructured rods and the extruded chalcogenide glass, step-index core / clad. rods were each drawn to
optical fibre (ϕ ~ 200 µm) using a customised Heathway fibredrawing tower, housed inside a Class-10,000 cleanroom.
The optical loss of the fibres was measured at 10.6 µm using a high powered CO2 laser by the cut-back method. Damage
tolerance to the CO2 laser power was tested at ≥ 50 mW, at 15 Hz with a pulse width of 50 µs. After exposure to the CO2
laser beam, fibres were examined by means of a Philips XL30 field emission gun environmental scanning electron
microscope (FEG ESEM) in auxiliary mode under a nitrogen atmosphere.

Proc. of SPIE Vol. 6852 685208-2

 3. Results and discussion

3.1 Transmission windows of bulk chalcogenide glasses

Typical optical loss spectra of small glass samples (2 – 4 mm optical pathlength) from six different compositions of
chalcogenide glasses produced in our laboratory are shown in Figure 1. From Figure 1 it can be seen that the addition of
germanium to the glass formulation changed the wavelength position of the peak of the generalised oxide impurity
absorption band from 14.2 µm, for a non-containing germanium glass, to 12.7 – 13.2 µm. Also, the addition of
germanium shifted the multiphonon edge to shorter wavelengths thereby restricting mid-infrared transmission.

Both of these effects are likely to induce extra optical absorption at 10.6 µm for germanium-containing glasses.
Germanium addition was beneficial in tending to increase Tg. Addition of tellurium (largest atomic mass of the elemental
precursors used) moved the multiphonon edge to longer wavelengths but decreased Tg (see Table 1).

3.2 Transmission of CO2 laser power through chalcogenide glass fibres

Optical loss values of chalcogenide glasses tested using the high power CO2 laser source at 10.6 µm are given in Table 1.
From Table 1, the lowest optical loss obtained was 2.3 dB m-1 at 10.6 µm for the Te20As30Se50 unstructured fibre7.

Se-H As-C

5 7 9 11 13 15 17 19
Wavelength I jun
Figure 1. FTIR spectra of the as-annealed chalcogenide glasses of optical pathlength 2 – 4 mm of batched compositions:
Ge30As10Se30Te30; Ge15As15Se11Te59 ; Ge17As18Se65; Te20As30Se50; As37.6Se56.4Sn6 and As40Se60 (atomic%). Please note, spectra
have been deliberately shifted vertically for clarity of presentation.

The damage caused to the launch face of a Te20As30Se50 fibre after being subjected to the CO2 laser (average power 100
mW, rate 25 Hz and pulse width 50 µs) was examined by means of FEG ESEM. Figure 2(a) shows a typical freshly
cleaved surface of the chalcogenide optical fibre. Figure 2(b) to 2(d) show micrographs of the launch face of two
Te20As30Se50 optical fibres after high power CO2 laser radiation had been launched into the fibre. The fibre imaged in
Figure 2(b) shows the fibre launch end after being subjected to an average power of 50 mW, at 15 Hz with pulse width
50 µs; the secondary electron image shows that the end of the Te20As30Se50 optical fibre had melted and possibly
volatilised in places. Figure 2(c) shows the launch face of a Te20As30Se50 fibre after being subjected to an average power
100 mW, at 25 Hz and pulse width 50 µs. Again the photomicrograph shows that the fibre had been damaged and Figure
2(d) shows under higher magnification where the Te20As30Se50 glass appears to have melted under the irradiation. From
the micrographs, it can be concluded that, although the Te20As30Se50 fibre exhibited the lowest optical loss at 10.6 µm of

Proc. of SPIE Vol. 6852 685208-3

the fibres studied (see Table 1) it did not withstand heating brought about by the optical absorption of the glass, probably
not helped by the very low Tg of this glass of 137°C (Table 1).

Table 1. Batch composition, Tg and optical loss of the chalcogenide optical fibres measured at 10.6 µm by means of a high
powered CO2 laser using the cut-back method.

Lowest optical loss

Chalcogenide glass Tg Preform Purification / dB m-1
compositions fabrication λ range λ=
method 2 – 6 µm 10.6 µm
Core As40Se60 180°C As-annealed Arsenic bake. 0.35 7.2
Clad. No clad rod O2 gettered and at 2.9 µm
distilled.
Core Ge17As18Se65 236°C Extrusion Arsenic bake. 1.8 10.3
Clad. Ge17As18Se62S3 O2 and H2 gettered at 5.5 µm
and distilled.
Core Te20As30Se50 137°C Extrusion Arsenic bake only. Not measured 2.3
Clad. No clad

Figure 2. Field emission gun environmental scanning electron microscope (FEG ESEM) images of two Te20As30Se50 optical
fibres showing: (a) a typical undamaged fibre cleave; (b) –(d) the damaged launch ends of optical fibres after high power CO2
laser radiation was had been launched into the fibres. (b), (c) average power 50 mW, and 100 mW, respectively, at 15 Hz and
pulse width 50 µs and (d) higher magnification of damage done to the launch end pictured in (c), showing evidence of melting.
Scale bars = 50 µm.

4. Conclusions
The effect of glass composition on the optical transmission of chalcogenide glass bulk specimens and fibres has been
studied using FTIR spectroscopy. The addition of germanium to the glass batch tended to move the multiphonon edge to
shorter wavelengths and shift the oxide absorption band occurring between 12 and 14 µm to shorter wavelengths. Both
of these effects may induce extra optical absorption at 10.6 µm suggesting that germanium is not a good additive for
glasses intended for laser power transmission at 10.6 µm. However, glasses not containing germanium tend to have
lower Tg and in particular optical fibre fabricated from Te-As-Se glass of Tg = 137°C was shown, not withstanding its
relatively low optical loss at 10.6 µm of 2.3 dBm-1, to exhibit extensive degradation after 10.6 µm laser irradiation (fibre
after exposure to ≥ 50 mW, at 15 Hz and 50µs pulse width) comprising glass melting and possible vaporisation at the
launch face.

Proc. of SPIE Vol. 6852 685208-4

 Acknowledgements
Helen Rowe wishes to thank Mrs Nicola Weston for the ESEM images and the Interdisciplinary Doctoral Training
Centre for Photonics and Electronics at the University of Nottingham for her PhD scholarship.

References
1. Le Coq D, Michel K, Kiersse J, Boussard-Pledel C, Fonteneau G, Bureau B, Le Quere J, -M, Sire O, and Lucas J,
’Infrared glass fibres for in-situ sensing, chemical and biochemical reactions‘, Comptes Rendus Chimie 5 907-913
(2002).

2. Sanghera JS, Aggarwal I, Shaw LB, Busse L, Thielen P, Nguyen V, Pureza P, Bayya S and Kung F, ‘Applications of
chalcogenide glass optical fibres at NRL‘, Journal of Optoelectronics and Advanced Materials 3 627-640 (2001).

3. Lucas P, Solis D, Le Coq D, Juncker C, Riley MR, Collier J, Boesewetter DE, Boussard-Pledel C and Bureau B,
‘Infrared biosensors using hydrophobic chalcogenide fibers sensitized with live cells’, Sensors and Actuators B:
Chemical 119 355-362 (2006)

4. Lucas P, Riley MR, Boussard-Pledel C and Bureau B, ‘Advances in chalcogenide fibers evanescent-wave biochemical
sensing‘, Analytical Biochemistry 351 1 (2006).

5. Hruby U and Stourac L, Chech J Phys 24 1132 (1974).

6. Furniss D and Seddon AB, ‘Towards monomode proportioned fibreoptic preforms by extrusion‘, Journal of Non-
Crystalline Solids 257 232-236 (1999).

7. Shiryaev VS, Adam JL, Zhang XH, Boussard-Pledel C, Lucas J and Churbanov MF, ‘Infrared fibres based on Te–As–
Se glass system with low optical losses‘, Journal of Non-Crystalline Solids 336 113-119 (2004).

Proc. of SPIE Vol. 6852 685208-5

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