Optical Materials 64 (2017) 468e473

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Optical Materials
journal homepage: www.elsevier.com/locate/optmat

Effect of heat treatment on absorption and uorescence properties of

PbS-doped silica optical bre
Fu Qin a, Yanhua Dong a, *, Jianxiang Wen a, Fufei Pang a, Yanhua Luo b, Gang-Ding Peng b,
Zhenyi Chen a, Tingyun Wang a
a
Key Laboratory of Specialty Fiber Optics and Optical Access Networks, Shanghai University, Shanghai 200072, PR China
b
Photonics & Optical Communications, School of Electrical Engineering & Telecommunications, University of New South Wales, Sydney 2052, NSW,
Australia

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

Article history: The effect of heat treatment on the optical properties of a PbS-doped silica optical bre was investigated.
Received 15 November 2016 The experimental results showed that the absorption peak of the bre red shifted from 1032 to 1133 nm
Received in revised form when the heat treatment temperatures were carried out at 900, 950, 1000, and 1100
C for 1 h,
5 January 2017
respectively. At the same time, when the heat treatment at 900
C was carried out for 2, 5, 10, 20, and
Accepted 6 January 2017
40 h, the absorption spectra of the bre showed a red shift from 1074 to 1143 nm. In addition, the in-
tensity of the absorption peak increased from 0.258 to 1.384 dB/m and the full width at half maximum
(FWHM) became narrower (from 130 to 50 nm) as the heat treatment proceeded. Moreover, the pho-
Keywords:
Optical bre
toluminescence (PL) intensity in the wavelength range of 1100e1500 nm decreased with an increase in
PbS quantum dot the heat treatment temperature. The theoretical analysis, using an effective mass method, showed that
Heat treatment the effective band gap energy and average size of the lead sulphide (PbS) quantum dots (QDs) in the silica
Spectroscopy bre core varied from 1.199 to 1.083 eV and from 4.28 to 4.81 nm, respectively. The results indicate that
Optical materials the size of the PbS QDs present in the silica bre core could be controlled by a proper heat treatment,
which is of great interest in optical bre ampliers and other bre optic devices.
2017 Published by Elsevier B.V.

1. Introduction
Broadband bre-optic ampliers have emerged as important
telecommunication network components. Rare earth (RE) element-
doped bre ampliers, especially erbium-doped bre ampliers
(EDFAs), have been successfully commercialized. However, because
of the intrinsic spectroscopic characteristics of RE ions, the oper-
ating waveband of RE ion-doped bre ampliers is restricted.
Although a series of novel technologies have been developed to
expand the operating waveband of EDFAs, they can only cover the C
band (1530e1565 nm) and L band (1565e1605 nm). This waveband
window is much narrower than the entire optical communication
window (1100e1700 nm) of commercial silica bres. To expand the
operating bandwidth of the optical communication network, it is
imperative to develop a novel gain medium in optical bre core that
can cover almost the whole optical communication window.
Recently, semiconductor QDs have been widely investigated
* Corresponding author.
E-mail address: dongyanhua@shu.edu.cn (Y. H. Dong).
because of their unique electronic and optical properties due to the
quantum connement effect [1]. One of the fascinating properties
of semiconductor QDs is that the wavelength range of their uo-
rescence spectrum can be tuned by controlling their size to cover a
broad bandwidth [2]. Semiconductor optical ampliers are cheap
and can provide a wide choice of operating wavelength and
bandwidth along with a high power output. Especially, PbS has a
small band gap of ~0.41 eV and a large Bohr radius of 18 nm [3e7].
Such a strong connement regime can be easily accessed by both
the charge carriers [8]. The PL spectra of PbS QDs with different
particle sizes covers a broad bandwidth of 1000e1600 nm [9],
which nearly covers the entire optical communication window
[10]. Therefore, PbS QDs-doped optical ampliers can be used in all-
optical communication systems [11,12].
PbS semiconductor materials have attracted an immense atten-
tion for optical bres. For example, PbS QDs are coated around
tapered bres to obtain optical bre-based optical ampliers with a
signal gain as high as 8 dB within the wavelength range of
1450e1650 nm [13,14]. However, such methods of incorporating PbS
into optical bres have some limitations such as poor homogeneity,
easier introduction of impurities, higher loss, sensitivity to

http://dx.doi.org/10.1016/j.optmat.2017.01.022
0925-3467/ 2017 Published by Elsevier B.V.
 F. Qin et al. / Optical Materials 64 (2017) 468e473 469

temperature, high packaging requirements, compatibility issues

with optical bre communication networks, etc. In order to over-
come these limitations, PbS materials should be directly doped into
silica bre cores. Dong et al. successfully incorporated PbS into silica
bre cores [15]. However, they found it difcult to control the size of
the PbS QDs during the bre preparation process. Heat treatment is
an effective method for controlling the size of QDs in host materials
[16e19]. The average size of PbS QDs in boroaluminosilicate host
glass increases and the absorption peaks exhibit a red shift with an
increase in the heat treatment temperature [18]. Silicate glasses
containing PbS QDs with narrow size distribution are prepared
through heat treatment. Tunable infrared luminescence ranging
from 1100 to 2200 nm has been achieved by controlling the glassy
matrix and preparation parameters, and optical amplication at
1550 and 1330 nm has been probed [19]. However, these are only
bulk glass material and do not have any optical bre. Thus, it cannot
be directly applied to bre ampliers for optical bre communica-
tion. However, little attention has been paid to tune the size of QDs in Fig. 1. RID of the PbS-doped silica optical bre.
silica bres by heat treatment processing.
In this study, the inuence of heat treatment on the absorption Table 1
and PL of a PbS-doped silica optical bre was investigated. The Composition of the PbS-doped bre core.
absorption peak of the silica bre could be tuned by controlling the
Elements Mass conc. (%) Atomic conc. (%)
size and distribution of the PbS QDs present in its core. The ab-
OK 47.97 63.55
sorption peak showed a red shift. In addition, the PL spectrum of
Si K 46.34 34.97
the bre was also measured by 1064 nm pumping. The relationship SK 0.33 0.22
between the PL spectrum of the bre and the heat treatment Ge L 3.79 1.11
temperature was also investigated. The proposed bre is expected Pb M 1.58 0.16
to be used in optical bre ampliers and broadband light sources. Total 100 100

2. Experimental section
2.1. Fabrication and performance testing of the PbS-doped silica
optical bre
A PbS-doped silica optical bre was fabricated using the atomic
layer deposition (ALD) technique and a modied chemical vapour
deposition (MCVD) method [15,20]. The fabrication process
involved four steps. First, a porous soot layer was formed on the
inner walls of a silica tube by the MCVD process; Then, PbS- and
Al2O3-doped layers were deposited on the surface of the porous
soot layer by ALD (Beneq TFS-200, Finland). Ge-doped SiO2 mate-
rials were then deposited as core layers by MCVD and a doped bre
preform was formed by collapsing. Finally, the preform was drawn
into an optical bre. The PbS material was deposited using
Pb(tmhd)2 (bis(2,2,6,6-tetramethyl-3,5-heptanedionato) lead(II))
(Shanghai HongRui New-Materials Technology Co., Ltd) as the Pb
precursor and H2S as the S precursor. Al2O3 was used to promote
the compatibility between PbS and the silica substrate and to adjust
the refractive index distribution (RID) in the bre core [21]. Here,
Al(CH3)3 and O3 were used as the Al and O precursors, respectively.
The diameters of the core and cladding of the PbS-doped silica
optical bre were about 16 and 127 mm, respectively. The RID of the
bre was analysed by an optical bre index analyser (S14, Photon
Kinetics Inc., USA), as shown in Fig. 1. The refractive index difference
of the bre core and cladding was about 0.11%, which is larger than
that of single-mode bres. This may be attributed to PbS doping in
the bre core.
The elemental composition of the silica bre core was analysed
by an energy dispersive spectrometer (EDS) (MX80-EDS, OXFORD,
England), as listed in Table 1. The concentration of Pb, S, and Ge was
found to be 0.16, 0.22, and 1.11 at%, respectively. The results showed
that PbS was successfully incorporated into the bre core. In
addition, the structural features of the doping materials were
examined by high resolution transmission electron microscopy
(HRTEM, JEM-2010F, Japan), as shown in Fig. 2. The HRTEM image
revealed the crystalline morphology of the PbS nanocrystals. The
nanocrystals were roughly spherical and homogeneous and
showed no agglomeration. The average diameter of the PbS QDs
was about 4.5 nm.
The absorption spectrum of the bre was measured using a cut-
back technique with a broadband optical spectrum analyser (OSA,
Yokogawa AQ-6315A) in the wavelength region of 550e1700 nm.
The resolution of the analyser was 0.2 nm. The uorescence spec-
trum of the bre was measured before and after the heat treatment
by a reversed pumping method employing a 1064 nm laser diode.
2.2. Heat treatment processing
In order to determine the optimum heat treatment temperature
range for the PbS-doped optical bre, a differential scanning calo-
rimetry (DSC) test was conducted using a differential scanning
calorimeter (DSC404C, NETZSCH, Germany). The temperature was
changed from 200 to 1400
C at a rate of 10
C/min. The results
showed that the incorporation of PbS into the bre core was
exothermic over the temperature range of 1000e1150
C. This can
be attributed to the melting of the PbS material in the optical bre
core, as shown in Fig. 3. This melting was advantageous to the
formation and growth of the PbS QDs. Thus, the heat treatment
temperatures (for 1 h) of 900, 950, 1000, and 1100
C were chosen.
The heat treatment was carried out in a tube furnace (SJX-1500,
China). In addition, the inuence of the heat treatment time on the
optical properties of the resulting bre was also investigated by
xing the heat treatment temperature at 900
C and varying the
heat treatment time (2, 5, 10, 20, and 40 h).
3. Results and discussion
3.1. Absorption properties
Prior to the heat treatment, the bre exhibited absorption peaks
470 F. Qin et al. / Optical Materials 64 (2017) 468e473

Fig. 2. HRTEM images of the optical bre core with PbS-doped materials.

Fig. 3. Differential scanning calorimetry of the PbS-doped silica optical bre core.

at 730 and 1032 nm. These peaks are attributed to the absorption of
the PbS QDs in the silica bre core region [15,22e24]. These peaks
matched well with those of PbS QDs of two different sizes. The
absorption coefcient at 1032 nm was 0.258 dB/m, and FWHM was
130 nm, as shown in Fig. 4. The peak at 1380 nm corresponds to the
absorption of -OH group [25]. During the process of the bre
fabrication, the PbS particles were formed in the bre core after
collapsing and drawing at high temperatures. In the process of
drawing, the temperature became greater than 2000
C. The
diameter of the preform was reduced signicantly. The thickness of
the PbS semiconductor thin lm in the matrix interface decreased
sharply. Turbulent diffusion was formed, with drawing axial trac-
Fig. 4. (a) Absorption spectra of the PbS QDs-doped silica optical bre after heat
tion in the molten state, and then resulted in lm rupture and treatment at 900, 950, 1000, and 1100
C for 1 h. (b) Magnied view of Fig. 4. (a). The
surface shrinkage. The PbS particles underwent a rapid agglomer- inset shows the shift in the absorption peak at 1032 nm with an increase in the heat
ation because of their surface structural and nano-size effects treatment temperature.
during the cooling. Thus two groups of different-sized PbS QDs
were formed. The wire drawing temperature and speed affected the and thus to improve the properties of the optical bres incorpo-
size and distribution of the PbS QDs. However, the wire drawing rating such QDs.
parameters were rigid and constant for most part of the process. The PbS-doped silica optical bre showed absorption peaks at
The experimental results showed that the size and surface 1074, 1098, 1120, and 1133 nm when the heat treatment was carried
morphology of the PbS QDs were anomalous and irregular, as out at 900, 950, 1000, and 1100
C, respectively, for 1 h. The ab-
shown in Fig. 2. Hence, it can be concluded that heat treatment is an sorption peak at 1032 nm showed a shift of 101 nm after the heat
effective method to control the size and distribution of PbS QDs, treatment (from 1032 to 1133 nm), while that at 726 nm showed a
 F. Qin et al. / Optical Materials 64 (2017) 468e473 471

Table 2
Diameter, effective bandgap energy, and peak absorption wavelength of the
PbS QDs at different heat treatment temperatures.

Temperature Absorption peak Diameter Effective bandgap

(
C) (nm) (nm) (eV)

900 1074 4.48 1.152

950 1098 4.59 1.127
1000 1120 4.70 1.105
1100 1133 4.76 1.092

Fig. 5. (a) Absorption spectra of the PbS QDs-doped optical bre after heat treatment
at 900
C for 2, 5, 10, 20, and 40 h. (b) Magnied view of Fig. 5. (a). The inset shows the
shift in the absorption peak at 1104 nm with an increase in the heat treatment time.
shift of 43 nm (from 726 to 769 nm), as shown in Fig. 4. As the heat
treatment time increased, the absorption peak red shifted. After the
heat treatment at 900
C for 40 h, the absorption peak at 1104 nm
shifted by 39 nm (from 1104 to 1143 nm), while that at 737 nm
shifted by 48 nm (from 737 to 785 nm), as shown in Fig. 5.
Furthermore, the FWHM of the absorption band reduced from 130
to 50 nm and the absorption coefcient increased from 0.258 to
1.384 dB/m with an increase in the heat treatment temperature and
with an increase in the heat treatment time at 900
C. These factors
contributed to the regular morphology and uniform size of the PbS
QDs in the bre.
The effective band gap energy and average size of the PbS QDs
were estimated using the following relations [26,27]:
Eg R Zu  aZu2
!

2 2Z2 Eg p2
Eg R Eg2
m R
where a is the absorption coefcient, Z is the Planck's constant, Zu
1.092 eV when the heat treatment was carried out at 900, 950,
1000, and 1100
C, respectively, for 1 h, as estimated from Eqs. (1)
and (2). These values are summarized in Table 2. After the heat
treatment at 1100
C for 1 h, the total increase in the average size of
the PbS QDs was 0.47 nm. The growth rate of the PbS QDs increased
with an increase in the heat treatment temperature from 900 to
1100
C. This happens because the relatively high temperature
contributes to the dispersion of particles in the bre core. However,
at temperatures higher than 1100
C, some of the PbS QDs structure
might have destroyed, which led to a decrease in the average
growth rate. The absorption peak of the bre was at 1104, 1121, 1131,
1140, and 1143 nm when the heat treatment was done at 900
C for
2, 5, 10, 20, and 40 h, respectively. The tting and calculation results
showed that the effective band gap energy of the PbS QDs was 1.121,
1.104, 1.094, 1.085, and 1.083 eV (estimated from Eqs. (1) and (2)),
while their average size was 4.62, 4.7, 4.75, 4.8, and 4.81 nm when
the heat treatment was done at 900
C for 2, 5, 10, 20, and 40 h,
respectively (Table 3). It is evident that the growth rate of the PbS
QDs was very high at the beginning of the heat treatment process
and then decreased slowly until the PbS QDs stopped growing.
Smaller PbS clusters existed in the bre core at the beginning of the
heat treatment process. These small clusters easily formed larger
QDs in the optical bre core. With an increase in the heat treatment
time from 2 to 40 h, the number of PbS clusters reduced, and hence
the distance between them increased. Thus, the merging of the PbS
clusters became difcult, which limited the PbS concentration in
the bre core. This restricted an increase in the size of the QDs.
Similar results have been reported in a previous study [18].
Therefore, an optimum size of PbS QDs is obtained by strictly
controlling the concentration of PbS material in bre cores and the
heat treatment parameters.
3.2. Fluorescence properties
For the PbS-doped silica optical bre, the PL spectra were
measured by 1064-nm pumping. The results indicate that the PL
spectrum covered a wavelength range of 1100e1500 nm, which
contributed to the different sizes of the PbS QDs in the optical bre
core. The smaller QDs exhibited a uorescence peak at 1153 nm,
while the larger QDs showed uorescence near 1320 nm, as shown
in Fig. 6. As the temperature increased from 25 to 1100
C, the PL
(1) intensity in the wavelength range of 1100e1350 nm decreased
linearly. It may be because of the increased loss of the bre. The
(2)
Table 3
Diameter, effective bandgap energy, and peak absorption wavelength of the PbS QDs
at different heat treatment times.

is the photo energy, and m is the reduced mass. m 0:085me , Time (h) Absorption peak (nm) Diameter (nm) Effective bandgap (eV)
where me is the effective electron mass. R and Eg R are the radius 2 1104 4.62 1.121
and effective band gap energy of the PbS QDs, respectively. 5 1121 4.70 1.104
Eg (0.41 eV) is the direct band gap of bulk PbS. 10 1131 4.75 1.094
The average size of the PbS QDs was 4.48, 4.59, 4.70, and 20 1140 4.80 1.085
40 1143 4.81 1.083
4.76 nm, while their effective band gap was 1.152, 1.127, 1.105, and
472 F. Qin et al. / Optical Materials 64 (2017) 468e473
Fig. 6. Fluorescence spectra of the PbS-doped optical bre under different treatment
temperatures.
absorption peaks showed a red shift and a narrow FWHM. The
absorption inefciency at 1064 nm decreased. In addition, at heat
treatment temperatures higher than 900
C, the uorescence in-
tensity at 1400 nm increased with an increase in the temperature. It
may be attributed to the thermoluminescence (TL) effect. This
phenomenon has also been reported in previous studies [28,29].
This TL effect is believed to arise from PbS or matrix materials
[30,31]. Next step, we will further investigated of this phenomenon.
And the PbS QDs-doped bre may be a potential candidate for bre
temperature sensing applications.
4. Conclusion
We investigated the effect of heat treatment on the optical
properties of a PbS-doped silica optical bre both experimentally
and theoretically. The absorption peak of the bre showed a red
shift from 1032 to 1133 nm as the heat treatment temperature
increased from 900 to 1100
C (900, 950, 1000, and 1100
C for 1 h,
respectively). At the same time, when the heat treatment pro-
ceeded at 900
C and the heat treatment time was varied from 2 to
40 h (2, 5, 10, 20, and 40 h, respectively) the absorption spectra
showed a red shift from 1074 to 1143 nm. The absorption peak
intensity also increased from 0.258 to 1.384 dB/m. Furthermore,
during the heat treatment process, the FWHM narrowed down,
from 130 to 50 nm. Moreover, the PL intensity in the wavelength
range of 1100e1500 nm decreased with an increase in the heat
treatment temperature. For theoretical analysis, we used an effec-
tive mass method to study the characteristics of the PbS QDs in the
silica bre core. The effective band gap energy and average size
varied from 1.199 to 1.083 eV and from 4.28 to 4.81 nm, respec-
tively. The results showed that the size of the PbS QDs could be
controlled by a proper heat treatment, which is of great interest in
optical bre ampliers and other bre optic devices.
Acknowledgment
This work was supported by the Natural Science Foundation of
China (61520106014, 61475096, 61227012, 61275051, 61635006,
61422507), and Science and Technology Commission of Shanghai
Municipality (15220721500).
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