Radiation Measurements 90 (2016) 47e50

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Radiation Measurements
journal homepage: www.elsevier.com/locate/radmeas

Luminescence spectroscopy of Eu3þ and Mn2þ ions in MgGa2O4 spinel

A. Luchechko*, O. Kravets, L. Kostyk, O. Tsvetkova
Ivan Franko National University of Lviv, Faculty of Electronics, Tarnavskogo str. 107, Lviv 79017, Ukraine

h i g h l i g h t s

 Host luminescence is presented by a broad band with a maximum at 430 nm and has a complex nature.
 Charge transfer bands from lattice to Mn2þ and Eu3þ ions were found around 260 and 280 nm, respectively.
 Activator luminescence intensity reaches the maximum at 4 mol.% of Eu3þ ions concentration.

a r t i c l e i n f o a b s t r a c t

Article history: Photoluminescence and excitation spectra of the spinel-type MgGa2O4 with 0.5 mol. % Mn2þ ions and
Received 23 October 2015 Eu3þ content from 0 to 8 mol. % have been investigated in this work at room temperature. Polycrystalline
Received in revised form samples were synthesized via high-temperature solid-state reaction method. Photoluminescence spectra
26 November 2015
of all samples exhibit host emission presented by a broad “blue” band peaking ~430 nm, which consists
Accepted 3 December 2015
of at least three elementary bands that correspond to different host defects. Excitation of the host
Available online 10 December 2015
luminescence showed the broad band with a maximum at 360 nm. Characteristic bands of d
ed transitions of Mn2þ ions and fef transitions of Eu3þ ions together with charge-transfer bands (CTB) of
Keywords:
Magnesium gallate MgGa2O4
these ions were also found on the excitation spectra. Mn2þ and Eu3þ co-doped samples emit in green and
Rare-earth ions Eu3þ red spectral regions. Mn2þ ions are responsible for the green emission band at 505 nm (4Т1/6А1
Transition metals Mn2þ transition). The studies of photoluminescence spectra of activated samples with different Eu3þ ions
Co-doping content show characteristic fef luminesecence of Eu3þ ions. The maximum of Eu3þ emission was found
Matrix luminescence at 618 nm (5D0/7F2) and optimal concentration of activator ions was around 4 mol. %.
Photoluminescence and excitation spectra © 2015 Elsevier Ltd. All rights reserved.

1. Introduction pure spinel compounds have the host luminescence in “blue”

MgGa2O4 and ZnGa2O4 spinels have attracted great attention of
researches due to their dielectric and optical properties, radiation
resistance and high temperature stability. Spinel crystals and ce-
ramics doped with rare-earth ions are promising materials in solid-
state laser, thin film electroluminescence displays (TFELD), field
emission displays (FED) and vacuum fluorescent displays (VFD) (Y.
Zhang et al., 2014). In particular, magnesium gallate doped with
Eu3þ ions has excellent luminescent properties in “red” and “or-
ange” spectral region (e.g. Ya. Li et al., 2009). Moreover, those spinel
compounds doped with transition metals could be used for fiber
optic thermometry (V. T. Gritsyna et al., 2006).
The prevailing number of researchers associate the matrix
luminescence with host defects, in particular, oxygen vacancies. All
spectral region. The presence of luminescence of lattice defects in
magnesium gallate spinel was reported in the research of (Zh. Lui
et al., 2009). A broad luminescence band peaking around 460 nm
has been found in these studies. The authors (S. S. Yi at al., 2002)
have studied the host luminescence of ZnGa2O4 films grown at
different oxygen pressure and obtained similar results. Also, here
were detected three overlapping emission bands at 420, 465 and
520 nm. Nevertheless, the mechanism of the “blue” host emission is
not established.
This paper reports about photoluminescence studies of
MgGa2O4 co-doped with Mn2þ ions and different content of Eu3þ
ions. Meanwhile, no phosphors with Eu3þ and Mn2þ co-doping
were reported. The emission mechanisms of samples synthesized
by solid state reaction method were also investigated.

2. Experimental details
* Corresponding author.
E-mail address: luchechko@electronics.lnu.edu.ua (A. Luchechko). Polycrystalline samples of MgGa2O4 with Eu3þ content from

http://dx.doi.org/10.1016/j.radmeas.2015.12.003
1350-4487/© 2015 Elsevier Ltd. All rights reserved.
48 A. Luchechko et al. / Radiation Measurements 90 (2016) 47e50

0 (nominal pure) to 8 mol. %, were prepared by high-temperature

solid state reaction method. Magnesium oxide (MgO), b-gallium
oxide (b-Ga2O3), europium (III) oxide (Eu2O3) and manganese oxide
(MnO) were used as the starting materials. All reagents were at
least 4N grade of purity. Powders of stoichiometric composition
with 0, 2, 4, 6, 8 mol. % of Eu2O3 and 0.05 mol.% of MnO were ground
in agate mortar for 6 h with further pressing in steel mold under the
pressure of 150 kg/cm2. Obtained tablets were annealed at 1473 K
for 8 h in air. These samples were 4 mm in diameter and 1 mm
thick.
XRD analysis were performed on STOE STADI P diffractometer
with linear position-sensitive PSD detector using X-ray tube with
Cu anode (Ka1-radiation, l ¼ 1.5406 Å). The sensitivity range of
detector is 5.5e7 2Q with a minimal step of 0.005 . Analysis of
diffraction peaks was realized with STOE WinXPOW software
package.
Photoluminescence measurements were carried out on spec-
trofluorometer CM2203 in 220e820 mn spectral range. All excita- Fig. 2. Photoluminescence excitation spectra of pure magnesium gallate sample
tion and luminescence spectra were obtained with a spectral monitored at 430 nm (black line) and 500 nm (red line). (For interpretation of the
references to colour in this figure legend, the reader is referred to the web version of
resolution of 1 nm. Excitation of luminescence was performed with
this article.)
150 W xenon lamp. A Hamamatsu R928 photomultiplier was used
as luminescence detector.

3. Results and discussions

X-ray diffraction measurements were performed on all investi-

gated samples. The XRD patterns were compared with standard
Powder diffraction data file ICSD data base No.37359. All investi-
gated samples are spinel type structure compound with Fd3m
space group (No. 227) with coordination number z ¼ 8. No addi-
tional phases were detected. The XRD pattern of MgGa2O4: 4 mol.%
Eu3þ, 0.05 mol.% Mn2þ samples is shown on Fig. 1. The average cell
parameter of MgGa2O4: 4 mol.% Eu3þ 0.05 mol.% Mn2þ samples was
determined: a ¼ 8,27333(8) Å.
Excitation spectra of pure magnesium gallate spinel monitored
at 430 nm (Fig. 2) shows a broad band peaking around 360 nm,
which is associated with excitation of defect levels of the matrix
inside the band-gap. In the spectral region 230e320 nm weak
excitation with two small maximums approximately at 260 and
280 nm is observed. The excitation spectra monitored at the long- Fig. 3. Photoluminescence excitation spectra of MgGa2O4: 4 mol.% Eu3þ, 0.05 mol.%
wavelength side of the host luminescence band (500 nm) shows a Mn2þ sample monitored at 430 nm (green line), 505 nm (red line) and 618 nm (blue
line). (For interpretation of the references to colour in this figure legend, the reader is
weak broad band in the spectral region 340e450 nm.
referred to the web version of this article.)
The excitation spectra of co-doped samples (Fig. 3) monitored at
430 show an additional band in near UV region peaking around

Fig. 1. XRD pattern of MgGa2O4: 4 mol.% Eu3þ, 0.05 mol.% Mn2þ samples.
 A. Luchechko et al. / Radiation Measurements 90 (2016) 47e50 49

260 nm and the broad band in the region 310e400 nm. The exci-
tation spectra registered at 505 nm show an intense broad band
around 260 nm that corresponds to charge transfer band from 2p
orbital of O2 ions to Mn2þ ions (Y. Zhang et al., 2014).
The excitation spectrum monitored at 618 nm shows a broad
asymmetrical band with a maximum around 280 nm which is
related to charge transfer band from O2 to Eu3þ ions (H. Liu et al.,
2013). This band consists of two overlapped sub-bands, which is
corresponded to energy transition to Eu3þ ions which substitute
Zn2þ at tetrahedral sites and Ga3þ at octahedral sites. Considering
the above, the higher energy emission band is attributed to Eu3þ at
tetrahedral sites and lower energy emission band to Eu3þ at octa-
hedral sites. But the excitation intensity of the second band prevails
over the excitation intensity of the Eu3þ ions at tetrahedral sites
band (J. S. Kim et al., 2007). The excitation bands at 324 nm
(7F0/5H4e6), 363 nm (7F0/5D4), 380 nm (7F0/5L7), 412 nm
(7F0/5D3), 466 nm (7F0/5D2) and at 393 nm (7F0/5L6) nm are
assigned to the fef transition within Eu3þ ions. The line at 393 nm is Fig. 5. Photoluminescence spectra of MgGa2O4: 4 mol.% Eu3þ, 0.05 mol.% Mn2þ sample
excited with 260 nm (black line), 278 nm (red line) and 393 nm (blue line). (For
the most intensive in the excitation spectra of MgGa2O4: Eu, Mn interpretation of the references to colour in this figure legend, the reader is referred to
samples. the web version of this article.)
The photoluminescence spectra of pure MgGa2O4 are shown on
Fig. 4. The luminescence of pure samples excited with 240 nm
wavelength, which is close to band-to-band absorption, shows a The luminescence of Mn2þ ions is presented by a broad intense
broad band from 350 to 600 nm with a maximum at about 430 nm. band at 505 nm (4Т1/6А1 transition). These transitions are very
A shoulder was observed around 400 nm, which can be explained sensitive to crystal field strength and symmetry of its position. In
by contribution of elementary bands related to different host de- this case, Mn2þ ion is located at tetrahedral sites with weak crystal
fects. The 350 nm excited luminescence shows asymmetrical band field. It results in very small splitting of this band (Y. Zhang et al.,
with a maximum shifted to 420 nm. The nature of the host lumi- 2014). The article (V. T. Gritsyna et al., 2006) reports that Mn2þ
nescence is complex and consists of at least three bands of different emission band in MgAl2O4 consists of two overlapping bands at
origins. The authors (V. T. Gritsyna et al., 2006) associate the host 2.39 eV (518 nm) and 2.33 eV (532 nm) of different widths 0.09 and
luminescence in the MgAl2O4 spinel single crystals with oxygen 0.15 eV, respectively.
vacancies and antisite defects. The authors of the (Zh. Lui et al., The luminescence of Eu3þ ions is presented by sharp peaks at
2009) paper define three bands peaking at 504, 466 and 415 nm 580 nm (5D0/7F0), 593 nm (5D0/7F1) and the most intense peak
in the broad host luminescence band. They also suggest the re- at 618 nm (5D0/7F2). The existence of 5D0e7F0 transition is an
lations of some of these bands with Mg2þ and Ga3þ vacancies levels indication of high asymmetry of Eu3þ ions in matrix. The low
close to valance band. However, the authors of the already symmetry also results in increasing of hyperfine structure of
5
mentioned paper (S. S. Yi et al., 2002) associate the host lumines- D0/7F1 band (Ya. Li et al., 2009). The intensity ratio of electric-
cence with emission of Ga3þ ions in GaeO groups. dipole 5D0/7F2 transition to magnetic-dipole 5D0/7F1 transition
The photoluminescence spectra of co-doped samples excited gives information about local asymmetry around Eu3þ ions (Wei-
with 260, 278 and 393 nm wavelengths are shown on Fig. 5. The min Guan et al., 2014). In our case, the 5D0/7F2 to 5D0/7F1 ratio
matrix luminescence with a maximum around 430 nm was is equal to 2.72 which confirms the distortion of the local sur-
observed at 260 and 278 nm wavelength excitation. The lumines- roundings around Eu3þ ions.
cence intensity decreases with excitation wavelength increasing. Fig. 6 exhibits the emission intensities of matrix (430 nm), as

Fig. 4. Photoluminescence spectra of pure magnesium gallate sample excited with Fig. 6. Luminescence intensity of MgGa2O4: Eu3þ, Mn2þ sample monitored at 430 nm
240 nm (black line) and 350 nm (red line) wavelengths. (For interpretation of the (black line), 505 nm (red line) and 618 nm (blue line) versus content of Eu3þ ions at
references to colour in this figure legend, the reader is referred to the web version of 260 nm excitation. (For interpretation of the references to colour in this figure legend,
this article.) the reader is referred to the web version of this article.)
50 A. Luchechko et al. / Radiation Measurements 90 (2016) 47e50
well as manganese (505 nm) and europium (618 nm) ions in the
MgGa2O4: Mn, Eu phosphor with various Eu3þ content at the
260 nm excitation. The behavior of these dependencies indicates
the complex process of energy transfer in magnesium gallate co-
doped with Eu3þ and Mn2þ ions. The luminescence intensity of
Eu3þ ions monitored at 618 nm increases with increasing of its
concentration and reaching maximum at about 4 mol.% of Eu3þ
ions. Further increasing of Eu3þ concentration results into
decreasing of the luminescence at 618 nm due to the concentration
quenching effect. The same dependence of the 618 nm emission of
the Eu3þ ions of its content was observed at the 393 nm excitation
wavelength corresponded to the 4f6 configuration in the Eu3þ ions.
Despite of the constant Mn2þ ions content in all samples the
emission intensity at 505 nm reaches maximum approximately at
5 mol.% of Eu3þ ions. At the same time, the blue emission band at
430 nm gradually decreases with increasing Eu3þ ions concentra-
tion. This indicates that energy transfer can occurs from the host
MgGa2O4 to activator Mn2þ ions. The further increasing of Eu3þ
content from 5 mol.% to 8 mol.% leads to the decreasing of the Mn2þ
emission at 505 nm. This can be explained by enhancing of prob-
able energy transfer between Mn2þ and Eu3þ activator ions caused
by shortening of distances between them.
4. Conclusions
All investigated MgGa2O4 samples have single phase samples
with a spinel type structure and Fd3m space group. Excitation band
of pure magnesium gallate spinel at around 360 nm is associated
with defect levels of the matrix inside the band-gap. The nature of
the host luminescence is complex and consists of at least of three
bands caused by oxygen vacancies and antisite defects. The lumi-
nescence of Mn2þ ions is exhibited by a complex broad intense
band at 505 nm. The excitation and luminescence spectra of Eu3þ
ions are presented by sharp peaks which correspond to the fef
transition in activator ions. The charge transfer bands from O2
anions to Mn2þ and Eu3þ ions were found at 260 and 278 nm in the
excitation spectra of MgGa2O4: Mn, Eu samples, respectively. The
maximum luminescence intensity around 618 nm was found at
Eu3þ ions content equal 4 mol.%. The emission intensity of Mn2þ
ions depends of Eu content and reaches maximum at 5 mol.% of
Eu3þ ions which is related with complex mechanisms of energy
transfer between host, Mn2þ and Eu3þ ions.
Acknowledgments
The authors are grateful to the organizing committee of LUM-
DETR 2015 international conference for financial support. The work
was partly supported by the NATO SfP Project NUKR.SFPP 984649.
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