Physica B 308–310 (2001) 942–944

Excitation mechanism of blue anti-Stokes and 2.4 mm infrared

emission in ZnSe : Cr
V.Yu. Ivanova,*, A.A. Shagovb, A. Szczerbakowa, M. Godlewskia
a
! 32/46, 02-668 Warsaw, Poland
Institute of Physics, Polish Academy of Sciences, Al. Lotnikow
b
Solar Laser Systems, Minsk, Byelorussia

Abstract

We report the observation and analyze the mechanism of efficient blue anti-Stokes emission in ZnSe : Cr. This
emission and the intra-shell transition of chromium Cr2+ at 2.4 mm are induced by 2+-1+ ionization transition of
chromium ions in ZnSe : Cr. The efficiency of the anti-Stokes photoluminescence anticorrelates with the efficiency of the
infrared emission. The latter emission dominates at increased temperatures. We conclude that the photoionization
excitation mechanism can be applied for optical pumping of 2.4 mm laser action in ZnSe : Cr. r 2001 Elsevier Science
B.V. All rights reserved.

Keywords: ZnSe; Chromium ion; Anti-Stokes emission; Infrared emission

1. Introduction or from the vapor phase by Markov–Davydov (MD)

We reported recently observation of efficient energy
up-conversion in chromium doped ZnSe [1]. Based on
the results of electron spin resonance (ESR) investiga-
tions, we concluded that the anti-Stokes luminescence
(ASL) in ZnSe : Cr is accompanying photoionization
excitation of chromium ions. In this work, we discuss an
inter-link between the ionization transition of Cr ions
and the 2.4 mm infrared emission, due to 5E-5T2
emission of Cr2+. The laser action was achieved for
the latter photoluminescence (PL) in chromium doped
wide bandgap II–VI materials [2–7]. The Cr2+ PL at
about 2.4 mm, due to 5E-5T2 intra-shell transition, has
a relative large PL line width of about 0.5 mm giving
possibility of tuning in relatively large spectral range.
2. Experimental
ZnSe samples studied were bulk crystals grown from
the melt by the Bridgman–Stockbarger (BS) technique
*Corresponding author. Tel.: +48-22-843-6861; fax: +48-
22-843-0926.
E-mail address: ivanov@ifpan.edu.pl (V.Yu. Ivanov).
technique. The first type crystals were purified by zone
melting with following treatment in the zinc melt. We
also studied some reference ZnSe epilayers obtained by
simple deposition from the vapor phase or by atomic
layer epitaxy in the gas flow version. Bulk BS crystals
were grown from a chromium doped melt, with resulting
chromium concentration, determined from the mass
spectral analysis of the crystals, varying between 1016
and 5  1019 cm 3, i.e., both lightly and heavily doped
samples were studied. Vapor phase MD crystals and
ZnSe epilayers were doped with chromium by diffusion
at 8001C temperature during 70–240 h treatment, with
Cr metal deposited on the surface by magnetron
sputtering. Cr concentration in these samples varied
from 5  1018 cm 3 to 8  1019 cm 3.
A conventional PL set-up was used with samples
mounted in a variable temperature cryostat. PL spectra
were dispersed with Ebert–Fasti monochromator and
detected with CCD camera (for visible and NIR region
detection) or InAs photovoltaic detector (1–3.5 mm). The
latter detector, assembled with digital oscilloscope was
used for the PL kinetics measurements in the infrared.
Visible light PL kinetics was measured with PMT
in time-correlated photon counting mode. For cw
excitation UV and visible lines of argon ion laser

0921-4526/01/$ - see front matter r 2001 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 1 - 4 5 2 6 ( 0 1 ) 0 0 8 7 5 - 4
 V.Yu. Ivanov et al. / Physica B 308–310 (2001) 942–944 943

(Innowa-400) together with dye-laser (with tuning range 2.47 µm

1.2 DAP

PL Intensity (arb.units)
of 1.65–2.25 eV) and HeaCd laser (2.807 eV) were used.
Excitation intensity was varied with a motorized 1.0 0.95µm
attenuator in the range of 1017–1024 photon/cm2 s. The
ESR experiments were performed with Bruker 300 0.8
T=4.2K
X-band spectrometer equipped with a continuous He Eex=2.34 eV
0.6
gas-flow Oxford Instruments cryostat. Photo-excitation Iex=0.25mJ
of the samples mounted in a microwave cavity was done 0.4
either with laser sources used in the PL study or with a
high-pressure mercury lamp and set of interference filters. 0.2 x10

0.0
0.40 0.45 0.50 0.55 1.20 1.25 1.30 1.35 2.6 2.7
3. Results and discussion Photon Energy (eV)
In Fig. 1 we present the PL spectra observed under Fig. 2. Chromium-related infrared PL emissions and the ASL
2.41 and 2.807 eV excitation for the relatively heavily emission observed in ZnSe : Cr under the photoionization
chromium doped sample (4.2  1018 cm 3) and at high excitation.
excitation density of 1019 photons/cm2 s. A very bright
blue color donor acceptor pair (DAP) emission is

ESR and PL Intensity (arb.units)

observed under 2.41 eV excitation with a weak red
DAP PL (not shown). The blue PL is excited by photons
of lower energy, thus, it is identified as the ASL [1]. It
should be mentioned, that neither excitonic transitions
(donor (DBE) and acceptor (ABE) bound exciton) nor
free-to-bound (FB) transition, which dominate at the
DAP ASL
above band gap excitation conditions, are observed
E SR infrared PL
under 2.41 eV excitation. This indicates efficient trapping
of free carriers by ionized Cr centers. In addition to the
visible light PL, two infrared intra-shell emissions of
Cr2+, the 2.4 mm PL due to 5E-5T2 transition and the 1.6 1.8 2.0 2.2 2.4 2.6 2.8 3.0
0.95 mm PL (see Fig. 2), are observed upon 2.41 eV Photon Energy (eV)
excitation. The latter PL was tentatively attributed to
3
T1-5T2 emission of Cr2+ [8]. Fig. 3. Comparison of the PL excitation spectra of the ASL
We measured temperature and excitation density and infrared PLs with the Cr1+ photo-excitation band
determined in the ESR study.
dependences of anti-Stokes and infrared emissions and
their excitation spectra. The PL excitation and photo-
ESR data (Fig. 3) prove that the 2+-1+ ionization
transition of chromium impurity excites the ASL and the Cr2+ intra-shell PL. The important question is, if the
ASL and the 2.4 mm PL emissions do not compete as
ABE
possible channels of energy relaxation. As explained
T=4.2 K DAP+FB previously, the ASL is excited due to two complemen-
PL Intesity (arb. units)

DBE
19 -1 -2 FB
J= 10 photon*sec cm tary ionization transitions of chromium ions [1]. Free
DBE
carriers, photo-created in conduction and valence bands
Eex=2.807 eV ABE-LO of ZnSe, participate in DAP PL responsible for the blue
DAP
ASL emission.
DAP-LO
For a two-quanta excitation mechanism, one could
expect a quadratic dependence on the light intensity. In
DAP-2LO fact we observed the quadratic dependence of the ASL
on excitation density for a two-photon excitation
Eex=2.41 eV process, studied by us for undoped ZnSe samples. In
2.55 2.60 2.65 2.70 2.75 2.80
the latter case a quantum efficiency of the ASL is fairly
low, and is below 10 5. The highly efficient ASL process
Photon Energy (eV)
observed by us in ZnSe : Cr (2  10 3 upon green color
Fig. 1. Low temperature photoluminescence spectrum of optical pumping and at helium temperature) shows, in a
ZnSe : Cr under above band gap excitation and the ASL large range of excitation densities, a linear dependence
excitation. of the ASL on excitation intensity. This, as results from
944 V.Yu. Ivanov et al. / Physica B 308–310 (2001) 942–944

our photo-ESR studies, is a consequence of a metastable neutralization transition of deep acceptors, and very
population of photo-excited Cr1+ centers, which is efficient photo-generation (see Fig. 3) for excitation,
observed at low temperatures. Free holes, created in the when deep acceptors are ionized, i.e., at the conditions
valence band under chromium 2+-1+ ionization, are when free electrons are created. This means, that the
efficiently trapped by shallow acceptor centers being Cr2+ centers can compete in electron trapping with
active in the ASL process. The second photon that is shallow donor centers active in visible emission of ZnSe,
absorbed by photo-generated Cr1+ state induces a whereas Cr1+ centers in trapping of free holes from the
complementary ionization transition to the conduction valence band. Thus, we can avoid limitation of optical
band. Thus, both the types of free carriers are photo- pumping and obtain efficient 2.4–2.5 mm infrared emis-
generated and can participate in the ASL. sion under injection of free electrons and holes.
The efficiency of the ASL emission is reduced at
increased temperatures, since required retrapping of
photo-generated free carriers by shallow donor and 4. Conclusions
acceptor centers active in the ASL becomes temperature
deactivated. This is, why the deactivation of the ASL is 2.4 mm PL of Cr2+ is efficient at room temperature
characterized by deactivation energies of about 110– and can be either optically pumped upon Cr ionization
120 meV (Fig. 4) related to the thermal ionization of transitions or it can be excited by injection of free
shallow acceptors. carriers. The former process can be important both for
The detrimental sensitivity of the ASL to the increase the optical pumping of this PL by easily available and
in the temperature turned out to be profitable for the very efficient light sources in green color. The latter
second process studied by us. With decreasing efficiency process may be important in light emitting devices
of the ASL process, the intra-shell emission of Cr2+ is working under carrier injection conditions.
more efficient (Fig. 4). The photo-generated holes are at
higher temperatures more efficiently retrapped by
Acknowledgements
ionized chromium centers. As a consequence, Cr1+
state, an intermediate state in a two-quanta excitation
We are indebted to A.A. Davydov for providing
transition, is no longer metastably occupied and a linear
vapor grown ZnSe crystals. This work was partly
dependence on a light density is not observed for both
supported by grant no. 5 P03B 007 20 of KBN for the
the ASL and the intra-shell excitation processes.
years 2001–2003.
High efficiency of the intra-shell PL means, that hole
retrapping by ionized Cr1+ centers proceeds via the
excited 5E (and also 3T1) state of Cr2+ impurity and that References
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