Appl. Phys. B 72, 253–255 (2001) / Digital Object Identifier (DOI) 10.
1007/s003400000503
Rapid communication
Efficient laser operation and continuous-wave diode pumping of
Cr2+:ZnSe single crystals
A.V. Podlipensky1 , V.G. Shcherbitsky1 , N.V. Kuleshov1 , V.I. Levchenko2 , V.N. Yakimovich2 , M. Mond3 ,
E. Heumann3 , G. Huber3 , H. Kretschmann3 , S. Kück3
1 International Laser Center, Belarus St. Politechnical Academy, Scorina Av. 65, Minsk 220027, Belarus
(Fax: +375-17/2326286, E-mail: kuleshov@ilc.unibel.by)
2 Institute of Solid State and Semiconductor Physics, National Academy of Science of Belarus, P. Brouki st. 17, Minsk 220072, Belarus
(Fax: +375/17-2840828, E-mail: levchen@ifftp.bas-net.by)
3 Institut für Laser-Physik, Universität Hamburg, Jungiusstr. 9a, 20355 Hamburg, Germany
(Fax: +49-40/42838-6281, E-mail: mond@physnet.uni-hamburg.de)
Received: 12 October 2000/Published online: 30 November 2000 –  Springer-Verlag 2000
Abstract. Efficient continuous-wave laser operation of
Cr2+ :ZnSe was demonstrated with an output power of
1400 mW at an absorbed pump power of 1900 mW from
a Tm:YAG laser. Under continuous-wave diode pumping
at 1.54 µm an output power of 15 mW was obtained from
a Cr+2 :ZnSe laser. Excited state absorption is shown to be
negligible in the pump and laser spectral region.
PACS: 42.70.Hj; 42.55.Rz; 78.45.+h
Cr2+ -doped chalcogenide crystals were shown recently to
be promising materials for highly efficient and broadly tun-
able mid-IR (2–3 µm) lasers [1–3]. Possible applications
of these lasers include medicine, remote sensing and trace-
gas analysis. Pulsed [4], continuous-wave (cw) [5, 6], gain-
switched [7] and diode-side-pumped laser operation [8] have
been demonstrated with Cr2+ :ZnSe, which exhibited thus far
a slope efficiency as high as 63% and a tunability between
2138 nm and 2760 nm [5]. However, one of the problems
encountered with these kinds of materials is their relatively
high level of passive losses at the laser wavelength [4]. In-
vestigation of the material synthesis by using various crystal
growth techniques is necessary to reduce as much as possible
what is due to extrinsic reasons such as unwanted impurities
and lattice defects. Detailed spectroscopic studies including
excited state absorption (ESA) measurements allow us to es-
timate the amount of intrinsic optical losses. Intra ionic ESA
transitions in Cr2+ -doped Zn-chalcogenides are not expected
to be a problem, since there are no terminal levels for spin-
allowed ESA transitions from the 5E emitting level. How-
ever, ESA measurements are of great interest since they could
answer whether other types of ESA transitions, for example
to charge-transfer states or to the conduction band, can af-
fect the laser efficiency. In this paper we report for the first
time to our knowledge on the results of ESA measurements
in Cr2+ :ZnSe, on the realization of 1.4 W cw laser operation
with Cr2+ :ZnSe single crystals and on the realization of direct
cw pumping with 1.54-µm laser diodes.
Applied Physics B
Lasers
and Optics
Cr2+ :ZnSe samples were prepared by a modified two-
stage diffusion doping method [9]. At the first stage, undoped
single crystals of high optical quality were grown by the sub-
limation traveling heater method without seeding. At the se-
cond stage we introduced the chromium impurity into the host
material by the thermal diffusion method from a solid metal
source. Chromium films were deposited upon the crystal sur-
faces by magnetron sputtering. Diffusion was carried out in
sealed ampoules under a pressure of 5 × 10 −6 Torr and a tem-
perature of 700–1000 ◦ C over 1–10 days. The advantages of
this two-stage process are a high quality of the final products
and the ability to control the impurity doping level by ad-
justing the diffusion time and temperature and by varying the
chromium film thickness.
Polished samples of 1–3 mm in thickness and up to
10 mm in aperture were used for the spectroscopic mea-
surements and the laser experiments. All measurements
were performed at room temperature. The absorption spectra
were measured with a Cary 17D spectrometer. The emission
spectrum was recorded with a liquid-nitrogen-cooled InSb
detector and a 0.5-m Spex monochromator and corrected
for the transmittance of the monochromator and the photo-
detector sensitivity. The experimental setup used for the ESA
measurements with a cw pump and probe technique and
based on a double-modulation method was described in [10].
A 100-mW Tm:YAG laser operating at 2013 nm was used as
an excitation source. A liquid-nitrogen-cooled InSb detector
in the infrared spectral range was used to detect a 250 W tung-
sten lamp probe beam passed through the sample and through
a 0.5 m Spex monochromator. The sample was placed be-
hind a pinhole of 0.5 mm in diameter in order to optimize
the overlap between pump and probe beams. The probe beam
was chopped at a frequency of about 700 Hz and analyzed by
a first lock-in amplifier in order to measure the transmission
spectrum T . The difference ∆T in the transmitted intensi-
ties through the pumped (I p ) and unpumped (I u ) sample was
measured by chopping the pump beam at about 10 Hz and
analyzing the resulting modulation of the probe-beam inten-
sity with a second lock-in amplifier. It can be easily shown
that ln(Ip /Iu )  ∆T/T for small ∆T , and we can use the fol-
254
lowing equation to evaluate the results of our measurements:


∆T/T = A n e d σse + σgsa − σesa , (1)
where A is the constant amplification factor of the second am-
plifier, σse , σgsa and σesa are the cross sections of stimulated
emission, ground state absorption and excited state absorp-
tion, respectively, n e is the population density in the excited
state and d is the crystal length. In order to calibrate the mea-
sured spectra of ∆T/T for absolute cross sections, the factor
A n e d can be determined by fitting the σgsa -spectrum to the
observed bleaching bands in the spectral range where no other
effects like excited state absorption or stimulated emission
occur. After calibrating the measurements in this way the dif-
ference spectra of (σse − σesa ) can be obtained by subtraction
of the σgsa -spectrum.
The infrared absorption and emission cross section spec-
tra of Cr2+ :ZnSe are plotted in Fig. 1. The broad absorption
band near 1.8 µm and a broad emission band with a peak at
2.4 µm belong to the transitions between the 5T2 ground state
and the 5E excited state of tetrahedrally coordinated Cr2+
(3d 4 electron configuration) ions [1]. The ∆T/T -spectrum at
room temperature in the spectral range from 1.2 to 3 µm is
also shown in Fig. 1. A strong broad positive band peak-
ing at 1.8 µm corresponds to the absorption saturation of the
Cr2+ -ions due to ground state depletion. The positive band
between 2 and 3 µm with a maximum near 2.4 µm belongs
to the stimulated emission. The negative signal in the range
of wavelengths shorter than 1.4 µm is assigned to ESA tran-
sitions from the 5E level. According to the energy level dia-
gram of 3d 4 ions the d − d transitions from the 5E excited
state to higher lying energy levels are spin-forbidden, and this
ESA band is associated most likely with transitions between
the 5E level and charge-transfer states or the conduction
band. The spectrum of ∆T/T was calibrated for the absolute
cross sections by fitting the σgsa -band to the bleaching band
in the spectral range between 1600 nm and 1800 nm (Fig. 1),
assuming that σse = 0, σesa is negligible in this range [11],
and the ground state absorption cross section at 1800 nm
is 8.7 × 10−19 cm2 [4]. The effective stimulated emission
cross section was determined from the resulting spectrum of
σ [10 -19cm2 ]
Fig. 1. σgsa - (dashed line), σse - (dotted line), (σgsa + σse − σesa )- (thin solid
line) and (σse − σesa )-spectrum (thick solid line) of Cr2+ :ZnSe at room tem-
perature. The sharp structure beyond 2500 nm is attributed to the water
absorption in air and the following normalization process
(σse − σesa ) to be 8 × 10−19 cm2 at 2400 nm. In comparison,
in [1, 5] σse was determined to be about 9 × 10 −19 cm2 . This
good agreement, and the fact that the (σ se − σesa )-spectrum
matches the σse -spectrum (Fig. 1) indicate that ESA is neg-
ligible in the whole emission range. Taking into account the
errors in the determination of the cross sections and in the
ESA measurements, the ratio σesa /σse does not exceed 10%.
A tunability up to 3 µm in the long-wavelength range should
be possible with Cr2+ :ZnSe.
Laser experiments were performed with a hemispherical
cavity configuration, consisting of a plane high reflector and
a 50-mm radius of curvature output coupler. The uncoated
laser crystal was mounted on a copper heat sink cooled by
water and placed at normal incidence near the high reflector.
A cw diode-pumped Tm:YAG laser emitting at 2013 nm with
an output power up to 4.1 W was used as a pump source. The
pump beam was focused into the laser crystal with a 45 mm
focal length lens. The pump-beam spot size and M 2 -factor
were measured to be 72–96 µm and 1.5 − 6, respectively, de-
pending on Tm:YAG laser output power. The best results
were obtained with a 2 mm thick laser crystal with an ab-
sorption coefficient of 5 cm−1 at the pump wavelength. An
output power of 1400 mW near 2500 nm at an absorbed pump
power of 1900 mW was demonstrated by using a 13.4% out-
put coupler (Fig. 2). The laser threshold measurements were
carried out using an optical isolator inserted between pump
and Cr:ZnSe laser in order to prevent feedback into the pump
laser. The threshold values were measured to be 84 mW,
58 mW, 35 mW and 29 mW of absorbed pump power for out-
put couplers with 13.4%, 6.7%, 2% transmission and for the
high reflector, respectively. The highest slope efficiency with
respect to the absorbed power was measured to be 73% for
the output coupler with a transmission of 13.4%. The free-
running output spectrum covered the wavelength range from
2454 nm to 2560 nm and was determined by the cavity optics
employed. The round-trip passive loss L d was estimated to
be approx. 2.5% from a Caird plot of inverse slope efficiency
versus inverse output coupling [12], see Fig. 3a:
 
1 1 Ld
= 1+ , (2)
η η0 T
where η is the slope efficiency, η0 is the limiting slope effi-
ciency and T is the mirror transmission. The derived limiting
Fig. 2. Input–output diagram of the Cr:ZnSe continuous-wave laser under
2.01-µm Tm:YAG-laser pumping

Fig. 3. a Caird plot of inverse slope efficiency versus inverse output coup-
ling, b Findlay–Clay plot of laser threshold versus output-coupler transmis-
sion
slope efficiency of approx. 76% (compared to the quantum
defect of 81%) also indicates the negligible influence of ex-
cited state absorption on the pump and laser wavelength. On
the other hand, from a Findlay–Clay analysis [13] (Fig. 3b)
of the threshold data for different output couplers the value
of L d was determined to be approx. 6.8%. The deviation be-
tween these values of round-trip losses obtained by these two
different methods can be explained by the existence of re-
sidual ground state absorption at the laser wavelength, which
increases the laser threshold but does not affect the slope effi-
ciency in the case of high luminescence quantum efficiency.
The above described results on laser efficiency, laser
threshold and pump-beam parameters indicated the possibi-
lity of direct cw diode-laser pumping of Cr:ZnSe crystals.
Laser experiments were performed with the same hemispheri-
cal laser cavity configuration as for the Tm:YAG-laser pump-
ing. A fiber-coupled laser diode emitting up to 400 mW at
1.54 µm was used as a pump source. The fiber had a core
diameter of 125 µm and a numerical aperture of 0.12. The
pump beam was focused with a collimating and a focusing
lens of 50 mm and 30 mm focal lengths, respectively, to a spot
size of 86 µm diameter in the crystal. The input–output dia-
gram for a 98% output coupler reflectivity is shown in Fig. 4.
A laser threshold of 75 mW and a slope efficiency of 14.2%
with respect to absorbed pump power were demonstrated.
The maximum output power was 15.4 mW. The spectrum in
free-running laser operation covered the spectral range from
2486 to 2540 nm.
255
Fig. 4. Input–output diagram of the Cr2+ :ZnSe continuous-wave laser under
1.54-µm diode-laser pumping
In conclusion, room temperature cw ESA measurements
were performed for Cr 2+ :ZnSe in the spectral range between
1.2 and 3 µm. A stimulated emission band was observed
from 2 to 3 µm with an effective peak emission cross sec-
tion of 8 × 10−19 cm2 at 2400 nm. Excited state absorption is
negligible in the pump and laser spectral range (1.5–3 µm).
An output power of 1.4 W has been demonstrated from
the cw Cr2+ :ZnSe laser with a slope efficiency as high as
73%. Direct cw diode-laser pumping of Cr:ZnSe laser was
realized.
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