Optics Communications 304 (2013) 75–79

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Optics Communications
journal homepage: www.elsevier.com/locate/optcom

Excited state assisted three-photon absorption based optical limiting

in nanocrystalline Cu2Se and FeSe2
Benoy Anand, Muralikrishna Molli n, Saikiran Aditha, Tanu Mimani Rattan,
Siva Sankara Sai S, Venkataramaniah Kamisetti
Department of Physics, Sri Sathya Sai Institute of Higher Learning, Prasanthi Nilayam, Andhra Pradesh, 515134, India

art ic l e i nf o a b s t r a c t

Article history: Transition metal selenides (FeSe2 and Cu2Se) are synthesized by the hydrothermal co-reduction method.
Received 15 July 2012 XRD results revealed the crystalline nature of their single phase and the elemental compositions are
Received in revised form obtained using EDS. TEM images of the as-prepared samples show the formation of nanorods of 10–
20 April 2013
20 nm diameter in case of iron selenide and nanoparticles of 10–35 nm diameter in case of
Accepted 24 April 2013
Available online 7 May 2013
copper selenide. The energy bandgap values are calculated using tauc plots obtained from UV–Visible
absorption spectra. The open aperture Z-scan measurements carried out using 5 ns pulses at 532 nm
Keywords: revealed that the samples showed excellent optical limiting behavior owing to strong nonlinear
Transition metal selenides absorption (NLA). Through numerical simulations, the mechanism of NLA is found to be effective
Hydrothermal method
three-photon absorption which has significant contribution from excited state absorption.
Nonlinear absorption
& 2013 Elsevier B.V. All rights reserved.
Optical limiting
Energy band gap

1. Introduction excellent nonlinear optical properties, especially the optical limiting

Low-dimensional nanostructures are not only interesting for
fundamental research, due to their unique structural and physical
properties relative to their bulk counterparts, but also offer fascinat-
ing potential for future technological applications. Nanostructures of
transition metal chalcogenides, owing to their chemical composition
and nanometer dimension, exhibit a variety of fascinating proper-
ties. Metal chalcogenides like selenide, sulfide, and telluride com-
pounds are semiconducting in nature, and are of considerable
technical interest in the fields of electronics, optical and electro-
optical devices, thermoelectrics, magnetic materials, superconduc-
tors and photovoltaics [1–5]. These chalcogenides with nanoscale
dimensions are highly attractive for technological applications like
thermoelectric cooling, optical filters, optical recording materials,
solar cells, supersonic materials, and sensor and laser materials [6,7].
Nonlinear optics (NLO) continues to be one of the actively
pursued research areas of recent times, owing to the wealth of
various novel phenomena unraveled by this exciting field of study
and its plethora of applications in photonics such as optical
processing, optical computing, optical data storage and optical limit-
ing (OL) [8,9]. Of the various nano chalcogenides, the transition metal
semiconducting selenides are of great importance due to their
n
Corresponding author. Tel.: +91 8555 286324; fax: +91 8555 286919.
E-mail addresses: muralikrishnamolli@sssihl.edu.in,
muralim.phy@gmail.com (M. Molli).
behavior. An optical limiter shows linear transmittance at low
incident intensities and attenuates the beam considerably at higher
intensities, so that it can protect human eyes and optical sensors
from intense laser radiation. For example, Lad et al. [10] observed
strong three-photon absorption (3 PA) in ZnSe quantum dots (QDs)
and found that 3PA cross-section increases with decreasing size of
the QD due to strong confinement effects. Ultrafast Z-scan measure-
ment done on CdSe nanoparticles showed that they posses size
dependent multiphoton absorption properties at 800 nm resulting in
OL behavior [11]. However due to their high sensitivity to tempera-
ture and existence of variable oxidation states of the metal and
selenium, the preparation of purely a single phase of these materials
is often a challenge. Therefore we have adopted a hydrothermal
route for the synthesis of these selenides. In hydrothermal process,
the use of water under supercritical conditions plays a major role in
the formation of a unique phase rather than a mixture of phases
under optimum experimental conditions. Also, this method allows
tailor making samples with required morphology by varying
three main parameters: pressure, temperature and reaction time.
Another advantage is its low synthesis temperature of o200 1C,
which facilitates the growth of products with uniform grain size,
homogeneity and monodispersity thereby improving their specific
properties.
In this work, we report the synthesis of nanocrystalline Cu2Se
and FeSe2 via hydrothermal co-reduction route and their linear
and third-order nonlinear optical characterizations. The sam-
ples are characterized by powder X-ray diffraction (XRD), High

0030-4018/$ - see front matter & 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.optcom.2013.04.037
76 B. Anand et al. / Optics Communications 304 (2013) 75–79

Resolution Transmission Electron Microscopy (HRTEM) and Energy
Dispersive Spectroscopy (EDS). The energy bandgap values are
calculated from their UV–Visible absorption spectra using tauc
analysis. The optical nonlinearity of the samples are investigated
by the open aperture Z-scan technique at nano second (ns) excitation
regime. The nonlinear absorption due to effective three-photon
absorption and the resulting optical limiting behavior are discussed
in detail.
2. Experimental procedure
light transmission through the sample as function of z position
result in intensity dependent transmittance data from which
co-efficients of nonlinearity can be extracted using numerical
fitting. In order to avoid the influence of accumulative thermal
effect, a single-pulse measurement is used with pulse repetition in
every two seconds by giving an external trigger to the laser so that,
each pulse of light is certain to encounter unexcited molecules in
the sample. This low repetition rate favours self replenishment in
the case of dispersed samples and avoids measurement from
photodegraded sample.

2.1. Materials 3. Results and discussion

Cupric chloride (CuCl2
2H2O) (499%), Sodium selenite (Na2SeO3)
(499%), and Hydrazine monohydrate (N2H4
H2O) (499%) are used
as starting materials for the synthesis of copper selenide. Ferric
chloride (FeCl3
6H2O) (99%) is used as starting material for the
synthesis of iron selenide. All these chemicals are obtained from Alfa
Aesar Co., USA.
2.2. Synthesis procedure
In a typical experimental procedure, an aqueous solution of
40 mL is prepared by dissolving 0.15 M CuCl2
2H2O, 75 mM Na2
SeO3, and 1.5 M N2H4
H2O in distilled water under constant stirring.
The mixture is then transferred to a stainless steel autoclave of 50 mL
capacity and heated at 100 1C for 12 h and then allowed to cool to
room temperature naturally. The final products which were greenish
black in color are filtered off, washed with absolute ethanol and
distilled water for several times, and dried in vacuum at 60 1C for 4 h.
Similar procedure is followed for the synthesis of iron selenide by
mixing 75 mM FeCl3
6 H2O, 75 mM Na2SeO3, and 1.5 M N2H4
H2O
in distilled water under the same reaction conditions.
2.3. Characterization
The phase compositions of the samples are studied by X-ray
diffraction using PANalytical X'pert Pro MPD diffractometer with
the following settings: voltage −45 kV, current −30 mA, scan rate
−21/min and step size 0.020. The powder particulate property is
studied by high resolution TEM using Tecnai F30 (FEI, Eindhoven,
Netherlands) microscope operating at 200 kV. Energy Dispersive
Spectroscopic (EDS) analysis is performed to get the stoichiometry
data. UV–Visible transmission measurements are carried out using
UV–Visible spectrophotometer (Shimadzu, UV-2450).
3.1. Materials characterization
3.1.1. Crystal structure and phase analysis
The as-prepared samples are characterized for their phase by
XRD. Fig. 1 shows the X-ray diffraction patterns of the prepared
selenides Cu2Se and FeSe2. All the diffraction peaks in iron
selenide can be indexed as orthorhombic phase FeSe2 (JCPDS
no.: 01-082-0269) with cell parameters a(Å) ¼4.800, b(Å) ¼5.782,
c(Å) ¼3.583, α(1) ¼β(1)¼γ(1) ¼90. Similarly the diffraction peaks in
copper selenide can be indexed as cubic phase Cu2Se (JCPDS no.:
01-088-2043) with cell parameters a(Å) ¼b(Å) ¼c(Å)¼ 5.694,
α(1) ¼β(1)¼γ(1)¼90. The broadening of the diffraction peaks is
due to the small size of the crystallites. Using the FWHM data and
Debye–Scherrer formula [12,13] average crystallite sizes for iron
selenide and copper selenide samples are calculated to be 84 nm
and 73 nm, respectively.
3.1.2. Morphology
The High Resolution Transmission Electron Microscope (HRTEM)
micrographs of the as-prepared samples given in Fig. 2a and b show
the formation of FeSe2 nanorods with length 40–75 nm and diameter
10–20 nm and Cu2Se nanoparticles with diameter 10–35 nm. The
EDS analysis shows that the elemental ratio of iron to selenium in
the iron selenide sample is 1:1.65 whereas in copper selenide the
elemental ratio of copper to selenium is 1.73:1.

2.4. Nonlinear optical measurements using the Z-scan method

The sample dispersions in ethanol are contained in 1 mm thick

quartz cells. Its NLO response in the ns excitation regime is
measured with linearly polarized 5 ns optical pulses from a
Q-switched frequency-doubled Nd: YAG laser. The concentration
of the samples is adjusted so that its linear transmission (LT) is 70%
at the excitation wavelength of 532 nm. The spatial profile of the
pulse is nearly of Gaussian form. The pulses are divided by a beam
splitter into two parts. The reflected part is taken as the reference
representing the incident light energy and the transmitted part is
focused on to the sample containing cuvette using a converging
lens of focal length 10 cm. Both the reference and transmitted
pulse energies are measured simultaneously by two pyroelectric
energy detectors (RjP-735, Laser Probe Inc.). The beam propaga-
tion direction is taken as the z-axis. The sample is mounted on a
computer controlled translation stage, and is translated from −z to
+z with z¼ 0 being the focal point. Since the cross-sectional area of Fig. 1. Powder X-ray diffraction pattern of nanocrystalline copper selenide and iron
the focused beam is different at different z points, measurement of selenide.
 B. Anand et al. / Optics Communications 304 (2013) 75–79
Fig. 2. HRTEM micrograph of (a) FeSe2 and (b) Cu2Se with insets showing the lattice fringes.
Fig. 3. Tauc plot for (a) FeSe2 nanorods and (b) Cu2Se nanoparticles and the calculated direct bandgap energy is 1.39 eV and 2.01 eV, respectively. Insets show the
corresponding linear absorption spectra.
3.2. Energy band gap measurements
One of the important features of semiconducting nanomater-
ials which determines their applications in the fields of optoelec-
tronics, thermoelectrics and photovoltaics is their energy band
gap. The UV–Visible absorption spectroscopy is frequently used to
determine the energy band gap of the powder samples from their
absorption spectra which is carried out by dispersing the sample
in a liquid media. In the present case, optical transmission spectra
of sample solutions in absolute ethanol are recorded between 200
and 900 nm. The absorption coefficient (α) is calculated from the
transmission values and a tauc plot of ðαhνÞ2 vs hν, is drawn [14].
The tauc equation used for the analysis is given by
ðαhνÞ2 ¼ const:ðhν−Eg Þ
where, Eg is the energy bandgap. The linear portion of the graph
was extrapolated to the energy axis as shown in Fig. 3a and b. The
intersection point gives the direct bandgap energy and is found to
be 1.39 eV for FeSe2 nanorods and 2.01 eV for Cu2Se nanoparticles.
3.3. Optical limiting in nanocrystalline Cu2Se and FeSe2
Strong nonlinear response is observed when ns open aperture
Z-scan was done on the sample solutions at 70% linear transmit-
tance. In a typical open aperture Z-scan, intensity dependent
transmittance is plotted against the sample position measured
relative to the beam focus. Nonlinear absorption is indicated by a
77
smooth valley shaped curve, symmetric about the focal (z¼0)
position. The Z-scan curves obtained for both the samples shown
in Fig. 4 indicate a typical nonlinear absorptive response. It is clear
from the Z-scan curves that the optical transmittance falls as
intensity increases, indicating optical limiting behavior in the
samples. For such an optical limiter, the depth of the valley in the
Z-scan curve is a direct measure of the extent of optical limiting.
Depending on the nature of the sample and the excitation
wavelength and pulse width, NLA can happen via a number of
mechanisms like multiphoton absorption, saturable absorption, free-
carrier absorption and excited state absorption (ESA). To identify the
exact nature of the nonlinearity resulting in the observed OL, the
Z-scan data are fitted to different nonlinear transmission equations,
and it turned out that the best fit is to a three-photon absorption
ð1Þ
process (3PA) as seen in Fig. 4. The nonlinear absorption coefficient
(α) in a 3PA process is given by αðIÞ ¼ α0 þ γI 2 , where I is the intensity
of the laser pulse, α0 is the unsaturated linear absorption coefficient,
and γ is the 3PA coefficient. The transmitted intensity for a given
input intensity is calculated by numerically solving the propagation
equation
dI
¼ −α0 I−γI 3 ð2Þ
dz′
Here z′ indicates the propagation distance within the sample
[8]. Input intensities for the gaussian beam are calculated from the
input energy, laser pulse width and irradiation area. The inten-
sities are then integrated in time to obtain the corresponding
78 B. Anand et al. / Optics Communications 304 (2013) 75–79
Fig. 4. Open aperture Z-scan curves of nanocrystalline Cu2Se and FeSe2 fitted with
3PA equation. The flat Z-scan curve obtained for the solvent (ethanol) suggests that
the solvent nonlinearity is too weak to measure.
fluences. The normalized transmittance is then calculated by
dividing the output fluence with the input fluence and normal-
izing it with the linear transmittance. The nonlinear parameter γ is
calculated from the best-fit curve for the experimental data and it
is in the range of 10−23 m3/W2 and 10−22 m3/W2 for FeSe2 and
Cu2Se respectively. As seen in Fig. 4, the absence of solvent
nonlinearity under the current excitation conditions suggests that
the OL arises solely from the NLA in the samples.
The optical limiting performance of the samples are quantified
using limiting threshold, which is defined as the input fluence at
which the transmittance falls to 50% of the linear transmittance. This
is calculated from the optical limiting curve of the sample (Fig. 5),
which is a plot between normalized sample transmittance and the
input laser fluence. The optical limiting response can be extracted
from the open aperture Z-scan curve directly as follows. In the case
of open aperture Z-scan using a Gaussian beam, the input fluence at
each Z-position is given by
pffiffiffiffiffiffiffiffiffi
FðzÞ ¼ 4 ln 2Ein =π 3=2 ωðzÞ2 ð3Þ
where, Ein is the input laser pulse energy and ωðzÞ is the beam radius.
ωðzÞ is calculated using the expression ωðzÞ ¼ ω0 ½1 þ ðz=z0 Þ2 1=2
where ω0 is the beam radius at the focus and z0 ¼ πω20 =λ is the
Rayleigh range. Since the beam radius is minimum at the focus, the
sample experiences maximum fluence at this point. The limiting
threshold values calculated from the optical limiting curves are
5.47 J/cm2 and 14.38 J/cm2 for Cu2Se and FeSe2 respectively, suggesting
that Cu2Se is a better optical limiter.
Fig. 6 shows the plot of calculated γ values versus on-axis peak
intensity, Io. The variation in γ with incident intensity suggests that
the observed 3PA arises not only due to a genuine 3PA, but also
from a sequential 3PA making it an effective 3PA process. In the
case of a sequential 3PA process (also known as ESA), electron
transitions from the ground state to the final state are mediated by
real intermediate states, and γ varies with the incident laser
intensity as it affects excited state populations. On the other hand,
in the case of genuine 3PA, where the intermediate states involved
are virtual, the absorption coefficient is a constant and is inde-
pendent of the incident laser intensity [15–17]. In general multi-
photon absorption processes arising from simultaneous absorption
of two/three photons are faster compared to ESA process which
rely on sequential electron transitions. All the absorption coeffi-
cients (αo, β, γ etc.) are dependent on the ground state population
N, because generically, an absorption coefficient is obtained by
Fig. 5. Optical limiting curves of nanocrystalline FeSe2 and Cu2Se.
multiplying the corresponding absorption cross-section (s) by N.
The absorption cross section is a microscopic parameter, indepen-
dent of N, which characterizes the average two photon/three
photon absorbability per molecule. A change in absorption coeffi-
cient will be evident only if there is a substantial change in the
ground state population due to the absorption. A genuine 3PA is a
weak process and the ground state depletion is negligible. So, the
absorption coefficient is a constant, and is independent of the
incident intensity. On the other hand in the case of sequential 3PA
where there is a strong excited state absorption (ESA) which
depletes the ground state population considerably, the absorption
coefficients become a function of incident intensity. The semitran-
sparent nature of the samples (LT of 70% which corresponds to
∼24% of linear absorption excluding reflection loss from the
cuvette surface) at the excitation wavelength also indicates that
the observed nonlinearity will have contributions from ESA invol-
ving real excited states. It may be noted that the strength of ESA
can be resonantly enhanced when the excitation wavelength
matches with the peaks in the linear absorption spectrum. Thus
strong ESA in the present case leads to interband and subsequent
intraband transitions in nanocrystalline Cu2Se and FeSe2 resulting
in the observed OL action. The occupied and unoccupied density of
states (DOS) near the Fermi level is one of the important factors
that determine the transition probability in an interband transition
[18]. Therefore, it is reasonable to assume that the better OL in
Cu2Se nanoparticles compared to FeSe2 nanorods may be due to
the availability of more occupied and unoccupied DOS near the
Fermi level.
4. Conclusions
We have synthesized iron selenide nanorods and copper selenide
nanoparticles with single phase using hydrothermal co-reduction
route and determined their energy band gaps using UV–Visible
absorption spectroscopy. Open aperture Z-scan measurements were
carried out on nanocrystalline FeSe2 and Cu2Se dispersions at ns
excitation regime. From measurements using 5 ns laser pulses at
532 nm, the material is found to have strong nonlinear absorption
which was attributed to an effective 3PA arising due to both genuine
and sequential three-photon absorption processes. The absorptive
nonlinearity observed in these samples is of optical limiting type
which can have potential applications in eye and sensor protection,
and in photonics.
 B. Anand et al. / Optics Communications 304 (2013) 75–79
Fig. 6. Variation of γ with incident on-axis peak intensity (Io) indicating a sequential 3PA process due to excited state absorption in (a) Cu2Se and (b) FeSe2.
Acknowledgments
Authors express their gratitude to Bhagawan Sri Sathya Sai
Baba, the founder chancellor of SSSIHL, for his constant support
and lab facilities. BA acknowledges UGC, and MMK acknowledges
CSIR for their research fellowships. VK and SSSS thank UGC and
DST for the financial support.
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