Journal of ELECTRONIC MATERIALS, Vol. 46, No.

12, 2017
DOI: 10.1007/s11664-017-5742-z
 2017 The Minerals, Metals & Materials Society

Optical and Structural Properties of Zn2TiO4:Mn2+

L.P. SOSMAN,1,4,5 A. LÓPEZ,1 A.R. CAMARA,1 S.S. PEDRO,1

I.C.S. CARVALHO,2 and N. CELLA3

1.—Instituto de Fı́sica, Universidade do Estado do Rio de Janeiro, Rua São Francisco Xavier 524,
sala 3030-D, Maracanã, Rio de Janeiro, RJ CEP 20550-900, Brazil. 2.—Departamento de Fı́sica,
Pontifı́cia Universidade Católica do Rio de Janeiro, Rio de Janeiro, RJ 22453-900, Brazil.
3.—Instituto Politécnico, Universidade do Estado do Rio de Janeiro, P.O. Box 97282, Nova Friburgo,
RJ 28601-970, Brazil. 4.—e-mail: sosman@uerj.br. 5.—e-mail: lpsosman@gmail.com

Polycrystalline Zn2TiO4 samples with Mn2+ doping level of 0%, 0.1%, 1.0%,
and 5.0% have been produced by conventional solid-state method and their
optical and structural properties investigated. Rietveld refinement of x-ray
diffraction patterns revealed the formed phases and the crystallographic
parameters. The chemical composition was obtained by x-ray fluorescence
measurements. The optical properties were studied by photoluminescence,
excitation, reflectance, and photoacoustic spectroscopy. All measurements
were performed at room temperature. The photoluminescence spectrum of the
pure sample (0% Mn2+) showed a band in the red region associated with
Zn2TiO4, while the sample with 0.1% Mn2+ exhibited two bands, in the green
and red spectral regions, assigned to Mn2+ ions at tetrahedral and octahedral
sites. No emission was observed for the samples with 1.0% or 5.0% Mn2+. The
excitation results for the sample with 0.1% Mn2+ ions showed characteristic
peaks of Mn2+ transitions. Tanabe–Sugano theory was used to obtain the
crystal field Dq, B, and C Racah parameters from the energy peak positions in
the excitation spectrum of the sample with 0.1% Mn2+. Photoacoustic mea-
surements revealed a broad band, characteristic of semiconductor materials,
hiding the Mn2+ transitions.

Key words: Mn2+ photoluminescence, reflectance, photoacoustic absorption,

crystallographic data

INTRODUCTION
The functional material Zn2TiO4 has been inves-
tigated in recent years for several interesting
properties. Among all its applications, one can cite
its use as a thermoelectric material (where addition
of TiO2 increases the electrical conductivity of
ZnO),1 as a catalytic sorbent of contaminants for
environmental protection,2 as a gas sensor,3 and as
a dielectric material for microwave devices used in
communication.4 Various studies have been dedi-
cated to the photoluminescence of Zn2TiO4 doped
with transition metals and rare-earth ions, for
example, disordered Zn2TiO4, either undoped or
(Received April 3, 2017; accepted August 4, 2017;
published online August 29, 2017)
doped with V5+, Cr3+, and Sn4+. These systems show
broad bands from 500 nm to 800 nm, and the
intensity of the luminescence of the doped samples
is higher than the emission intensity of the undoped
samples, by 300% for V5+, 400% for Cr3+, and 800%
for Sn4+.5 Zn2TiO4:Tb3+ nanophosphor is a green
light-emitting material for use in white light-emit-
ting diodes (wLEDs), having an emission peak at
493 nm.6 Zn2TiO4:Eu3+ luminescence sensors show
a band from 600 nm to 650 nm with barycenter at
630 nm. This material is also considered useful for
wLEDs and display applications.7 Cu-doped
Zn2TiO4 shows a photoluminescence band with
peak at 386 nm.8
Host materials with tetrahedral and octahedral
sites are interesting because they allow doping with
several kinds of ion. Some ions usually occupy
tetrahedral sites (Co2+), while other ions are

6848
Optical and Structural Properties of Zn2TiO4:Mn2+
common at octahedral sites (Cr3+). On the other
hand, Mn2+ is an example of an ion which can be
found at both tetrahedral and octahedral sites.9–11
The energy position of the emission and absorption
bands will depend on the symmetry of the ion
neighborhood and can occur over wide wavelength
intervals. These facts motivate study of
Zn2TiO4:Mn2+, in which Zn2+ ions are located at
tetrahedral and octahedral sites. In this system,
Mn2+ ions can occupy Zn2+ sites, generating emis-
sion in different spectral regions.
EXPERIMENTAL PROCEDURES
Samples were obtained by traditional solid-state
reaction using ZnO, TiO2, and MnCO3 with high
purity (99.9%) as precursors. The quantities of the
oxides were calculated to obtain 2 g of stoichiomet-
ric Zn2TiO4 according to the equation
2ð1  xÞZnO þ TiO2 þ 2xMnCO3 ! Zn2ð1xÞ Mn2x TiO4
þ 2xCO2
ð1Þ
with x = 0, 0.001, 0.01, and 0.05, corresponding
respectively to 0%, 0.1%, 1.0%, and 5.0% of Mn2+,
that is, Zn2TiO4, Zn1.998Mn0.002TiO4, Zn1.98
Mn0.02TiO4, and Zn1.90Mn0.10TiO4, respectively.
The raw oxides were milled in an agate mortar to
obtain homogeneous and fine powder. Next, the
oxides were pressed into three disks, each with
12 mm diameter, 3 mm thickness, and mass of
0.67 g, which were placed in alumina crucibles for
heating at 1000C for 12 h. After this procedure, the
oven was turned off and the samples were cooled to
room temperature by thermal inertia.
CHARACTERIZATION
X-ray diffraction (XRD) data were obtained using
a PANalytical X’Pert PRO powder diffractometer at
40 kV and 40 mA using Cu Ka radiation (x-ray
wavelength 1.5418 Å). The data were refined by the
Rietveld method using the FullProf free package.12
An Artax 200 (30 kV, 200 lA, molybdenum anode)
was used to perform x-ray fluorescence (XRF)
measurements. Photoluminescence and excitation
measurements were performed using a Quan-
taMaster QM 300 system with a 75-W xenon lamp
at spectral resolution of 2 nm. Reflectance data
were obtained using an Ocean Optics visible–near
infrared (Vis–NIR) USB4000 spectrometer. Photoa-
coustic data were obtained using a 300-W Xe lamp
(Newport) and an Oriel 77200 monochromator with
spectral resolution of 2 nm to select the light
wavelength. The absorbing radiation was chopped
at 10 Hz using an Oriel model 75095. The detection
system was a B&K model 4943 microphone in a
homemade photoacoustic cell with quartz window,
and a Stanford Research Systems model SR830
lock-in amplifier to analyze the signal. All optical
6849
spectra were corrected for the response of the
detection system.
RESULTS AND DISCUSSION
Figure 1 shows photographs of the samples with
(a) 0%, (b) 0.1%, (c) 1.0%, and (d) 5.0% Mn2+ under
white light. The undoped sample (0% Mn2+) had
white color, while the color of the other samples
intensified greatly as the doping level was
increased, from light brown (0.1% sample) to deep
brown (5.0% sample).
The color is associated with the immediate neigh-
borhood of the impurity ion and its electronic
configuration, as well as the doping level in each
sample. In this case, the color is due to absorption
transitions of Mn2+ ions, which have d5 electronic
configuration.
Figure 2 shows the x-ray diffraction (XRD) pat-
terns for the samples with (a) 0%, (b) 0.1%, (c) 1.0%,
and (d) 5.0% Mn2+, as refined by the Rietveld
method using a pseudo-Voigt mathematical function
to fit the diffraction peaks.12 The measured Bragg
lines were identified using data files from the
International Centre for Diffraction Data (ICDD).13
The observed phases were cubic Zn2TiO4 (first set,
PDF 86-0156) and hexagonal ZnO (second set, PDF
80-0075). The difference between the simulated and
experimental patterns is the dotted baseline. The
results show the presence of almost pure Zn2TiO4
phase, with ZnO peaks of very low intensity. The
samples with 0%, 0.1%, and 1.0% Mn2+ contained a
small amount (<5.0%) of ZnO compound as residual
phase. The sample with 5.0% Mn2+ was single-
phase Zn2TiO4, without traces of ZnO. Similar
results with 1% to 3% unreacted ZnO were obtained
earlier.14,15 Table I presents the crystallographic
data, quality refinement parameters, and phase
composition of the samples.
The results in Table I show that the unit cell
volume did not change. According to Vegard’s law,16
the lattice parameter changes linearly when an ion
of different size substitutes a host ion. In the
Zn2(1x)Mn2xTiO4 sample, the ionic radii are: Zn2+
(rtet = 0.60 Å and roct = 0.74 Å), and Mn2+
(rtet = 0.66 Å and roct = 0.83 Å).17 Therefore, it is
expected that increasing the Mn2+ doping level will
lead to a linear increase of the lattice parameter of
Zn2(1x)Mn2xTiO4.
On the other hand, Jacob et al.18 argued that the
linearity predicted by Vegard’s law does not apply
for all solid solutions, being more appropriate for
solutions in which the difference in atomic radius
between the host and substitutional ions is less than
5.0%. As the ionic radius of Zn2+ ion is 12%
smaller than that of Mn2+, the dependence of the
lattice parameter on doping level is probably not
linear. In addition, Yoder-Short et al.19 affirmed
that Vegard’s law is more easily observed for ions in
tetrahedral coordination.
6850
Fig. 1. Photographs of samples with (a) 0%, (b) 0.1%, (c) 1.0%, and (d) 5.0% Mn2+.
Zn2TiO4 is an inverted spinel, with some Zn2+
ions occupying octahedral sites. If a majority of the
Mn2+ ions substitute for Zn2+ at octahedral sites, it
would be difficult to observe linear dependence of
the lattice parameter on doping level. In this case,
the dependence of the lattice parameter on the
doping level is unknown.
Changes in the lattice parameter (and thereby the
cell volume) are commonly observed in solid solu-
tions with high concentration of substitutional ions;
For example, in Mn1xZnxTiO3 (0.1 £ x £ 0.8),20 in
which Mn ions are substituted for Zn ones, the cell
parameter decreased linearly with increasing Zn
content from x = 0.1 to x = 0.8. In Ref. 19, the
authors also showed that the unit cell parameter
values of cubic Zn1xMnxSe with x = 0, 0.015, and
0.05 were 5.6675 Å, 5.6784 Å, and 5.6721 Å, respec-
tively. It was observed that the lattice parameter
increased from x = 0 to x = 0.015 but decreased from
x = 0.015 to x = 0.05, revealing a nonlinear depen-
dence of the lattice parameter on the doping ion
concentration. A similar effect was observed in
Zn2(1x)Mn2xTiO4, where for x = 0 and x = 0.05 the
lattice parameter value was 8.467 Å and 8.465 Å,
Sosman, López, Camara, Pedro, Carvalho, and Cella
respectively. These results indicate that it is possi-
ble that x-ray diffraction measurements of samples
with very low doping level, such as those studied in
this work, are not sufficient to identify small
changes in lattice parameter with high precision.
It is important to note that no Bragg lines for
Mn2TiO4 were identified in the x-ray diffractogram
(Fig. 2). Therefore, the quantity of Mn2TiO4 pro-
duced lies below the instrumental capability.
As seen from the XRD measurements, all samples
presented Zn2TiO4 as main phase, with small
quantities of unreacted ZnO. Zn2TiO4 has Zn ions
at two different sites, with tetrahedral and octahe-
dral symmetry. Due to the 2+ valence and similar
values of ionic radius, as mentioned in the previous
paragraph,17 replacement of Mn2+ ions at Zn2+ sites
is expected. Due to the small quantities of ZnO in
the samples, the probability of Mn2+ occupying Zn
sites in this phase is very low. Therefore, the data
analysis in this work considers the samples to be
single-phase Zn2TiO4 when considering the Mn2+
ion occupation.
Figure 3 shows the x-ray fluorescence data for the
samples with (a) 0%, (b) 0.1%, (c) 1.0%, and (d) 5.0%
Optical and Structural Properties of Zn2TiO4:Mn2+ 6851

Fig. 2. XRD data for samples with (a) 0%, (b) 0.1%, (c) 1.0%, and
(d) 5.0% Mn2+.

Mn2+. These measurements show that the samples

contained Zn and Ti (all samples), and Mn (doped
samples). These results indicate that the intensity
of the signal attributed to the Mn ion increased as
the sample color intensified. This fact is important
because it means that the color change does not
occur because of spurious impurities, but only due to
the change in the quantity of divalent Mn ions.
Figure 4 shows photoluminescence spectra for the
pure and 0.1% Mn2+-doped samples, obtained at
room temperature when excited at 350 nm and
chopped at 200 Hz. The spectrum of Zn2TiO4 with
0.1% Mn2+ (solid line) from 500 nm to 850 nm
exhibits two bands: a weak band at 532 nm (green
region) and an intense band with barycenter at
690 nm (red region). The shape and wavelength
position of the observed bands are similar to the
4
T1(4G) fi 6A1(6S) spin-forbidden transition of
Mn2+ ions observed elsewhere,11 in tetrahedral
and octahedral coordination, respectively. The full-
width at half-maximum (FWHM) of the red band is
equal to 0.17 eV (665 nm to 731 nm) for the 0.1%
Mn2+ sample. The pure sample exhibited an intense
band at 717 nm with FWHM of 0.20 eV (690 nm to
775 nm). A similar band, from 500 nm to 850 nm,
with barycenter at 720 nm and FWHM of 0.2 eV,
was observed by Markevich et al.,21 but those Fig. 3. x-Ray fluorescence data for samples with (a) 0%, (b) 0.1%,
authors did not explain the origin of the red (c) 1.0%, and (d) 5.0% Mn2+.
6852 Sosman, López, Camara, Pedro, Carvalho, and Cella

Table I. Crystallographic and Rietveld refinement parameters for samples

Mn2+ (%) 0 0.1 1.0 5.0

Observed phases
(a) Zn2TiO4 (%) 98.70 98.57 99.14 100
Space group 
Fd3m 
Fd3m 
Fd3m 
Fd3m
Crystal system Cubic Cubic Cubic Cubic
Database code ICSD 080851 080851 080851 080851
Unit cell parameters
a (Å) 8.467 (1) 8.467 (5) 8.466 (8) 8.465 (7)
V (Å3) 607.10 607.10 606.78 606.57
a, b, c () 90, 90, 90 90, 90, 90 90, 90, 90 90, 90, 90
(b) ZnO (%) 1.30 1.43 0.86
Space group P63mc P63mc P63mc
Crystal system Hexagonal Hexagonal Hexagonal
Database code ICSD 067849 067849 067849
Unit cell parameters
a = b (Å) 3.249 (3) 3.249 (3) 3.249 (3)
c (Å) 5.207 (3) 5.207 (3) 5.207 (3)
V (Å3) 47.61 47.61 47.61
a, b, c () 90, 90, 120 90, 90, 120 90, 90, 120
Half-width parameters
U 0.0042 (9) 0.0064 (8) 0.0046 (2) 0.0085 (6)
V 0.0081 (5) 0.0081 (7) 0.0081 (4) 0.0083 (9)
W 0.0085 (8) 0.0085 (1) 0.0089 (8) 0.0086 (1)
Agreement factors
Rwp 9.9 9.8 9.5 10.6
Rp 10.7 10.4 10.1 11.5
Rexp 7.13 7.06 6.99 7.31
v2 1.92 1.93 1.86 2.12
GOF 1.4 1.4 1.4 1.4
Goodness of fit, GOF = Rwp/Rexp.

Fig. 4. Room-temperature photoluminescence spectra of Zn2TiO4:

pure (black circles) and 0.1% Mn2+ (solid line).

emission of the Zn2TiO4 (pure) sample. One can

speculate that the red band is due to defects in the
host that originate in the Zn/Ti disorder.22 Further Fig. 5. Room-temperature excitation spectrum monitored at 690 nm
investigations are required to explain this point. for Zn2TiO4:Mn2+ (0.1%).
Optical and Structural Properties of Zn2TiO4:Mn2+
Fig. 6. Diffuse reflectance spectra of samples with (a) 0% (pure
sample), (b) 0.1%, (c) 1.0%, and (d) 5.0% Mn2+.
Figure 5 shows the excitation data at room tem-
perature for the sample with 0.1% Mn2+. The
spectrum was obtained by monitoring the emission
at 690 nm with light excitation chopped at 200 Hz.
The excitation signal of the band at 532 nm is not
shown because the weak signal leads to very low
signal-to-noise ratio.
The peak at 422 nm provides the strongest evi-
dence that the observed optical properties are due to
Mn2+ ions, because this transition is characteristic of
Mn2+ ion. This peak is attributed to the 6A1(6S) fi
4
A1,4E(4G) transition, and all other transitions are
identified after this first attribution. The remaining
peaks are assigned as follows: 6A1(6S) fi 4T1(4P)
(310 nm), 6A1(6S) fi 4E(4D) (345 nm), 6A1(6S) fi
4
T2(4D) (361 nm), 6A1(6S) fi 4T2(4G) (445 nm), and
6
A1(6S) fi 4T1(4G) (460 nm).23 The energy parame-
ters that describe the impurity–ligand system are
the strength of the crystalline field (Dq), and the
interelectronic Racah parameters B and C, which
characterize the covalent or ionic character of the
impurity–ligand bond.23–25 The energy parameters
Dq, B, and C were obtained using Eqs. 2, 3, and 4
and the energy positions of the peaks in the excita-
tion spectrum15:
6



A1 6 S !4 A1 ;4 E 4 G ¼ 10B þ 5C; ð2Þ
6



A1 6 S !4 E 4 D ¼ 17B þ 5C;



pigments.
6
A1 6 S !4 T2 4 G ¼ 10Dq þ 18B þ 6C 26B2 =10Dq :
The obtained values were Dq = 887 cm1,
B = 756 cm1, and C = 3227 cm1. The Dq value is
characteristic of Mn2+ at octahedral site. The Racah
parameters point to covalent character of the impu-
rity–anion bond. The ratio C/B = 4.3 lies in the
interval of 4.2 to 4.9 mentioned in literature.23–25
6853
Fig. 7. Photoacoustic measurements of Zn2TiO4 with (a) 0.1% and
(b) 5.0% Mn2+.
Figure 6 shows the diffuse reflectance spectra of
samples with (a) 0% (pure sample), (b) 0.1%, (c)
1.0%, and (d) 5.0% Mn2+. Figure 6a presents the
characteristic spectrum of pure Zn2TiO4, showing
the fundamental absorption edge at 400 nm. A
similar spectrum was observed earlier by Jang
et al.26 For the doped samples (b–d), the absorption
edge remained close to 400 nm, indicating that the
bandgap energy was not shifted significantly when
compared with the undoped sample. The reflectance
signal weakened as the Mn2+ concentration was
increased. This feature means that the absorption
intensity increased with increasing Mn2+ doping
level. The diffuse reflectance of the samples with
0.1%, 1.0%, and 5.0% Mn2+ was high in the interval
from 600 nm to 700 nm, being close to 90%, 80%,
and 45% of the reflectance intensity for the pure
sample, respectively. This is an important charac-
ð3Þ teristic of materials regarding their potential use as
Photoacoustic (PA) measurements of the samples
ð4Þ with (a) 0.1% and (b) 5.0% Mn2+ are shown in Fig. 7.
A broad absorption band from 320 nm to 700 nm
can be seen in the photoacoustic spectrum for these
samples. The same occurred for the 1.0% Mn2+
sample (not shown in this paper).
The spectrum for the 5.0% Mn2+ sample is more
intense than that of the 0.1% Mn2+ sample, as
expected due to its higher doping level. Generally,
PA measurements are performed on samples with
6854
high doping level, which present a more intense
signal. Consequently, it is possible to observe
energy structures in more detail, allowing identifi-
cation of weak transitions. Despite the expected
weak signal, the 0.1% Mn2+ sample was investi-
gated by PA spectroscopy because this was the only
sample, among those studied in this work, that
presented photoluminescence. The importance of
PA spectroscopy for emitting systems is due to the
fact that the PA spectrum shows bands from all
absorber centers present in the material. Therefore,
it is expected that the photoacoustic spectrum will
show a structure similar to that observed in the
excitation spectrum, including signals from
spurious optical centers present in the sample.
However, d–d transitions of Mn2+, which would be
similar to the peaks in Fig. 5, are not seen in Fig. 7,
which shows broad absorption bands characteristic
of semiconductor materials. Mayén-Hernández
et al.27 studied pure cubic phase of Zn2TiO4 by
photoacoustic spectroscopy, observing a band from
283 nm to 700 nm with an energy bandgap at
336 nm (3.7 eV) in the photoacoustic absorption
spectrum, a result similar to that shown in Fig. 7. In
a previous paper,28 Liang et al. showed an absorp-
tion band for Zn2TiO4 single crystal from 3.2 eV to
3.8 eV (387 nm to 326 nm). Figure 7 shows the
energy gap at 350 nm. The shift to higher wave-
length could be due to the Mn2+ doping. This shift
causes the peaks of the Mn2+ ions to be hidden by
the absorption band.
The hypothesis regarding the lack of d–d transi-
tions is that the strong absorption transitions of
bulk Zn2TiO4 overlapped with the Mn2+ transitions
and the observed absorption band is only due to the
Zn2TiO4 host. Moreover, comparing the photoacous-
tic absorption and luminescence spectra, one notes
that there is strong overlap between the absorption
and emission bands. Dexter et al.29,30 proposed that
such overlap of the emission and absorption bands
induces energy transfer via nonradiative processes.
Hence, energy transfer is expected among Mn2+ ions
for samples with higher doping level, in which the
impurities are closer, as well as from the Zn2TiO4
host to the Mn2+ ions and vice versa, via nonradia-
tive processes. In addition, the lack of luminescence
for the samples with 1.0% and 5.0% Mn2+ is
probably due to concentration effects (concentration
quenching) in the Zn2TiO4:Mn2+.
CONCLUSIONS
2+
Zn2TiO4:Mn was obtained by facile solid-state
reaction, forming almost pure Zn2TiO4 samples. The
emission band observed from 500 nm to 850 nm was
assigned to the spin-forbidden transitions of Mn2+
(d5 electronic configuration). The bandwidth indi-
cates that Zn2TiO4:Mn2+ is a potential candidate for
development of tunable light sources. Photoacoustic
and photoluminescence results showed that the
sample with 0.1% Mn2+ could be appropriate for
Sosman, López, Camara, Pedro, Carvalho, and Cella
use as a semiconductor material or radiation emit-
ting source. The Mn-doped samples were intensely
colored. The samples doped with 0.1% and 1.0%
presented high diffuse reflectance. These two
results make this system interesting for applica-
tions in the pigment industry.
ACKNOWLEDGEMENTS
The authors are grateful to Fundação Carlos Cha-
gas Filho de Amparo à Pesquisa do Estado do Rio de
Janeiro (FAPERJ), Coordenação de Aperfeiçoa-
mento de Pessoal de Nı́vel Superior (CAPES), and
Conselho Nacional de Desenvolvimento Cientı́fico e
Tecnológico (CNPq) for their financial support, to the
CBPF for XRD data, and to the LIETA/IFADT/UERJ
for XRF measurements. I.C.S.C. and L.P.S. thank
CNPq for Research Productivity fellowships.
CONFLICT OF INTEREST
The authors declare that there are no conflicts of
interest regarding the publication of this article.
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