Optical Materials 109 (2020) 110343

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Optical Materials
journal homepage: http://www.elsevier.com/locate/optmat

The two-photon absorption coefficient in a wide spectral range of

Cd1-0.45Mn0.45Te
Nathan Chalus, Maxwell A. Elmendorf, H. Garcia *
Physics Department, Southern Illinois University, Edwardsville, IL, 62026, USA

A B S T R A C T

We are reporting, for the first time to our knowledge, measurement of the degenerate two-photon absorption (TPA) coefficient in Cd1-xMnxTe (x = 0.45) in a wide
spectral range (690–1040 nm), with a 5 nm resolution. The spectral dependence of the TPA is modeled as a combination of a-a and f-f transitions. The time response is
ultrafast at 780 nm with a relaxation time on the order of 14.1 ps and a large TPA coefficient on the order of 60 cm/GW at 690 nm.

Dilute magnetic semiconductors (DMS) have been around since the
late seventies [1]. There is a large amount of literature in terms of band
structure calculation, optical properties, and magneto-optical properties
of these semiconductors [2–5]. Cd1-xMnxTe is a dilute magnetic material
that has a wide range of applications in photonic devices such as solar
cells, optical isolators, and magnetic field sensors [6–8]. Recently,
Cd1-xMnxTe has been identified as a promising material for applications
in X-ray and Gamma-rays detectors [9,10].
CdMnTe is a direct wide-gap semiconductor where Cd cations are
substituted by Mn ions in the CdTe crystal structure. It has been
experimentally shown that as the composition of Mn is increased, the
energy gap increases such that at some value of Mn concentration, the
system becomes transparent in the visible region. The semiconductor is
crystalized in a zinc blende structure, and its optical properties have
been explained in terms of direct gap materials. The introduction of the
Mn2+sd [5] configuration lead to new magnetic and optical properties.
The presence of the Mn2+sd [5] results in an exchange interaction be­
tween the sp electrons and the d electrons that result in a large Zeeman
splitting of the electronic levels [11]. This extremely large spin effect
produces large Faraday rotations, magnetic induced metal-insulator
transitions and bound magnetic polarons, to mention a few.
In contrast to the vast research on the properties of Cd1-xMnxTe, and
in particular, on its optical and magnetic properties, there is a lack of
information on the third-order nonlinear response in this material. In
this paper we report on the Two-Photon Absorption (TPA) coefficient of
Cd0.55Mn0.45Te single crystal in the range of 690–1040 nm using a
tunable broadband source (Spectra-Physics Mai Tai HP, USA). The laser
was characterized and the experimental technique to measure the TPA is
described elsewhere [12,13].
CdMnTe crystal was prepared at Brimrose Technology Corporation
for the ongoing collaboration on magneto-optic materials. CdMnTe
crystallizes in Zincblende structure. The band gap of Cd 1-xMnxTe varies
with mole fraction x [14]. The composition of crystals reported in this
paper is: Cd1-xMnxTe (x = 0.45). The pseudo-binary phase diagram [15]
of CdTe-MnTe indicates that Cd1-xMnxTe (x = 0.45) crystals can be
grown with the reasonably good homogeneity. The crystal was grown
using vertical Bridgman technique reported elsewhere [16,17]. The
synthesis of the nutrient material was carried out using high purity
(99.9999%) cadmium and tellurium. The Manganese was purified by
Brimrose Technology Corporation with commercially available
99.998% pure manganese, using an in-house proprietary technique. The
vacuum sealed pre-synthesized material was molten in a 3-zone furnace
and was lowered in the furnace at a rate of 2 mm/h, thru a temperature
gradient of 20 ◦ C/cm. Upon cooling, the crystal was carefully removed
from the ampoule and samples were prepared via cutting and cleaning
and optically polished by mechanical polishing. The final sample
thickness was down to 1.58 mm.
The linear absorption of the sample was measured using an Ocean-
Optics spectrometer (HR2000, USA) in transmittance mode with an
integration time of 9000-μsec (see Fig. 1). In transmittance mode the
spectrometer measurement is given by
S− D
T(λ) = (1)
Rref − D
where S is the signal, D is a background level and Rref is the reference.
The above equation does not take into account the reflection from both
of the sample faces, so to correct for the reflection the above equation is
divided by (1-R) [2] where R is the reflection coefficient at normal

* Corresponding author.
E-mail address: hgarcia@siue.edu (H. Garcia).

https://doi.org/10.1016/j.optmat.2020.110343
Received 12 May 2020; Received in revised form 14 August 2020; Accepted 16 August 2020
Available online 7 September 2020
0925-3467/© 2020 Elsevier B.V. All rights reserved.
N. Chalus et al. Optical Materials 109 (2020) 110343

Thus, using the well-known expression for Z-scan open aperture archi­
tecture [20],
β(1 − R)I0 Leff
T(z) = 1 − √̅̅̅ (3)
2 2(1 + x2 )

where β is the TPA coefficient, I0 is the maximum irradiance of the beam

at z = 0, R is the reflection coefficient at normal incidence,
Leff = (1 − e− αL )/α is the effective length, α is the linear absorption, L is
the sample thickness, x = z/z0 , z is the position of the sample with
respect to the beam waist, and z0 is the Rayleigh range. By taking the
highest and lowest transmittance, using Eq. (3), the relation TL/TH will
be equal to
/
TL √̅̅̅
= 1 − β(1 − R)I0 Leff 2 2 (4)
TH

and the TPA coefficient for wavelength λ can be found from the relation
( )/
√̅̅̅ 1 − TL
β(λ) = 2 2 (1 − R)I0 Leff (5)
Fig. 1. Linear optical absorption of Cd0.55Mn0.45Te. It can be observed that the TH
bandgap is equal to 2.054 eV
The values of TL and TH are plotted in Fig. 2 as a function of
in agreement with Eq. (2). Inset (a) Tauc Plots of the absorption with a direct
wavelength.
allowed transition.
CdMnTe is a zinc blende semimagnetic semiconductor, so to under­
stand the experimental results, we measured the emission spectra of the
incidence. We observed that at long wavelengths there is about 80%
sample after being illuminated with a strong 390 nm line coming from
transparency while at 690 nm, which is the smallest wavelength of our
doubling the 780 nm laser line in a BBO crystal. The 390 nm laser line
laser system, is close to 70%.
with an average power of 40 mW was focus with a 5 cm focal length lens
The semiconductor bandgap has been shown to have a linear de­
(a fluence on the order of 2.04 × 10− 4 J/cm2). The photoluminescence
pendency on the Mn concentration up to x < 0.771 and shows a bowing
signal was collected normal to the plane of the sample using a 3 cm focal
at small x < 0.1. In our case it is safe to use the linear approximation. The
length lens and send to a HR2000 Ocean Optics spectrometer with an
energy gap was also determined from Fig. 1 using a Tauc plot assuming
integration time of 9000 μsec. Fig. 3 shows the experimental results. We
that the main contribution to the absorption come from a direct-allowed observed a band center around 577.4 nm with and edge around the edge
transition, this is shown in insect (b) of Fig. 1 giving a value for the band-
of the bandgap of the system. This band is the Stokes shift band around
gap energy of 2.054 eV, which is in agreement with the phenomeno­ the 544 nm found in the absorption spectrum and is the 6A1→4T1 Mn2+
logical equation on Mn concentration of the system given by [19].
intra-ion transition [18]. Therefore, to explain the large measured value
Eg = 1.47 + 1.33x (2) for β, we propose the band structure shown in Fig. 4. Where the 577.4
nm band can be described as an intermediate band with a Γ8i symmetry
where x is the Mn2+ concentration of the sample. Using the value of 0.45 with J = 5/2, 7/2 … and a Γ6i symmetry with J = integer values [18].
in Eq. (2) the value of Eg is on the order of 2.068 eV, in excellent The calculation of the TPA absorption in a zinc blende semiconductor
agreement with the value found experimentally. has been performed in the past [21,22]. The difference between the two
The experimental setup used in the two-photon absorption mea­ approaches is in the number of bands taken into consideration. In
surement has been described elsewhere [13]. The tunable laser gener­ Braunstein [21] an additional band is introduced in the system as an
ates on average 75 fs pulses at 80 MHz. The light passes through a intermediate state that permits forbidden transitions to take place, while
continuous neutral density filter mounted on a computer-controlled in Van Stryland [22] a two-band model is used with opposite curvature
rotational stage in a closed-loop with a feedback mechanism to main­ where the only allowed-forbidden transition is permitted. Independent
tain the average power of the laser at the sample almost constant (in our
case at values ranging from 20 mW to 22 mW, within the experimental
error). This was accomplished using a circular continuous neutral den­
sity (NF) filter mounted in a Newport 8401 picomotor rotational stage
controlled in an open-loop by a Newport 8742 controller, the feedback
loop set the power of the laser before the sample between 20 and 22 mW.
After passing through the NF, the beam reaches the EFTL, focusing or
defocusing it at the sample plane. The light transmitted through the
sample is focused into the integrating sphere D1 by the lens L1 and
corresponds to the Nonlinear Absorption (NLA) open aperture archi­
tecture. The signal is sent to the lock-in amplifier set with a time con­
stant of 30 ms, each reading is recorded 40 times and averaged to reduce
the noise coming from the output of the laser intensity. The wavelength
of the laser is changed by the computer and the process is repeated until
it reaches the maximum wavelength of the oscillator (1040 nm). The
measurements were perform at room temperature (300 K) for all the
wavelengths.
The system records the values of the low and high-intensity points for
each wavelength of the laser at constant power [13]. The highest
transmittance TH is at z→∞ and the lowest transmittance TL is at z = 0. Fig. 2. High and low-intensity traces as a function of wavelengths for a 20 mW
average power across the spectrum.

2
N. Chalus et al. Optical Materials 109 (2020) 110343

contribution to the TPA for CdMn0.45Te0.55 comes from the f-f transition.
Fig. 5 shows the experimental results (blue triangles) and the best fit to
the data using Eq. (6) where the main contribution come from the f-f
transitions. It was pointed out in Ref. [23] that the f-f becomes relevant
as the energy ℏω approaches Eg. The experimental value for β is
extremely large with a value of 55 cm/GW at 690 nm. This value can be
compared to the value of CdTe of 26 at 1064 nm found previously [27],
unfortunately there is no other information available in the literature.
This makes CdMn0.45Te0.55 an excellent candidate for optical limiting
applications.
The thermal contribution to the TPA should be negligible (small
energy per pulse ≈ 0.25 nJ, and fluences on the order of 29.4 μJ/cm2).
To estimate the temperature increase of the sample at these fluences we
used the following expression [24].
Θ = Θmax N(r, Z, W) (7)

Where Θmax is the maximum temperature change in the sample and N(r,
Z, W) is a function of the beam profile radius r at the sample, Z = αz and
W = αw, here α is the absorption coefficient and w is the diameter of the
Fig. 3. Emission spectrum for CdMn0.45Te0.55 at 300 K using a femtosecond beam at the sample. The maximum temperature change happens at the
laser
surface of the sample and in the middle on the beam (z = 0, and r = 0) in
centered at 390 nm. There is a clear emission at 577.4 nm. The peak fit is to
this case the function N(0, 0, W) can be expressed as
guide the eye.
∫∞ ( )
1 1 W
of the symmetry of the valence band and the conduction band, there are N(0, 0, W) = 1 exp − λ2 dλ (8)
π 4 W+λ
three types of TPA transitions that can be classified as “allowed-allowed,
2
0

” “forbidden-allowed,” and “forbidden-forbidden” transitions. The

allowed transitions are those where the selection rules for the total and
angular momentum (ΔJ = 0, ±1) are observed. In general, the TPA P π2
1

coefficient can be written in the form of a sum as Θmax = (9)

2πKo w
( )12+i
( )i+1 2ℏω
K i Eg − 1 ( ) Where P is the average power of the laser, and Ko is the thermal con­
∑
2 Eg
2ℏω
β(ω) = ( ( ) )2 H − 1 ductivity of the sample. Using a value of 32 μm for w, a value of 0.1 cm− 1
( ) Eg for the absorption coefficient [25], and Ko = 1.836 W/m-K [26] we
i=0
4(2ℏω)3 ΔE + ααnc ++ααvv 2ℏω − Eg − ℏω
obtained a temperature increased on the order of 0.015 K, this contri­
(6) bution is extremely small and we are confident that the process is ul­
In the above equation, Ki can be used as a fitting parameter, i = 0, 1, 2 trafast and electronic in origin.
for a-a, a-f, and f-f transitions, respectively. Eg is the energy gap and ΔE is Time-resolved measurements were also performed on the sample in a
the energy between the valence band and the intermediated band. The standard pump-probe configuration using a Spectra physics Mai-Tai Ti:
α′ s are the inverse of the effective masses of the conduction band, Sapphire laser with a pulse duration of 75 fs centered around 780 nm.
valence band and the intermediate band, and H corresponds to the After passing through a beam splitter, one of the beam’s frequency
Heaviside step function. Assuming that the effective masses are all the doubles in a BBO crystal producing a 390 nm (3.17 eV) pump with an
same, and that ΔE ≈ Eg = 2.054 eV, it was found that the most important average power of 50 mW and is focused into the sample with a 7 cm focal
length lens. The pump pulse has an energy of 0.625 nJ/pulse, yielding a

Fig. 4. Energy band structure of Cd0.55Mn0.45Te at k = 0. SO (Split Off Band), HH (Heavy Hole), LH (Light Hole), CB (Conduction Band) and IB (Intermediate Band).
They are shown with the appropriated band Symmetry [19].

3
N. Chalus et al.
Fig. 5. (a) Two-photon absorption for CdMn0.45Te0.55. The blue triangles are
the experimental data, and the red line is the fit obtained using Eq. (6) with Eg
= 2.065 eV and K = 48726.5 such that β is given in units of cm/GW. The TPA
coefficient is largest at 690 nm on the order of 60 cm/GW. (For interpretation of
the references to colour in this figure legend, the reader is referred to the Web
version of this article.)
peak power density of 4.22 × 104 W/cm [2]. The probe beam was
focused at the sample with a 5 cm focal length lens giving a spot size
smaller than the pump. The results are shown in Fig. 6. It can be seen
that there are three relevant time scales. A short time scale of 0.3 ps
corresponding to the athermal regime and two relaxation times, one on
the order of 1.28 ps that can be identified as the coherent regime created
by a virtual excitation that corresponds to the Γ8i or Γ6i bands. After a
fast relaxation to the bottom of the CB, the electrons decay back to the
VB in a time scale on the order of 14.1 ps.
The decay process was modeled as a fast-rising exponential with a
double decay exponential function
[ ][ ] [3] A.E. Merad, M.B. Kanoun, G. Goumri-Said, Ab initio study of electronic structures
− ττ
(10)
− ττ τ
Iprobe (τ) = H(τ) 1 − e th e ph + e− τee
Where H is the Heaviside step function, τ is the delay time between
the pump and the probe, and τth = 0.3 ps, τph = 1.28 ps, and τee = 14.1
ps, respectively.
In conclusion we have determined the two-photon absorption coef­
ficient for CdMn0.45Te0.55 using a compact and fully automated system
and with a broad spectral range (690 nm–1040 nm) nonlinear absorp­
tion spectrometer. The giant value for the TPA coefficient on the order of
60 cm/GW at 690 nm can be explained based off a two-band model
where all the possible transitions were included. An additional band
must be introduced to the system to permit f-f transitions. The data was
fit to the theoretical model and it was found that the most important
contribution comes from the f-f transition. We also measured the time
response of this nonlinearity and found an extremely fast response on
the time scale of 14.1 ps.
Funding
Dr. H. Garcia thanks Southern Illinois University, Edwardsville
(SIUE), for financial support.
CRediT authorship contribution statement
Nathan Chalus: Experimental setup, Data curatio. Maxwell A.
Elmendorf: Experimental setup, Data curatio. H. Garcia: Experimental
setup, design, manuscript preparation, students, Supervision, Writing -
review & editing.
4
Optical Materials 109 (2020) 110343
Fig. 6. Pump-probe signal at 780 nm(probe)/390 nm(pump) it can be seen that
the system shows.
three relevant time scales, fast rise ~ 0.3 ps, a 1.28 ps initial decay and a 14.1
ps long decay process.
The autocorrelation of the pulse is shown in green with a pulse width ~
75 fs.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
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