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 Astro Ltd Laser Physics

Laser Phys. 26 (2016) 045702 (6pp) doi:10.1088/1054-660X/26/4/045702

Random lasing in Cr:ZnS

microstructure-textured grooves
Xianheng Yang1, Guoying Feng1, Chao Yang1, Shutong Wang1
and Shouhuan Zhou1,2
1
  Institute of Laser and Micro/Nano Engineering, College of Electronics and Information Engineering,
Sichuan University, Chengdu 610064, People’s Republic of China
2
  North China Research Institute of Electro-Optics, Beijing 100015, People’s Republic of China

E-mail: guoing_feng@scu.edu.cn and zhoush@scu.edu.cn

Received 16 September 2015, revised 18 December 2015

Accepted for publication 18 December 2015
Published 8 March 2016

Abstract
We report a random lasing emission based on microstructure-textured grooves of Cr:ZnS
crystal. The microstructures include horizontal ripples and a vertical periodic structure
with dozens of micrometers of periods, which are induced by the Fresnel diffraction of
femtosecond laser in the grooves and the interference of laser light through the micropores,
respectively. The microstructures multiple-scatter the light, resulting in lasing emission with
a center wavelength of 2250 nm and a relatively low lasing threshold of ~80 μJ/pulse. There
is a dramatic shortening of the emission lifetime as the pump energy increases. The emission
peaks are shifted by pumping at the microstructures with different vertical periods. It shows a
structural stable property for potential random laser applications.

Keywords: random lasing, microstructure, lifetime

(Some figures may appear in colour only in the online journal)

1. Introduction Lawrence Livermore National Laboratory scientists [19, 20]

Random lasers are of great interest in recent years for their
low threshold, small size and low spatial coherence [1–3].
Based on disordered structures in laser active materials, posi-
tive feedback is provided by multiple scattering that confines
the light in the gain medium for very long paths [4, 5]. In
1996, Wiersma [6] presented closed-loop paths that supported
coherent backscattering for random lasing emission. And then
Cao [7–9] made experiments to demonstrate the physics by
discrete lasing modes in the emission spectra. Coherent back-
scattering is known as weak localization. It means that weak
localization of light will occur when the scattering wave-
length is less than or close to the scattering mean free path,
and coherent backscattering is possible. Since then, random
laser behaviors have gained much more attention and been
extensively studied with a variety of experiments [10–13] and
theoretical calculations [14, 15].
Transition-metal (TM) ion-doped II–VI semiconductors
are of great interest in solid-state lasers and optoelectronic
devices as a new class of active materials owing to their avail-
able spectra in the mid-infrared (mid-IR) region [16–18].
first reported that the heavy ions in II–VI chalcogenide hosts
are transparent in a wide spectral region and decrease the effi-
ciency of non-radiative decay, leading to high luminescence
yield at room temperature (RT). Soon afterwards, Mirov’s
[17, 18, 21] and Sorokina’s [22–24] groups made great efforts
to research Cr2+-doped chalcogenides and found out some sig-
nificant phenomena. Chromium-doped zinc sulfide (Cr:ZnS)
crystal features widely tunable laser wavelengths between 1.8
and 2.8 μm, corresponding to the 5E  →  5T2 state transitions
of Cr2+ ions in the ZnS host. TM-ion-doped chalcogenide
random powder lasers were demonstrated in [25–28]. In part­
icular, Cr:ZnS random powders lase at center wavelengths of
2200 nm, 2246 nm and 2264 nm with particle sizes of 27 nm,
250 nm and 3 μm, respectively. Widely tunable random lasers
between 2 and 3 μm show great potential for laser applica-
tions in spectroscopic investigations, noninvasive medical
diagnostics and environmental monitoring [17, 22, 29].
In this work, we introduce a Cr:ZnS random laser with sta-
ble structures of long-periodic ripple-textured microgrooves.
With increasing pump energy, the lasing threshold, radical
narrowing of the emission linewidth and dramatic shortening

1054-660X/16/045702+6$33.00 1 © 2016 Astro Ltd  Printed in the UK

Laser Phys. 26 (2016) 045702
of the emission lifetime are observed. We also show the strong
dependence of the emission wavelength on the periodic
microstructures.
2.  Experimental methods
The microstructure-textured grooves of the Cr:ZnS crystal
were prepared using a titanium-doped sapphire femtosecond
laser (800 nm center wavelength and 45 fs pulse duration)
with a fluence of ~160 mJ cm−2 on the surface of the Cr:ZnS
crystal in a high-vacuum chamber. The Cr:ZnS crystal was
mounted on a rotating stainless-steel target holder. The vac-
uum chamber was pumped to a pressure below 9  ×  10–4 Pa.
The repetition rate of the femtosecond laser was 1 kHz and
the revolving speed of the target was 10 rpm. The preparation
details have been reported in our previous works [30]. So as
to clear out the surface adhesive powders, the Cr:ZnS crystal
was cleaned with alcohol, acetone and deionized water in an
ultrasonic cleaner for several minutes after laser ablation.
The mid-IR photoluminescence (PL) spectra of the Cr:ZnS
microstructure-textured grooves were measured under
1600 nm laser radiation from a tunable optical parametric
oscillator (OPO) operating with 7 ns pulse duration and a 10 Hz
repetition rate. The focus spot diameter of the pump light was
about 200 μm. A monochromator and InGaAs near-infrared
detector were used to detect the emission signal. The grat-
ing in the monochromator was 600 lines mm−1 and its blaze
wavelength was around 1.6 μm. The response wavelength
and time resolution of the InGaAs detector were from 1.0
to 2.6 μm and ~2 μs, respectively. A digital phosphor oscil-
loscope and HgCdTe mid-IR detector were used to measure
the PL lifetime. The response wavelength and time resolution
of the HgCdTe detector were from 2 to 5 μm and ~20 ns,
respectively.
3.  Results and discussion
Figure 1(a) shows the model of the microstructure-textured
grooves. In the deep grooves, there are some micropores, and
on the side wall of the micropores there are some periodic
structures. The scanning electron microscope (SEM) results
reveal that there are two grooves with an average width of
~200 μm on the surface of the Cr:ZnS crystal, and in each
groove there is one row of micropores with an average size of
~30 μm, as depicted in figure 1(b). We cut open one groove
in the perspective of a microscope, and the side wall of the
micropores in the deep groove was observed by SEM, as
shown in figures 1(c) and (d). The bright structure in the bot-
tom of figure 1(c) is the fracture surface of the Cr:ZnS crystal,
which is deeper than the groove and micropores. The average
depth of the groove is about 360 μm. It has a smooth side
wall covered by sputtering particles. The average depth of the
micropores is about 250 μm and their side walls are covered
by a ripple structure. The period of the horizontal ripples is
averaged at about 10 μm, which is one order of magnitude
higher than the femtosecond laser-induced periodic structures
(FLIPSS) [31, 32]. Furthermore, the period of the horizontal
2
X Yang et al
ripples gets larger as the depth goes deeper. The laser-induced
long-periodic structures can be explained by the Fresnel dif-
fraction in the grooves resulting in the intensity modulation
of the laser light’s transverse intensity profile [33–35]. The
groove is regarded as a slit, and the phenomenon is calculated
by the Fresnel zone plate method
ρ2N ⎛ R⎞
N=
(1) ⎜ 1 + ⎟,
λR ⎝ r0 ⎠
where N is the number of wave zones, ρN is the radius of the
slit, λ is the light wavelength, R is the radius of the wave zone,
which can be offset in the post process, and r0 is the diffraction
distance between the slit and the reference point. On the basis
of the SEM results, we assume ρN  =100 μm, λ  =  800 nm, and
r0  = 300 μm. As a result, the calculated period of the horizon-
tal ripples (Δr  ≈  14.4 μm) matches the experimental results
(~15 μm) very well. In addition, there is a vertical periodic
structure with an average period of ~30 μm on the side wall of
the micropores. When we slowed down the femtosecond-laser
scanning speed, there resulted a single groove without micro-
pores in it. And on the side wall of the groove, there are only
some horizontal ripples rather than a vertical periodic struc-
ture. By our analysis, the vertical periodic structure is caused
by the diffraction and interference of the femtosecond laser.
Laser light passing through the row of micropores is similar to
a multiple-slit diffraction. The principal maximum diffraction
and constructive interference will occur simultaneously at the
midperpendicular of the micropore line. As a result, laser light
in these positions with the strongest intensity will ablate the
material extremely, leading to vertical periodic structure.
Figure 2(a) exhibits the RT emission spectra of the Cr:ZnS
microstructure-textured grooves with various pump pulse
energies. At low pump energy (60 μJ/pulse), the multiple scat-
tering cannot provide enough positive feedback, leading to a
single broad and weak spontaneous emission signal. When
the pump energy nearly exceeds the threshold (100 μJ/pulse),
multiple narrow spikes emerge in the emission spectra around
2250 nm. The linewidth of the spikes is less than 4 nm, as
depicted in the upper left inset of figure 2(a). The multiple
spikes correspond to the resonant modes of the scattering light
within the random media which are stimulated by coherent
feedback [36]. As the pump energy increases further (500 μJ/
pulse), more and stronger sharp spikes appear. By our anal-
ysis, the spike linewidth is limited by the resolution of the
apparatus. Though the rotating grating in the monochromator
could distinguish Δλ  =  0.1 nm light wavelengths by chro-
matic dispersion, the slit width before the detector restricts the
limiting resolution of the monochromator. The adjacent lasing
wavelengths could be detected simultaneously by the detec-
tor, resulting in a single emission peak with much broader
linewidth. Only when the pump energy is around the thresh-
old can sharp spikes (~4 nm) be observed. As the pump energy
increases further, many more lasing modes oscillate and sharp
spikes turn to a relatively broad envelope curve (~50 nm). In
addition, the broad spontaneous emission fluorescence spectra
also get stronger as the pump energies get higher. For laser
action, an abrupt increase of peak intensity with the increasing
Laser Phys. 26 (2016) 045702 X Yang et al

Figure 1.  (a) Model of Cr:ZnS microstructures. (b) SEM image of the grooves’ and micropores’ surface morphology. (c) SEM image of the
grooves’ and micropores’ side wall. (d) Partially magnified picture of the micropores’ side wall.

Figure 2.  (a) RT emission spectra of Cr:ZnS microstructure-textured groove at various pump energies. The upper left inset is a partially
magnified picture of the PL spectrum at a 100 μJ/pulse pump energy. (b) Evolution of integrated peak intensity as a function of pump
energy.

pump energy is regarded as a laser-like threshold. Figure 2(b)
shows the integrated peak intensity as a function of the pump
energy. As one can see, a lasing threshold of ~80 μJ/pulse
behavior is observed. Above the pump threshold, there is an
abrupt change in the slope and a nearly linear increase in the
output signal with the pump energy. Due to the gain satur­
ation of the laser active medium, the slope of the growth curve
decreases when the pump energy is above 400 μJ/pulse.
3
The RT decay profiles of the random lasing based on
the Cr:ZnS microstructure-textured grooves were investi-
gated. Figure  3 shows the normalized emission decay pro-
files obtained at 2250 nm for different pump energies. At a
50 μJ/pulse pump energy, the spontaneous emission lifetime
is about 1.2 μs, which is much shorter than reported results
[18, 19]. What causes the emission lifetime shortening of the
microstructure-textured groove is the large number of crystal
Laser Phys. 26 (2016) 045702 X Yang et al

Figure 3.  RT normalized temporal profiles of Cr:ZnS

microstructure-textured groove measured at 2250 nm for different
pump energies. The inset is a magnified temporal profile at a
500 μJ/pulse pump energy.

Figure 4.  Emission spectra of Cr:ZnS groove pumped at the same

position with ~600 μJ/pulse energy. The inset is the SEM image of
the pump area’s side wall.

defects [25]. Besides, high chromium doping concentrations

would also decrease the emission lifetime [37]. The doping con-
centration of chromium in our sample is about 5  ×  1019 cm−3.
As the pump energy increases, a remarkable shortening of
the pulse profile is observed, which is caused by a multi-
exponential decay including a rapidly falling laser spike
and a slowly falling portion. While far above the threshold
(500 μJ/pulse), the lasing emission lifetime is kept a constant
of ~30 ns as depicted in the inset of figure 3, which is limited
by the temporal response (~20 ns) of our detector.
In order to demonstrate the stability of our random lasing
emission, the ~23 μm vertical period structure-textured groove
was pumped at different times with ~600 μJ/pulse energy. The
data was recorded every 15 min in the experiment, as shown in
figure 4. The emission center wavelengths remain in the domi-
nant position at around 2250 nm, though there is a slight shift
due to the energy fluctuations of the pump pulses. Besides, the
emission intensities also stay nearly the same except for some
undulations of pump energy. According to the experimental
Figure 5.  Emission peak shifting of Cr:ZnS grooves textured with
(a) 23 μm, (b) 40 μm and (c) 75 μm vertical period microstructures.
The insets are the SEM images of the pump areas’ side walls.
results, a stable lasing emission based on the microstructure-
textured groove is obtained.
Since the horizontal ripples at different positions affected
by the groove depth are almost the same, there should be
no relation to the emission spectra. But the vertical periodic
structures vary with the micropores, so the emission peak
wavelength might be influenced by them. To confirm this,
we pumped at different vertical periodic structure-textured
grooves and measured the spectra, as depicted in figure  5.

4
Laser Phys. 26 (2016) 045702
The Cr:ZnS grooves were pumped under a 1600 nm wave-
length and 500 μJ/pulse energy. As can be seen, there is a pro-
nounced blue shift of the emission peaks as the vertical period
gets shorter. In our experiments, the largest center wavelength
shift is about 25 nm. The long vertical periodic structure (~75 μm)
and short vertical periodic structure (~23 μm) result in emis-
sion peaks at around 2275 nm and 2250 nm, respectively.
As we have reported previously [30], a groove without
micropores inside would not give rise to random lasing emis-
sion. There is just a broad spontaneous emission. It means that
grooves textured with just horizontal ripples and deposited
particles cannot support positive feedback. A vertical periodic
structure with a critical period would also be of help. As the
output center wavelength shows great dependence on the peri-
odic structures, we could prepare stable microstructures with
some specific periods that vary the emission wavelengths.
4. Conclusions
In conclusion, a random lasing emission based on the micro-
structure-textured grooves of Cr:ZnS crystal is demonstrated.
The structures include micron-sized horizontal ripples and a
vertical periodic structure, which are induced by the Fresnel
diffraction of femtosecond laser in the grooves and the inter-
ference of laser light through the micropores, respectively.
With increasing pump energy, radical narrowing of the emis-
sion linewidth, laser threshold-like behavior and dramatic
shortening of the emission lifetime are observed. Positive
feedback is supplied by the periodic microstructures that
multiply scattering light. The emission peak wavelengths are
affected by the periodic microstructures. Compared with ran-
dom powder lasers, microstructure-textured grooves with a
structural stable property would be a potential candidate for
random laser applications.
Acknowledgments
The authors would like to acknowledge funding support from
the National Natural Science Foundation of China (NSFC)
(11574221).
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