Author’s Accepted Manuscript

On the excitation spectra of Cr3+/ Cr2+ and V3+ co-

doped ZnAl2S4 single crystals

S. Anghel, M.G. Brik, C.-G. Ma, K. Sushkevich,

L. Kulyuk

www.elsevier.com/locate/jlumin

PII: S0022-2313(15)00297-5
DOI: http://dx.doi.org/10.1016/j.jlumin.2015.05.050
Reference: LUMIN13381
To appear in: Journal of Luminescence
Received date: 2 April 2015
Revised date: 21 May 2015
Accepted date: 22 May 2015
Cite this article as: S. Anghel, M.G. Brik, C.-G. Ma, K. Sushkevich and L.
Kulyuk, On the excitation spectra of Cr3+/ Cr2+ and V3+ co-doped ZnAl2S4
single crystals, Journal of Luminescence,
http://dx.doi.org/10.1016/j.jlumin.2015.05.050
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 On the excitation spectra of Cr3+/ Cr2+ and V3+ co-doped ZnAl2S4 single
crystals
S. Anghel1,2,*, M.G. Brik3,4,5,6, C.-G. Ma3, K. Sushkevich7, and L. Kulyuk1
1
Institute of Applied Physics, Academiei Str. 5, Chișinău MD-2028, Republic of Moldova
2
Ruhr-Universität Bochum, Anorganische Chemie III, Universitätsstrasse 150, D-44801 Bochum, Germany
3
College of Sciences, Chongqing University of Posts and Telecommunications, Chongqing 400065, PRChina
4
Institute of Physics, University of Tartu, Ravila 14C, Tartu 50411, Estonia
5
Institute of Physics, Jan Dlugosz University, Armii Krajowej13/15, PL-42200 Czestochowa, Poland
6
Institute of Physics, Polish Academy of Sciences, al. otni w 32/46, 02-668 Warsaw, Poland
7
State University of Moldova, Mateevici Str. 60, Chișinău MD-2009, Republic of Moldova
* - corresponding author: anggell@gmail.com

ABSTRACT
The excitation spectra of the ZnAl2S4 spinel crystals codoped with chromium and vanadium are
investigated in order to explain some features of the Cr3+ ions optical spectra and the inconsistency of the
experimental absorption/emission bands position with the Tanabe-Sugano diagram, as well as the “missing”
band in the absorption spectrum of V3+ ion although this band should be present as it is due to a spin allowed
transition. The unusual high Racah parameters of the C/B ratio for Cr3+ ions have been induced to recalculate
the Tanabe-Sugano diagram for the d3 electron configuration and the ratio C/B=8 in order to use it for the
experimental results interpretation. The presence of Cr2+ ions in the low spin electron configurations in the
octahedral coordination was confirmed; the temperature dependence of the Cr2+ emission at about 1.9eV was
studied and the Huang-Rhys factors were estimated for different temperatures. Despite the fact that the V3+ C/B
ratio has a different value compared to the case of Cr3+ ions, the electron-phonon interaction is similar for both
ions, with the Huang-Rhys parameter equal to 10 in both cases. Further research into optimizing the ZnAl2S4:Cr,
V system to get an efficient enhancement of the vanadium emission on account on re-absorbing the chromium
emission is suggested.

Keywords: A. Sulfide Semiconductor; B. Spinel; C. Optical spectroscopy; D. Crystal field calculations; E.

Tanabe-Sugano diagram

I. INTRODUCTION

Synthetic α-ZnAl2S4 single crystals doped with various transition metal ions such as
Ti, Cr, Co or V have been the subject of investigations in our group in the past few years [1-
5] due to their potential applications as optically active media for tunable laser systems.
Unlike the crystals containing trivalent chromium, materials with other transition metal ions,
especially in other oxidation states, are not easy to deal with. It is well known that those ions
like Ti, V and Co exhibit a strong tendency to form mixed valence systems, which can be
simultaneously found even in the same crystal. Moreover, two possible cation sites (tetra- and
octahedral) co-existing in spinels make spectroscopic analysis for such systems ambiguous.
All above-mentioned problems are fully applicable to the title system. In particular,
energy levels of the Cr3+ ion, as derived from the excitation spectrum, are not consistent with
the Tanabe-Sugano diagram for the d3 ions in the octahedral coordination. Another issue is
related to a “missing” 3T1 (3F) -3T2(3F) band in the absorption spectrum of V3+ ions in

1
ZnAl2S4, although this band should be present due to a spin allowed transition. Moreover, the
V3+ emission at room temperature takes place namely from the 3T2(3F) excited level.
So, the main aims of the present paper were set as follows: i) assign all prominent
spectroscopic features of several dopant ions in ZnAl2S4 and elucidate existing deviations
from the corresponding Tanabe-Sugano diagrams; and ii) estimate the main parameters of the
electron-phonon coupling so as to use them to explain the temperature behavior of the
luminescence spectra.
The α-ZnAl2S4 single crystals were co-doped at the same time with Cr3+ and V3+ ions;
however their concentrations were kept as low as possible in order to exclude any reciprocal
influence on spectroscopic properties. As can be seen from what follows, such a goal has
been successfully achieved and the spectra of both impurities fully resolved. A surprising fact
was the monitoring of a new band in the emission spectrum of chromium ions, which – after
a careful analysis - was attributed to Cr2+ ions.
The structure of the paper is as follows: in Section II, we give the experimental and
theoretical background, and then proceed with analysis and interpretation of the optical
spectra of each considered impurity in ZnAl2S4 (Section III) before we sum up the results in
Section IV - Conclusions.

II. EXPERIMENTAL AND THEORETICAL PROCEDURES

The synthetic Cr and V co-doped ZnAl2S4 single crystals were grown by means of the
chemical vapor transport (CVT) method[6]. The raw materials Zn, Al, S, Cr and V were of
high purity (Sigma Aldrich – from 99.7% – to 99.999%). Iodine was used in the
concentration of cT =5 mg I2/cm3.as a CVT agent. The concentration of Cr and V atoms was
the same - 0.05% mole ratio. The evacuated sealed quartz ampoules with the initial material
were slowly heated up to the synthesis temperature of 1150oC. After that the ampoules with
the polycrystalline material were placed in a two-zone tube furnace. The crystallization
chamber temperature was set at around 750oC in the region of the crystals growth, according
to [6]. The ampoules were held inside the furnaces for a period of up to 21 days, after that
they were slowly cooled until room temperature.
The obtained single crystals were structurally characterized by the single crystal X-ray
diffraction (XRD) method. The stoichiometry of the bulky samples was confirmed by
similarities between the simulated and experimental XRD spectra. The XRD data were
obtained at room temperature using an Xcalibur E diffractometer.
The photoluminescence (PL) and excitation spectra of the photoluminescence (PLE)
spectra were registered using a standard set-up Flourolog. All spectra were corrected for the
characteristics of the experimental optical system. The temperature dependence experiments
were carried out using a cold finger close cycle cryostat.
In addition to the experimental studies of optical spectra of the obtained samples, we
performed crystal field calculations of the energy levels of Cr3+ ions in ZnAl2S4. The
obtained energy level schemes were compared to those of the experimental spectra, which
allowed for performing the assignment of the most prominent features in the spectra and
analyzing the crystal field effects on the optical spectra of impurities. Having noticed some

2
discrepancies between the experimental/calculated levels and the Tanabe-Sugano diagram for
the d3 electron configuration for the C/B=4.5 (this ratio of the Racah parameters C and B
does not hold true for ZnAl2S4:Cr3+), we re-plotted the Tanabe-Sugano diagram for the actual
C/B ratio for the considered system.

III. RESULTS AND DISCUSSIONS

The X-ray characterization (the obtained XRD pattern is not presented here for the
sake of brevity) confirmed that the grown crystals belong to the spinel type crystals [7-9], i.e.
α-ZnAl2S4 single crystals crystallize in a defect cubic spinel-type crystal structure with the
space group Fd3m (Oh7) and the lattice parameter a=10.00Å. Sulfur atoms form a face
centered cubic (dense-packed) sublattice with eight formula units per an elementary cell. The
first octant contains a Zn2+ ion in the center and has a tetrahedral coordination of S2- ions with
a full Td symmetry; the second octant has a six-fold octahedral coordination of the Al3+ ion
belonging to the Oh point group. ZnAl2S4 has 96 cation sites, with only 24 being occupied by
the cations, 8 of 64 A-sites are occupied by Zn2+ and 16 of 32 B-sites are occupied by Al3+.
The doping ions can replace either Zn2+ ions in a tetrahedral coordination or Al3+ ones in the
octahedral coordination giving rise to various combinations of different ions in different
oxidation states.
The emission spectra of V and Cr co-doped ZnAl2S4 single crystals at room
temperature are presented in Fig.1. The concentration of dopants was chosen intentionally
low in order to exclude any interaction between impurity ions. Indeed, as it could be seen
from Fig. 1, both the V3+ emission around 0.9eV and Cr3+ emission around 1.6eV have the
same spectral position and shape, as was previously reported for each of them separately, in
Refs. [10] and [4], respectively. However, there is an additional broad band centered at
1.9eV, which is due to the optical transitions of Cr2+ ions, as we prove below. In the next
subsections, we describe the optical properties of each impurity ion separately.
ZnAl2S4:Cr3+
We will start with the analysis of the Cr3+ emission. The spectroscopic properties of
ZnAl2S4:Cr3+ were studied in Ref. [10], which showed that the emission around 1.6eV is due
to the spin allowed 4T2g-4A2g transition of Cr3+ ions in the octahedral coordination. The
configurational coordination diagram (CCD) was constructed using the results of the
absorption and PL spectra at different temperatures and different excitation intensities. The
room temperature excitation spectra monitored at 1.59eV and 1.62eV are shown in Fig. 2, i.e.
exactly in the maxima of the emissions corresponding to the dipole electric and spin
forbidden transitions 2Eg – 4A2g and 2T1g – 4A2g of Cr3+ ions. There are two broad and not
very intense bands with the FWHM (full width at half maximum) approximately 0.15meV,
located at 1.97eV and 2.5eV, respectively.
A third band, more intense and much wider (the FWHM ~ 0.5eV), is located at around
3.3eV. A shoulder in the last one located at around 4eV indicates that there is another closely
located energy level which manifests itself in the absorption spectra.

3
 The first two bands have been also observed in the absorption spectra; they are due to
the spin allowed transitions from the ground state 4A2g to the 4T2g(4F) and 4T1g(4F) excited

ZnAl2S4: Cr, V
V3+ emission Cr3+/Cr2+ emission T- 300K
1.0
Intensity, arb. units

0.5

Cr3+ Cr2+

0.0
0.7 0.8 0.9 1.0 1.1 1.5 1.6 1.7 1.8 1.9 2.0 2.1 2.2 2.3
E., eV

Fig.1 (Color online) Room temperature emission spectra of Cr and V doped ZnAl 2S4 single crystals

levels of the Cr3+ ions in the octahedral coordination.

Their shape and location exactly correspond to their counterparts in the absorption
spectra recorded at low temperatures [10]. It is worth mentioning that we have also registered
the excitation spectra at low temperatures, but since they are not different from those
presented in Fig. 2, they are not shown for the sake of brevity. So far, the only difference with
the previously recorded absorption spectra [10] is that we could not identify the spin
forbidden transitions to the 2T2g excited level, neither at room nor at low temperatures.
However, this transition can be easily masked by a much broader and more intense spin
allowed 4A2g to the 4T2g(4F), 4T1g(4F) transitions. The third band in the excitation spectrum is
probably mostly due to the charge transfer spectra, caused by the fact that around 3eV the
fundamental absorption of the host material (whose band gap is 3.4eV) already starts. This
band has not been identified earlier in the absorption spectra, just because it is overlapping
with the fundamental absorption of the host material. Also, it is well known that the charge
transfer transitions are more intense, since the parity restrictions are completely lifted,
contrary to the intraconfigurational d-d transitions. The last band is probably due to the
transition to the 4T1g(4P) excited level, however, the exact position of this band is hard to
estimate from the excitation spectra even at low temperatures. We can make a rough
approximation of the location of this band, knowing that the energetic interval between the
4
T1(4F) and 4T1(4P) excited levels in an ideal octahedral crystal field is, according to the

4
 Charge transfer band (or band-to-band transition)
1,5
ZnAl2S4:Cr3+ Emission at 1.59eV
Emission at 1,62eV
T - 300K
Inten. arb. units

1,0
Emission levels

4
0,5 4
T2g(4F) T1g(4F) 4
T1g(4P)

2
Eg, 2T1g(2G) 2
T2g(2G)

0,0
1,5 2,0 2,5 3,0 3,5 4,0 4,5
eV

Fig.2 (Color online) Room temperature excitation spectra of the Cr 3+ emission in ZnAl2S4 and calculated
positions of the excited levels (blues verticals lines – spin-quartet states giving rise to spin-allowed transitions,
dark verticals lines – spin-doublet states corresponding to the spin-forbidden transitions)

Tanabe-Sugano theory,
2 2 1/2
(225B – 180BDq + 100Dq ) .
Knowing the Racah parameter B and the crystal field strength Dq, this energetic
interval can be easily calculated. The 4A2g–4T2g(4F) transition, i.e. the first absorption
(excitation band), gives directly the value of Dq = 1590cm-1. The Racah parameter B can be
also easily calculated from the Tanabe-Sugano matrices as B= (ν2-2ν1)(ν2-ν1)/(15ν2-27ν1),
where ν1, ν2 represent the energy maxima of the 4A2g → 4T2g(4F) and 4A2g → 4T1g(4F)
transitions, respectively. Then, the value of B=400cm-1 calculated using the above equation
gives the energy separation between the 4T1(4F) and 4T1(4P) excited levels, approximately
1.63eV or the 4T1(4P) level should be positioned at around 4.1eV, which is consistent with the
broad excitation band at around 4.0eV(see Fig.2). However, a more detailed inspection of the
Tanabe-Sugano diagram for the d3 electron configuration reveals some inconsistency between
the experimental positions of the transitions and those which can be derived from the
diagram. The Dq/B ratio for Cr3+ in ZnAl2S4 is around 4.0, then, knowing the E/B ratio for
each of the transitions, we can easily localized them on the Tanabe- Sugano diagram. For all
transitions the calculated experimental ratio perfectly fits the levels in the diagram, except for
the 4A2g → 2Eg (2G), 2T1g(2G) transitions, i.e. the emitting levels. As the crystalline filed does
not affect those excited levels and the electron phonon interaction is weak for these spin-
doublet states, these transitions should have a zero phonon line, which indeed can be seen in
the emission/absorption spectra at low temperatures [10]. The experimental E/B ratio of these
transitions to the 2Eg (2G), 2T1g(2G) excited levels is then around 32, whereas in the typical

5
Tanabe-Sugano diagram the E/B value for these levels is about 22. Such a big difference
between the experimental value and that deduced from the diagram could be tentatively
explained by different C/B ratios, which in our case is around 8, whereas the Tanabe-Sugano
diagrams were plotted for the ratio of 4.5 [11].
In the next sub-sections we shall confirm the suggested assignments and recalculate the
Tanabe-Sugano diagram for the d3 electron configurations taking into consideration the new
value for the C/B ratio estimated for Cr3+ ions in ZnAl2S4.
As the next step toward the analysis of the energy levels of Cr3+ in ZnAl2S4, we use the
crystal field theory. The energy levels of impurity ions with an unfilled d-shell (in our case,
Cr3+ ion with its 3d3 electron configuration) in a crystal field (CF) of an arbitrary symmetry
can be represented by the eigenvalues of the following CF Hamiltonian [12]:
p
H   B pk O pk , (1)
p  2, 4 k   p

where O pk are the linear combinations of the irreducible tensor operators acting on the
angular parts of the impurity ion wave functions (exact definition of the operators used in the
exchange charge model (ECM) can be found in Ref [12]), and B kp are the crystal field
parameters (CFPs), which can be calculated from the crystal structure data. The latter include
all the structural and geometrical information about the host lattice. The Hamiltonian (1) is
defined in the space spanned by all wave functions of the free ion LS terms (which arise due
to the Coulomb interaction between electrons of an impurity ion). In the ECM, the CFPs are
written as a sum of two terms [12]:

B kp  B kp,q  B kp,S , (2)

where the first term:

V pk  i ,  i 
B pk ,q   K pk e 2 r p
 qi , (3)
i Ri p 1

is the point charge contribution to the CFPs, which originates from the electrostatic
interaction between the central ion and the lattice ions denoted by index i with charges qi and
spherical coordinates, Ri , i ,  i (with the reference system centered at the impurity ion itself).
The averaged values r p , where r is the radial coordinate of the impurity ion unfilled shell
electrons, can be obtained either from literature or calculated numerically, using the radial
parts of the corresponding ion wave functions. The values of the numerical factors K kp ,  p (the
latter appears in Eq. (4) below), the expressions for the polynomials V pk and the definitions of
the operators O kp can all be found in Ref. [12] and thus are not shown here for the sake of
brevity. The second term of Eq. (2) is proportional to the overlap between the wave functions

6
of the central ion and ligands and thus includes all covalent effects. It can be calculated using
the following equation:

2 V p  i ,  i 
 
k
2(2 p  1)
B pk , S  K pk e 2  s     
2 2
G S ( s ) i G S ( ) i G
p  S ( ) i . (4)
5 i Ri

Table 1. The crystal field (in Stevens normalization) and Racah parameters (in cm–1) for Cr3+ in
ZnAl2S4. G is the dimensionless ECM parameter.
B pk , q B pk , S B pk
B20 -818.8 1951.0 1132.2
B40 -274.4 -2738.0 -3012.4
B43 7871.5 67873.3 75744.8
G (ECM parameter) 10.685
B 400
C 3236

Table 2. The calculated energy levels (in eV) of Cr3+ in ZnAl2S4 in comparison with
experimental data. The orbital doublet states are denoted with an asterisk.
Oh group irreps.
D3d group Observed
and LS parent Calc.
irreps. (this work)
term
4
A2g (4F) 4
A2g 0
2
Eg (2G) 2
Eg 1.588* 1.587
2 2 2 2 *
T1g ( G) Eg, A2g 1.620 , 1.641 1.623
4 4 4 4 *
T2g ( F) Eg, A1g 1.961 , 1.971 1.970
2
T2g (2G) 2
A1g, 2Eg 2.371, 2.426*
4
T1g (4F) 4
A2g, 4Eg 2.459, 2.524* 2.500
2 2 2
A1g ( G) A1g 3.366
2 2 2 2
T2g ( H) Eg, A1g 3.532*, 3.541

7
 2
T1g (2H) 2
A2g, 2Eg 3.545, 3.558*
4
2
Eg (2H) 2
Eg 3.727* T2g
90
2
T1g (2H) 2
A2g, 2Eg 3.909, 3.938*
4 80
T1g (4P) 4
Eg, 4A2g 4.105*, 4.197 ~4.10
with S (s), S ( ), S ( ) corresponding to the 70
4
overlap integrals between d-functions of 60 T1g
the central ion and p- and s-functions of 4
50 T2g
the ligands:

E/B
2
T2g
S (s)  d 0 s0 , S ( )  d 0 p0 , S ( )  d1 p1 40
The Gs , G , G entries are dimensionless 2 2
30 T1g, Eg
2
adjustable parameters of the model, whose G
values are determined from the positions 20
4
of the first three bands in the excitation P
10
spectrum. They can be approximated to a 4
4
single value, i.e. Gs  G  G  G , which F0 A2g
then can be estimated from one absorption 0 1 2 3 4 5
band only [12]. The main advantages of the Dq/B
ECM are the following: i) a small number
of fitting parameters; ii) an opportunity to
calculate the CFPs and energy levels of the impurity ions in crystals without invoking any
assumption about the impurity center symmetry, but by using only crystal structure data, and
iii) a possibility to treat the covalent effects quantitatively (via the calculations of the overlap
integrals). In the present work, the calculations of the crystal field parameters were performed
using a large cluster consisting of 29208 ions, which ensures a proper convergence of the
crystal lattice sums. The overlap integrals between Cr3+ and S2- ions were calculated using
the corresponding wave functions from Ref. [13]. Table 1 summarizes the calculated non-
zero CFPs values calculated in the system of reference, in which the third order rotation axes
coincides with the (-1,1,1) crystallographic direction. Such a choice of the system of
reference ensures full use of the D3d local symmetry of the Al position [14].

8
 A very unusual C/B ratio (around 8) Fig. 3 (Color online) Calculated Tanabe Sugano diagram
can be noticed in Table 1, a value far from (d3 ions) for a C/B=8 value. Only the level observed in
the absorption/excitation spectra are labeled.
the usual ratio of C/B=4.5 used for the
calculations of the Tanabe-Sugano
diagrams. The same C/B value has been obtained from the experimental spectra. In fact, this
is the reason why there is no concordance between the experimental positions of the 2Eg (2G)
and 2T1g (2G) excited levels and those extracted from the usual Tanabe-Sugano diagram (see
above). However, this high value of the C/B ratio is not as unusual as it seems to be at first
glance, the same ratio for the whole range of the trivalent 3d ions in the crystal field of the
III-V semiconductor GaAs, where the 3d ions replace the Ga ion in a perfect Td symmetry,
has a value practically constant and only slightly varying around 7.1[15]; a value not far from
what it was obtained in our case. Both GaAs and ZnAl2S4 are highly covalent systems, and
such a high reduction of the Racah parameters due to the nephelauxetic effect is explained by
a high degree of covalency of chemical bonds in these materials.
The calculated CFPs values from Table 1 were used to diagonalize the crystal field
Hamiltonian in the space spanned by the wave functions of all 8 LS terms of the 3d3 electron
configuration. The calculated energy levels are given in Table 2 and their positions have been
drawn, as the vertical lines, on the excitation spectrum (see Fig.2). Moreover, the Tanabe-
Sugano diagram for the C/B=8 ratio has been also constructed and is presented in Fig.3. For
the sake of simplicity, only those levels involved into the absorption/excitation and emission
transitions have been labeled in Fig. 3. As it can be seen from Table 2 and Figs.2-3, now
there is a perfect concordance between the calculated and experimental positions of the
excited levels; for the 2Eg (2G) and 2T1g (2G) levels whose experimental positions are located
at the value of Dq/B=4 and E/B=32; the same values can be easily deducted from theoretical
calculations and fit perfectly into the new Tanabe-Sugano diagram presented in Fig. 3. The
assumption that the position of the 4T1g (4P) excited level is located around 4.1eV is also
confirmed by theoretical calculations (in Fig. 3 it has the energy of about 84B, or 33600 cm-1
≈ 4.17eV).

ZnAl2S4:Cr2+

9
 To the best of our knowledge, the emission presented in Fig. 1 or Fig.4 as a broad
band situated around 1.9eV, is observed for the first time in this compound. Its presence is
quite unexpected because it was not previously detected in the ZnAl2S4:Cr3+ emission spectra.
Spectroscopic measurements at varying temperatures did not reveal any change in the
emission shape, although the “maximum” is shifted towards higher energies; in contrast to the
Cr3+ emission represented by narrow lines at low temperatures (see Fig.4). We suppose that it
originates from the electronic transitions between the energy levels of Cr2+ ions in the
octahedral coordination and the following arguments are presented in order to support our
assumption. Firstly the Cr2+ ion in the tetrahedral coordination can be easily excluded because

2,0
Cr3+ emission

1,5
Cr2+ emission

T - 7K
Emission

1,0

0,5

T - 300K
0,0
1,5 1,6 1,7 1,8 1,9 2,0 2,1 2,2 2,3
eV

Fig.4 (Color online) The visible part emission of the ZnAl2S4: Cr and V. The Cr3+ emission spectrum becomes
narrow at low temperatures whereas Cr2+ spectrum is still broad at this temperature, although the maximum is
shifted to higher energy.

the emission of the Cr2+ ions in the ZnS single crystals [16], where chromium ions are only in
the tetrahedral coordination of sulfide ions, is in the near – infrared at around 2μm. A
tetrahedral coordination is very unusual for Cr3+ ions, it is never met in inorganic compounds
and can be formed only in the molecular complexes, where Cr3+ ions can be found in a
distorted tetrahedral coordination[17]. The Cr4+ emission has been studied in chromium
doped forsterite [18], where chromium ions replace Si at the tetrahedral sites. The emission is
located in the NIR around 1.1μm (1.12eV), which is far

10
 1.2
T - 7K

1.0
Excitation

0.8

0.6

3
0.4 T1g to 3T2g(3H),3Eg(3H),3A1g(3G),3A2g(3G)

0.2 T - 300K

0.0

2.0 2.5 3.0 3.5 4.0 4.5

E, eV

Fig.5 (Color online) PLE spectra of Cr2+ emission in ZnAl2S4. The room temperature excitation spectrum was
monitored at 1.9eV emission and the low temperature excitation spectrum was monitored at 2.1eV emission.
The highlighted area represents the transition from the ground state 3T1g(3F) to the four close laying 3T2g(3H),
3
Eg(3H), 3A1g(3G) and 3A2g(3G) exited levels. Due to a different electron-phonon interaction the mentioned part
of the excitation spectrum is still a broad band even at low temperatures.

from the emission presented in Fig.3. Moreover, since the distance between Cr4+ and S2- ions
in ZnAl2S4 is longer than between Cr4+ and O2- ions in forsterite, it can be anticipated that
emission of Cr4+ ions in the sulfide tetrahedral coordination should be located at lower
energies (due to a weakened crystal field). This is not consistent with the emission energy in
ZnAl2S4 (1.9eV). The situation is similar in Y2SiO5:Cr4+ [19] where the tetravalent chromium
substitutes for Si4+ in this crystal, and there is no evidence of the presence of chromium in any
other valence state. Consequently, this oxidation state in the tetrahedral coordination in our
crystals is also excluded. In the octahedral coordination, Cr4+ ions can also exist, as well the
Cr2+ oxidation state, however a short inspection of the emission (Fig.4) and excitation
spectrum (Fig.5) allows us to discriminate between these two oxidation states. First of all,
since the Cr4+ ion has a 3d2 electronic configuration, it is expected that the temperature
behavior of its emission follows the same trend as in the case of Cr3+ ions, i.e. broad bands at
high temperatures and narrow emission lines at low temperatures (electric-dipole and spin
forbidden transitions from the 1Eg, 1T2g excited states to the 3T1g ground state), as the 1Eg, 1T2g
levels are first excited states (3d2 Tanabe-Sugano diagram).
However, that is not the case, the emission spectrum centered at 1.9eV is also a broad
band even at low temperatures (Fig.4), although its emission maximum is shifted, which
indicates a strong electron-phonon coupling in the first excited state. Secondly, if such an

11
oxidation state could have be present, then in the absorption/excitation spectra, at least, two
distinct spin allow transitions from the ground level 3T1g(3F) to the 3T2g(3F) and 3T1g(3P)
excited levels should be seen, as this was the case of Cr3+ excitation spectrum (see the
previous part). Although in the excitation spectra in Fig. 4 there are two broad bands located
at 2.65eV and 3.1eV, it is hard to assign them to the previously mentioned transitions as their
locations and the energy barrier between them should be different. Moreover, the band
centered at 3.1eV is very close to the fundamental band of the host, which means that it could
originate from a charge transfer transition.
Taking into consideration the above mentioned arguments we think that the emission
at 1.9eV and the corresponding excitation spectra are due to the intra-configurational Cr2+
transitions in an octahedral environment. Such an assumption is confirmed by the comparison
of these spectra with the Tanabe-Sugano diagram for the 3d4 electronic configuration. Under
certain conditions (depending on the crystalline field intensity) the total electronic
configuration could be in a low spin state, which in turns change completely the ground state
and the levels involved into the spin allowed transitions. In our case, the intensity of the
crystalline field and Racah parameter B was calculated in the previous section to yield the
Dq/B ratio around 4.0. It should be mentioned here that the magnitude of the Racah parameter
B goes downs with decreasing charge of an ion (by about 10-15 % in the case of Cr2+ ion if
compared to the Cr3+) [15]. Taking into account that the transition from the high spin (weak
CF) to the low spin (strong CF) configurations for the d4 ions is realized at the value of the
Dq/B ratio about 2.5 [8], it is clear that in our compound Cr2+ ions have a low spin electronic
configuration. The only spin allowed transitions, in this case, are from the ground state
3
T1g(3F) to the 3T2g(3H), 3Eg(3H), 3A1g(3G) and 3A2g(3G) exited levels. Although the excited
states, laying close to each other, have the same or almost the same electron-phonon
interaction (they are all nearly parallel to each other in the corresponding Tanabe-Sugano
diagram), the intensity of the electron–phonon interaction in the ground state is different.
Therefore, the transitions between these states always appear as a broad band regardless of
temperature, as Figs. 4-5 show.
Now we will discuss the emission spectra (Fig. 4) and try to figure out why the Stokes
shift is smaller at low temperature compared to that at room temperature (this is manifested
by the shift of the emission maximum from 2.1eV (7K) to 1.9eV (300K). Such situation is
quite unusual. However, it can be explained by thoroughly considering the energy level
sequence in the Tanabe-Sugano diagram for the 3d4 electronic configuration. Below the group
of four levels the transition to which are spin allowed, there is another excited level, namely
1
A1g(1I), which also has a different electron-phonon interaction in comparison with the ground
state, but much weaker compared to that for above mentioned levels.

12
 This means that in the single
3
A2 configurational coordinate diagram (SCCD)
40 3
A
3
1
(Fig. 6) the minimum of the 1A1g(1I) excited
T2
3
E state is less shifted from the minimum of
30 1
A
the ground state compared to those minima
of the 3T2g(3H), 3Eg(3H), 3A1g(3G) and
1

3
5
T
A2g(3G) excited states.
E/B

Low spin 2
20 Between these groups of levels there
1
E is a potential barrier (~20meV, estimated
1
T2 from the temperature dependence of the
10
5
emission spectra), which at low
High spin E
temperatures, is sufficiently high for the
3
T1 emission to take place from the minimum of
0
0 1
Dq/B
2 3 4 the 1A1g(1I) excited level and for the
Fig.6 (Color online) Tanabe-Sugano diagram for the d4 prevention of the redistribution of the
configuration in octahedral crystal field of ZnAl2S4. electron population in favor of the laying
The calculations were done for a C/B=8 ratio. higher excited levels. At high temperatures
this barrier is overcome by the electrons so
that the emission takes place from the minima of the 3T2g(3H), 3Eg(3H), 3A1g(3G) and 3A2g(3G)
exited levels; but because these levels interact stronger with the crystal environment (they are
steeper in the Tanabe-Sugano diagram for the 3d4 configuration Fig. 7), the Stokes shift is
greater compared to the low temperatures emission.
The Huang-Rhys coupling parameter
3
S also confirms the above supposition; 1
A1g(1I) T2g(3H)

taking into account that the phonon energy 3

in ZnAl2S4 is 39meV [1], and knowing the
experimental positions of the emission and ~ 20 meV
em= 1,9eV, T-300K, -s

absorption/excitation peaks maxima, we can 2

em= 2,1eV, T-7K, -ms
E, eV

abs= 2,65eV

easily calculate its value -

(2S-1)ћΩ = Ea-Eem. The obtained
estimations are S=7 for low temperature 1

emission and S=10 for high temperature.

Moreover, the decay times (not presented
here) are also different: in the range of
milliseconds for the low temperature
emission (which is in a typical value for the
spin-forbidden transitions)
microseconds at high temperature, that is a
Cr2+ - Ground state
0 3
T1g(3H)
Fig.7 (Color online) The single configuration
coordinate diagram for Cr2+ in ZnAl2S4. For the
and simplicity of the figure the 3Eg(3H), 3A1g(3G) and
3 3
A2g(3G) excited levels laying higher than T2g( H)
3

typical range for the spin allowed but are not presented.
electric dipole forbidden transitions.
If we assume that Cr2+ ions replace Al3+ ions, then there should be the charge
compensation in order to maintain the electrical neutrality of the whole system. This
compensation is easily achieved in crystals with a defect cubic spinel-type crystal structure.

13
 ZnAl2S4:V3+
The spectroscopic properties of the ZnAl2S4:V3+ single crystals were investigated by
our group in Ref. [4] and the theoretical calculation on the V3+ level location within the band
gap of the host material was carried out in [3]. Although the reader can find a more detailed
description in the above mentioned references, we will present here a short summary of those
two publications in order to emphasize what we want do describe further. Single crystals of
ZnAl2S4:V3+ exhibit a strong (for an electric dipole forbidden transition) near-infrared
emission centered at 1400nm (~0.9eV), having an unusually large Stokes shift relative to the
8
ex= 560 nm

Integral PL intensity
6
140
20 K 4
120 75 K
Intensity, arbitrary units

150 K
100 300 K 2
1/T

80 0,00 0,02 0,04 0,06 0,08 0,10

EPL2a EPL2b

60
EPL1
40

20 EPL3
E, eV

0,75 0,80 0,85 0,90 0,95 1,00 1,05 1,10 1,15 1,20

Fig.8 (Color online) The PL spectra of the V3+ emission in ZnAl2S4[4]. The intensity at room temperature is
increased by a factor of four compared to low temperatures (see the Inset). The EPL3 component is due to the
transition between the excited levels, an unusual characteristic for transition metals. The E PL2 and EPL1
components of the emission are due to the 3T2g(3F) to 3T1g(3P) and 1T2g(1D), 1Eg(1D) to 3T1g(3P) transitions,
respectively.

first observed/monitored absorption band (whose intensity increases by a factor of four going
from low to room temperatures, see Fig. 8). The V3+ emission of the ZnAl2S4:V, Cr single
crystals is exactly the same as in case of ZnAl2S4:V materials, i.e. no reciprocal influence of
the Cr and V ions on their spectroscopic properties was monitored. All bands observed in the
absorption and emission spectra were identified and labeled corresponding to the Tanabe-
Sugano diagram transitions for the d2 electron configuration in an octahedral crystal field.
One interesting feature of vanadium ions in this crystal is that some peaks in the emission
spectrum are due to the transitions between different excited levels (denoted as the PL1 in
Fig.8), which is more typical for the lanthanides rather than for the transition metals ions. At
room temperature the emission is due to the 3T2g(3F) to 3T1g(3F) spin allowed transition,

14
which explains the higher intensity compared to low temperature, when the emission is
mainly due to the 1T2g(1D), 1Eg(1D) to 3Tg(3F) transitions.
3+
1 1 1 1 1 1 1 1 ZnAl2S4:V
E, T2( D) A1( G) T2, T1( G)

1,6

3 3
1,4 T1( P)
1,0
3 3 3 3
1,2 T2( F) A2( F)
Optical density

Intesnity, arb. units

1,0

0,8
0,5
0,6 Excitation

0,4

0,2
Absorption
0,0 0,0
1,0 1,5 2,0 2,5 3,0 3,5
Energy,eV

Fig.9 (Color online) The PLE and absorption spectra for comparison of the V 3+ ions in ZnAl2S4. The 3T2g(3F)
energy level is well visible in the excitation spectrum compared to the absorption one. The transition to the
3
T1g(3P) excited level is the predominant band in the PLE spectrum. Except for the first band in the PLE there is a
perfect coincidence between this one and the absorption spectrum. The vertical bars represent the calculated
levels of V3+ in ZnAl2S4[3].

The only issue in all these spectra and related interpretations was the failure to
monitor the absorption band associated with the 3T2g(3F) excited level.
These band should have a predominant character in the spectrum as it is the case of
the others two spin allowed transitions 3T1g(3F) to 3T1g(3P) and 3A2g(3F), which are observed
in the absorption spectrum. All attempts of the authors to reveal this band failed and a
possible explanation was given in terms of phonon-assisted tunneling mixing of the 3T2g(3F)
vibronic wave function with that of the 1T2g(1D), 1Eg(1D) lowest state, resulting in a
“partially” spin forbidden 3Tg(3F) to 3T2g(3F) transition. It is well known that the PLE spectra
are much more sensitive compared to the absorption spectra, as can be easily seen from Fig.
9, where we successfully have been able to monitor the “missing” band in the absorption
spectrum. Indeed, around 1.5eV there is a prominent band with a complicated structure that
can be explained by the presence of several sublevels in each of the initial and final triplet
states split by the CF). Compared to the absorption spectra there is an obvious difference in
the intensity of this band related to the other two spin allowed transition; the intensity is now
of the same order as for the latter two. Also, it is worth nothing that the band around 2.2eV,
due to the 3T1g(3F) to 3T1g(3P) transition, is dominant in the spectrum, and on one of its

15
shoulders(around 2.6-2.7eV) the spin forbidden transitions from the ground state to the 1T2g,
1
T1 g(1G) excited levels could be easily observed. The calculated energetic positions of the
V3+ ions have been also drawn in Fig. 9 to show the agreement between the experiment and
theory.
Another interesting point is that although the V3+ ions replace the Al3+ ions in an
octahedral coordination as Cr3+ ions do, the C/B ratio for the former one is in the “normal”
range, i.e. has a value of 4.65, which is pretty close to that used for calculating the Tanabe-
Sugano diagrams. So, in this case it was not necessary to re-calculate and re-plot the above
mentioned diagram in order to use it for the interpretation. The difference between the C/B
ratio of V3+ and Cr3+ ions could be searched in the surplus of one electron for the latter in its
electronic configuration, which would lead to a stronger electrostatic repulsion compared to
that with V3+. Despite the fact that the C/B ratio for V3+ ions is different from that for Cr3+
ions, the Huang-Rhys coupling parameter S at room temperature has the same value as for
Cr3+ ions. This indicates that the strength of the electron-phonon interaction is similar in both
cases.

IV. CONCLUSIONS

The analyses of the excitation spectra of Cr3+ and V3+ ions in the ZnAl2S4 matrix have
confirmed and completed the available information from previous research papers on this
compound. The concentration of both ions was chosen in such a way that it did not affect the
spectroscopic properties of each other.
In the case of Cr3+, the experimental data indicate a strong electron-phonon interaction
and the C/B ratio of about 8, which is unusual for the transition metal ions. This made us re-
plot the Tanabe-Sugano diagram for the d3 configuration and C/B=8. This newly plotted
diagram allowed us to interpret the experimental data which are now in good agreement with
the experimental ones, thus allowing us to finish with the spectroscopic investigations of Cr3+
ions in this type of matrix. Such a strong decrease of the Racah parameter B is associated
with a high covalency in ZnAl2S4.
Spectroscopic analysis of the excitation spectra of vanadium ions clarified the
problem with the “missing” spin allowed transition 3T1g(3F) to 3T2g(3F) in the absorption
spectrum; this band was clearly monitored in the excitation spectrum. Despite the fact that the
C/B ratio has a different value for V3+ compared to the case of Cr3+ ions, the electron-phonon
interaction is similar for both ions, i.e. the Huang-Rhys parameter is equal to 10 in both cases.
The unexpected emission spectrum at around 1.9eV was attributed to the Cr2+
emission in an octahedral coordination; the arguments proving such an assignment have been
given in this paper. The emission and excitation spectra allowed finding out that Cr2+ ions
have a low spin electronic configuration.
After having obtained the completed picture of the spectroscopic properties of Cr3+,
Cr2+and V3+ in ZnAl2S4, we can set future directions of research in this system using the
available information. One tentative direction will be to have the energy transfer from
chromium to vanadium ions (by re-absorbing Cr emission by V ions), thus enhancing the
vanadium emission. At first glance, this should be possible as the emission of Cr3+ ions is

16
almost in the same spectral range as the first spin allowed transition in the V3+absorption. The
concentration of both impurities should be optimized to achieve this goal. So, intensive
experiments are needed to optimize the characteristics and parameters of the ZnAl2S4:Cr,V
system, which will be the subject for our further studies.

ACKNOWLEDGMENT

We would like to thank Dr. Olga Iliasenco for the technical assistance. M.G. Brik
appreciates support from the Ministry of Education and Research of Estonia, Project
PUT430, and the Program for the Foreign Experts offered by Chongqing University of Posts
and Telecommunications.

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[12] B.Z. Malkin, A.A.Kaplyanski, B.M. Macfarlane, in: Spectroscopy of solids containing rare-earth ions,
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Figure Caption
Fig.1 (Color online) Room temperature emission spectra of Cr and V doped ZnAl 2S4 single crystals

Fig.2 (Color online) Room temperature excitation spectra of the Cr3+ emission in ZnAl2S4 and calculated
positions of the excited levels (blues verticals lines – spin-quartet states giving rise to spin-allowed transitions,
dark verticals lines – spin-doublet states corresponding to the spin-forbidden transitions)

Fig. 3 (Color online) Calculated Tanabe Sugano diagram (d 3 ions) for a C/B=8 value. Only the level observed in
the absorption/excitation spectra are labeled.

Fig.4 (Color online) The visible part emission of the ZnAl 2S4: Cr and V. The Cr3+ emission spectrum becomes
narrow at low temperatures whereas Cr2+ spectrum is still broad at this temperature, although the maximum is
shifted to higher energy.

Fig.5 (Color online) PLE spectra of Cr2+ emission in ZnAl2S4[4]. The room temperature excitation spectrum was
monitored at 1.9eV emission and the low temperature excitation spectrum was monitored at 2.1eV emission.
The highlighted area represents the transition from the ground state 3T1g(3F) to the four close laying 3T2g(3H),
3
Eg(3H), 3A1g(3G) and 3A2g(3G) exited levels. Due to a different electron-phonon interaction the mentioned part
of the excitation spectrum is still a broad band even at low temperatures.

18
Fig.6 (Color online) Tanabe-Sugano diagram for the d4 configuration in octahedral crystal field of ZnAl2S4. The
calculations were done for a C/B=8 ratio.

Fig.7 (Color online) The single configuration coordinate diagram for Cr 2+ in ZnAl2S4. For the simplicity of the
3
figure the 3Eg(3H), 3A1g(3G) and 3A2g(3G) excited levels laying higher than T2g(3H) are not presented.

Fig.8 (Color online) The PL spectra of the V3+ emission in ZnAl2S4. The intensity at room temperature is
increased by a factor of four compared to low temperatures (see the Inset). The E PL3 component is due to the
transition between the excited levels, an unusual characteristic for transition metals. The E PL2 and EPL1
components of the emission are due to the 3T2g(3F) to 3T1g(3P) and 1T2g(1D), 1Eg(1D) to 3T1g(3P) transitions,
respectively.

Fig.9 (Color online) The PLE and absorption spectra for comparison of the V3+ ions in ZnAl2S4. The 3T2g(3F)
energy level is well visible in the excitation spectrum compared to the absorption one. The transition to the
3
T1g(3P) excited level is the predominant band in the PLE spectrum. Except for the first band in the PLE there is
a perfect coincidence between this one and the absorption spectrum. The vertical bars represent the calculated
levels of V3+ in ZnAl2S4[3].

highlights

The spectroscopic properties of Cr and V codoped α-ZnAI2S4 have been investigated.

The crystal field calculations have been performed.

The Huang-Rhys factors have been estimated for different temperatures.

The theoretical calculations have been correlated with the excitation spectra.

19