Mid-infrared
emissions
of
Pr
3+
-doped
GeS
2
–Ga
2
S
3
–CdI
2
chalcohalide
glasses
Chunfeng
Lu
a
,
Haitao
Guo
a,
*
,
Yantao
Xu
a
,
Chaoqi
Hou
a
,
Min
Lu
a
,
Xin
He
b
,
Pengfei
Wang
a
,
Weinan
Li
a
,
Bo
Peng
a,
*
a
State
Key
Laboratory
of
Transient
Optics
and
Photonics,
Xi’an
Institute
of
Optics
and
precision
Mechanics,
Chinese
Academy
of
Science
(CAS),
Xi’an,
Shaanxi
710119,
PR
China
b
School
of
Applied
Physics
and
Materials,
Wuyi
University,
Jiangmen,
Guangdong
529020,
PR
China
A
R
T
I
C
L
E
I
N
F
O
Article
history:
Received
8
July
2013
Received
in
revised
form
12
July
2013
Accepted
1
September
2014
Available
online
3
September
2014
Keywords:
A.
Chalcogenides
A.
Glasses
B.
Luminescence
B.
Optical
properties
A
B
S
T
R
A
C
T
For
elucidation
of
the
glass
composition’s
influence
on
the
spectroscopic
properties
in
the
chalcohalide
system
and
the
discovery
of
a
new
material
for
applications
in
mid-infrared
fiber-lasers,
a
serial
Pr
3
+
-doped
(100
x)(0.8GeS
2
0.2Ga
2
S
3
)xCdI
2
(x
=
5,
10,
15
and
20)
chalcohalide
glasses
were
prepared.
4.6
m
m
mid-infrared
fluorescence
emission
from
Pr
3+
in
the
sulfide
glass
is
successfully
observed
at
room
temperature
excited
by
a
2.01
m
m
Tm
3+
:YAG
ceramic
laser
system,
and
the
effective
line-width
of
fluorescence
band
is
106–227
nm.
Intense
compositional
dependence
of
mid-infrared
emissions
is
found.
The
radiative
rates
of
Pr
3+
ions
in
these
glasses
were
calculated
by
using
the
Judd–Ofelt
theory.
ã
2014
Elsevier
Ltd.
All
rights
reserved.
1.
Introduction
Compact
and
solid
state
laser
sources
emitting
in
the
3–5
mm
transparency
window
of
the
atmosphere
have
both
military
and
commercial
applications
for
imaging
and
remote
sensing
[1,2].
Pumping
the
rare
earth
(RE)
ion
doped
glass
fiber
by
near-infrared
(NIR)
laser
is
an
effective
and
direct
way
to
achieve
mid-infrared
(MIR)
laser.
So
far,
the
longest
emission
wavelength
of
infrared
fiber
laser
is
3.95
mm,
which
is
achieved
in
cryogenic
Ho
3+
ion
doped
ZBLAN
glass
fiber
[3].
Extending
to
a
longer
wavelength
is
difficult
because
that
even
for
the
fluoride
glasses,
they
have
limited
transmission
in
the
mid-wave
spectral
regions,
and
most
importantly,
relatively
high
phonon
energy
quenches
RE
ion
transitions
in
these
spectral
regions.
In
order
to
extend
the
emission
wavelength
of
fiber
lasers
beyond
4
mm
working
at
room
temperature,
host
glasses
with
lower
phonon
energy
are
necessary
[3].
As
hosts
for
rare
earth
ions,
chalcogenide
or
chalcohalide
glasses
possess
the
lowest
phonon
energy
of
250–450
cm
1
in
various
glasses,
resulting
in
low
non-radiative
decay
rates
and
high
spontaneous
emission
probabilities
in
MIR
region.
In
the
1990s,
studies
of
K.
Wei,
J.
Heo
and
D.W.
Hewak
[4–6]
have
shown
the
probability
of
room-temperature
MIR
fluorescence
beyond
4
mm
emitted
in
some
well-established
chalcogenide
glasses
such
as
Ge
30
As
10
S
60
,
Ge
25
Ga
5
S
70
and
70Ga
2
S
3
30La
2
S
3
.
The
RE
ions
are
mainly
Dy
3+
or
Tb
3+
.
We
also
investigated
the
4.3
mm
MIR
fluorescence
emissions
and
compositional
optimization
in
the
Dy
3
+
/Tm
3+
-codoped
GeS
2
–Ga
2
S
3
–CdI
2
,
GeS
2
–In
2
S
3
and
GeS
2
–Ga
2
S
3
–AgI
glasses
in
recent
works
[7–9],
proving
that
compositional
optimiza-
tion
can
effectively
improve
the
RE
ion’s
MIR
fluorescence
emission.
In
this
work,
we
prepared
the
Pr
3+
doped
GeS
2
–Ga
2
S
3
–CdI
2
glasses.
Compared
with
Dy
3+
ion,
Pr
3+
ion
has
an
advantage
that
it
has
large
absorption
cross
section
at
2
mm,
which
is
just
the
output
wavelength
of
Tm
3+
laser.
Whereas
the
best
pumping
for
Dy
3+
ion
is
the
unusual
1.7
mm
[10]
and
its
absorption
cross
section
at
general
808
nm
LD
pumping
is
very
small
[9].
In
the
past
several
years,
MIR
fluorescence
emission
at
room
temperature
from
Pr
3+
in
the
Ge–Ga-based
selenide
glass
have
been
reported
by
Shaw
et
al.
[11–14],
and
it
shows
a
very
broad
MIR
emission
band
which
covers
from
3.5
to
5.5
mm.
However,
in
the
Ge–Ga-based
sulfide
glass,
most
MIR
emissions
beyond
2.5
mm
from
Pr
3+
were
observed
at
cryogenic
temperature
(20
K)
[15].
In
this
work,
an
investigation
on
the
characterization
of
the
MIR
fluorescence
emissions
of
Pr
3+
ions
in
GeS
2
–Ga
2
S
3
–CdI
2
serial
glasses
was
carried
out.
MIR
fluorescence
emission
from
Pr
3+
in
the
Ge–Ga-based
sulfide
glass
is
successfully
observed
at
room
*
Corresponding
authors.
Tel.:
+86
29
88882501;
fax:
+86
29
88882501.
E-mail
addresses:
guoht_001@opt.ac.cn
(H.
Guo),
bpeng@opt.ac.cn
(B.
Peng).
http://dx.doi.org/10.1016/j.materresbull.2014.09.003
0025-5408/ ã
2014
Elsevier
Ltd.
All
rights
reserved.
Materials
Research
Bulletin
60
(2014)
391–396
Contents
lists
available
at
ScienceDirect
Materials
Research
Bulletin
journal
homepage:
www.else
vie
r.com/locat
e/mat
resbu
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