Journal of Advanced Ceramics

2015, 4(4): 267–271 ISSN 2226-4108

DOI: 10.1007/s40145-015-0160-2 CN 10-1154/TQ
Research Article 

Structural and photoluminescent properties of the MgGa2O4:Co2+ 
ceramic compound revisited after two decades 
S. S. PEDRO*, M. A. F. M. DA SILVA, A. LÓPEZ, L. P. SOSMAN
Instituto de Física, Universidade do Estado do Rio de Janeiro, RJ 20550-900, Brazil

Received: February 27, 2015; Revised: May 11, 2015; Accepted: June 12, 2015
© The Author(s) 2015. This article is published with open access at Springerlink.com

Abstract: In this work, we revisit and show how the structural and photoluminescent properties of the
MgGa2O4 ceramic compound have been kept unchanged for more than two decades. The obtained
results confirm the high quality, radiative efficiency, and chemical stability of this ceramic, proving that
the material is a strong candidate to be used in optical device applications with relatively long useful
life.
Keywords: ceramic compound; cobalt; solid-state reaction; photoluminescence

1    Introduction  optical systems doped with transition metals [3,4,9].

Cobalt is one of the transition metals exhibiting
The study of materials with luminescent properties has luminescent properties when inserted in ceramic hosts.
been active for several decades, and in the last few years, Particularly, the cobalt ion is found in several oxidation
the research in this area has been focused on the states (+2, +3, and +4) and in distinct crystal
development of new systems with optimized optical environments, but the divalent state is well known by its
properties. The research is intensified for materials that, capacity to generate luminescence in the visible and
beyond presenting remarkable luminescent properties, infrared regions [10–12]. From the point of view of the
also present features satisfying certain market energy level structure, the divalent ion d7 in tetrahedral
requirements, such as long life usefulness and radiative coordination presents a level splitting similar to the d3
efficiency. This causes a direct impact on the production ion’s level splitting in octahedral coordination, where
cost, with raw material economy resulting in optimized the ground level is the 4A2(4F) and the first excited
financial costs, also being environmentally friendly. energy levels are 4T2(4F), 4T1(4F), and 4T1(4P) for small
Transition metals and rare earth doped materials exhibit values of Dq/B [9]. In the absence of spin-orbit coupling,
such features, being widely used in several applications only the 4T2(4F)→4A2(4F) transition is detected in the
as solid-state lasers [1,2], scientific research [3,4], visible region, with the appearing of a broad and intense
medicine and dosimetry [5–7], and sensing and optical emission band, due to the fact that the 4T2(4F) energy
communications [8], just to name a few examples. level is strongly dependent on the crystal field
In the scientific literature, it is possible to find several parameter Dq, generating a spin-allowed transition.
works concerning the photoluminescent properties of Sosman et al. [13,14] investigated the MgGa2O4
system doped with Co2+ two decades ago. This
 compound presents a partially inverted spinel structure,
* Corresponding author. where the tetrahedral sites are occupied by Ga3+ ions
E-mail: sandrapedro@uerj.br and the octahedral sites contain Ga3+ and Mg2+ ions

www.springer.com/journal/40145
268 J Adv Ceram 2015, 4(4): 267–271

randomly distributed. It was reported by Sosman and indicating that there is not an apparent degradation even
collaborators an intense luminescence at 77 K for this under the adverse storage conditions.
system, with an emission band at the visible region with To investigate possible degradation suffered by the
barycenter around 675 nm, attributed to the Co2+ sample, it was performed Fourier transform infrared
transition in tetrahedral coordination site [13], but the spectroscopy measurements, using a ThermoScientific
luminescence at room temperature was not explored in spectrometer model NICOLET iS50 FT-IR, with
the mentioned paper. resolution of 4 cm1.
In the present work, we report measurements To investigate if any crystal structural change
performed on the same MgGa2O4:Co2+ (0.1%) sample occurred over the years, X-ray diffraction experiments
produced 24 years ago, whose results can be seen in were performed at room temperature. It was used an
Refs. [13] and [14]. The aim of this work is to X-Pert Pro Panalytical diffractometer working at 40 kV
investigate whether the photoluminescence early and 40 mA (Cu Kα radiation, λ = 1.54056 Å). Data were
observed in this sample at low temperature also occurs collected in the range of 10° < 2θ < 90° in Bragg–
at room temperature and whether some luminescence Brentano geometry with 0.02° step and 100 s/step. The
features as emission band profile and energy position structure pattern was refined by Rietveld method for
remain with the change of temperature and time. It is of identification of the space group, lattice parameter, and
great importance the study of the optical properties at phase quantification.
room temperature, since this is the temperature of Photoluminescence measurements at room
interest in most optical devices. Fourier transform temperature were performed in 2014 using a solid-state
infrared spectroscopy and X-ray diffraction at room laser with 532 nm/50 mW as excitation source,
temperature were also performed to determine if the modulated by a chopper with variable speed Newport
structure suffered degradation and if the crystal model 75160 operating at 200 Hz. One spectrometer
structure profile remained unchanged after this long Acton model AM510 was used to scan the emission in
time. The results of this brief study can open a way for the range of 600–800 nm with 1 nm/step. To detect the
the development and improvement of this material, signal, we used a photomultiplier Newport Oriel model
which keeps the luminescent properties and its 77348 with the signal amplified by a Princeton lock-in
composition stable for several decades besides model 5209. All data were corrected by the apparatus
exhibiting intense emission in the visible at low and sensitivity response.
room temperature, even with the compound stored in
adverse conditions of temperature and humidity.
3    Results and discussion 

2    Experimental details  The X-ray powder diffractogram of the sample is shown

in Fig. 1. Two phases are identified in the 1991
Mg1xCoxGa2O4 compound with x = 0.001 was synthesized compound: the main phase MgGa2O4
synthesized by conventional solid-state reaction, using followed by a small quantity of Ga2O3. For the present
magnesium oxide (MgO), gallium oxide (Ga2O3), and work, the structural data were refined using the FullProf
cobalt II carbonate (CoCO3) with high purity in Suite [15] using the data corresponding to the MgGa2O4
stoichiometric quantities. The reactants were mixed and (ICSD code 61449) and Ga2O3 (ICSD code 83645) as
sintered at 1673 K in vacuum furnace during 48 h, in basis.
order to assure that the cobalt ions acquire the divalent Details of the Rietveld refinement can be seen in
state. Further information concerning the preparation Table 1. Input data related to the experimental
method can be found in other references [13,14]. The conditions and the structural data of each identified
sample was prepared in 1991 and stored under phase were introduced in the software in order to
environmental conditions of Rio de Janeiro city, Brazil, compare data with the experimental diffractogram, with
where the temperature changes in the range of 21–42 ℃ 13 refined parameters. The profile shape used was the
and the average air relative humidity is around 80% Pseudo-Voigt and the background was fit in linear
during the year. After stored under these conditions for interpolation mode between a set of background points
more than two decades, the sample still presents the with refinable heights. The weighted profile factor Rwp,
deep blue color reported in the 1992 work [13], the reduced chi-square χ2, and the difference between

www.springer.com/journal/40145
J Adv Ceram 2015, 4(4): 267–271 269

Table 2 Crystallographic parameters of the main

phase
Molecular formula MgGa2O4 (ICSD 61449)
Proportion 88.8%
Formula weight 4259.96
Crystal system Cubic
Intensity (a.u.)

Space group Fd3m

Unit cell dimensions a = b = c = 8.2780 Å; α = β = γ = 90°
Cell volume 567 Å3
Formula units per cell 8
Density calculated 5.32
Temperature 300 K
Atomic coordinate
Atom Oxidation Wyck Occ X Y Z
Mg1 +2.00 8a 0.05177 0.12500 0.12500 0.12500
2θ (°) Ga1 +2.00 16d 0.05938 0.12500 0.12500 0.12500
Fig. 1 Sample diffractogram showing the observed Mg2 +3.00 8a 0.02860 0.50000 0.50000 0.50000
profile (red circles), calculated profile from Rietveld Ga2 +3.00 16d 0.11943 0.50000 0.50000 0.50000
refinement (black line), and the difference between the O1 2.00 32e 0.35029 0.25376 0.25376 0.25376
calculated and observed profile (blue line).
Table 3 Crystallographic parameters of the secondary
the calculated and observed profiles were evaluated at phase
each refinement cycle to determine the refinement Molecular formula Ga2O3 (ICSD 83645)
quality. The phase qualitative analysis can be calculated Proportion 11.2%
from refinement of the scale factors, where the most Formula weight 817.97
Crystal system Monoclinic
intense peaks are always related to the predominant Space group C12/m1
phase. a = 12.2325 Å; b = 3.0407 Å; c = 5.8091 Å; α =
Unit cell dimensions
The main phase MgGa2O4 crystallizes in the cubic γ = 90°; β = 103.8285°
Cell volume 210 Å3
symmetry Fd3m space group with lattice parameter a =
Formula units per cell 4
8.2780 Å and volume V = 567 Å3; the secondary phase Density calculated 5.96
Ga2O3 belongs to the monoclinic space group C12/m1, Temperature 300 K
with lattice parameters a = 12.2325 Å, b = 3.0409 Å, c = Atomic coordinate
Atom Oxidation Wyck Occ X Y Z
5.8091 Å, β = 103.8285°, and volume V = 210 Å3. The
Ga1 +3.00 4i 0.50000 0.09050 0.00000 0.79460
quantitative analysis obtained from the refinement Ga2 +3.00 4i 0.50000 0.15866 0.50000 0.31402
indicates the proportions of 88.8% for the main phase O1 2.00 4i 0.68134 0.16450 0.00000 0.10980
MgGa2O4 and 11.2% for the secondary phase Ga2O3. O2 2.00 4i 0.48473 0.17330 0.00000 0.56320
O3 2.00 4i 0.69843 0.00410 0.50000 0.25660
The value of the S parameter is 1.3, which indicates the
high quality of the refinement. Further details about the
quality factors and crystal structure of the main and chemical degradation or significant changes in the
secondary phases can be seen in Tables 1–3. Comparing structure, which points to the high quality and long
the results of X-ray diffraction acquired in 2014 with durability of the material.
the data obtained in 1991 [13], we do not notice any The obtained Fourier transform infrared
spectroscopy measurements show only a noise profile,
Table 1 Rietveld quality parameters and FWHM which confirms that the sample does not suffer any kind
factors of degradation by the moisture and/or CO2 presence in
RP (profile factor) 10.5 the air, or any another organic component.
Rwp (weighted profile factor) 12.5 The unpublished luminescence spectrum obtained at
Rexp (expected weighted profile factor) 9.43
room temperature in 1992 can be seen in Fig. 2(a). The
χ2 1.75
S (= Rwp/Rexp, goodness of fit) 1.3
excitation source was a 1 kW xenon lamp positioned at
U = 0.021780 λexc = 545 nm and it is possible to observe a symmetrical
FWHM (MgGa2O4)
V = 0.002049 emission broadband, with maximum intensity at
(profile function: Pseudo-Voigt)
W = 0.010391 680 nm. In Fig. 2(b), it is shown the emission spectrum
U = 0.034640
FWHM (Ga2O3) of the same sample at room temperature, but now
V = 0.006243
(profile function: Pseudo-Voigt)
W = 0.001769 acquired in 2014 with a laser as excitation source
operating at λexc = 532 nm.

www.springer.com/journal/40145
270 J Adv Ceram 2015, 4(4): 267–271

λexc=545 nm (1992)
intensity at 675 nm. The photoluminescence
measurements reported in the present work correspond
to the same sample (not the same sample synthesized
again, but the same sample used in the 1991
measurements), whose spectrum at room temperature
was not published until now (Fig. 2(a)). Comparing
both spectra obtained at room temperature in 1992 and
2014, it is noticed a small shift to higher wavelength
(lower energy) in the band maximum intensity, which is
explained by the use of distinct equipment to acquire
both spectra in distinct times.
Wavelength (nm)
A very important difference between experiments is
λexc=532 nm (2014)
related to the excitation wavelength of the sample. In
the excitation spectrum [13], we see that the intensity of
the luminescence at 680 nm is about 20% higher when
the sample is excited with 545 nm than with 532 nm
wavelength. This fact can contribute to the signal
difference (of 0.2 mV) observed in the spectra showed
in this paper. In this way, we are able to say that exciting
the sample using 545 nm is more favorable than using
532 nm, because the former generates a more intense
signal than the latter.
The luminescence lifetime, calculated by the shift
Wavelength (nm) phase method [16] is around 8 µs, a characteristic value
Fig. 2 Luminescence spectra at room temperature of for systems containing Co2+, and this value has the same
MgGa2O4:Co2+ (0.1%). (a) Spectrum obtained in 1992 with order of magnitude of the value previously reported
excitation source (Xe lamp) positioned in 545 nm; (b)
spectrum obtained in 2014 with excitation source in
[14]. The same magnitude of the lifetime in both
532 nm (solid-state laser). measurements indicates that the radiative transitions are
originated from the same emission state and that this
In the 2014 spectrum, the luminescence consists of a state was kept unchanged over the years. This
broad band in the visible–near infrared region with observation indicates that the environment of the dopant
maximum intensity at 682 nm. This emission band ion remains unchanged, without crystallographic
corresponds to the spin-allowed electronic transition variation, as observed also in the X-ray results.
4
T2(4F)→4A2(4F) of the Co2+ ion in tetrahedral
coordination site. In Table 4, it is shown a comparison
between the luminescence data obtained at room 4    Conclusions 
temperature in 1992 and 2014: the wavelength of the
respective excitation sources (λexc), the wavelength After 24 years stored, we performed photoluminescence
where the maximum intensity of the broad band occurs measurements at room temperature in the MgGa2O4
(λem), and the FHWM in nm and cm1 units. with 0.1% of cobalt sample to verify if the optical
In the 1992 paper [13], the authors presented properties early observed in the material changed
the emission spectra of this compound, and reported during this long time. Concerning the structural features,
the emission band obtained at 77 K with maximum we did not observed any chemical degradation and
structural changes in the sample. The optical properties
Table 4 Data comparison extracted from the 1992 and remain unchanged even after this long time, with the
2014 spectra at room temperature appearing of the same broad band and an intense
FHWM luminescence already reported in previous works at low
Year λexc (nm) λem (nm)
(nm) (cm1) temperature. We observed a significant shift in the
1992 545 680 41 885 emission band and the radiative lifetime with the
2014 532 682 43 940 change of temperature and time, indicating that the site

www.springer.com/journal/40145
J Adv Ceram 2015, 4(4): 267–271 271

remains unchanged even after the time, temperature, [5] Yukihara EG, Gasparian PBR, Sawakuchi GO, et al.
and humidity actions. Such observations show that the Medical applications of optically stimulated luminescence
dosimeters (OSLDs). Radiat Meas 2010, 45: 658–662.
studied material presents high quality and efficiency,
[6] Gai M, Chen Z, Fan Y, et al. Synthesis and luminescence in
non-reactivity, longevity, and stability, which makes it a LiMgPO4:Tb,Sm,B phosphors with possible applications in
very good system as a material for technological real-time dosimetry. J Rare Earth 2013, 31: 551–554.
applications with relatively long useful life. [7] Knežević Ž, Stolarczyk L, Bessieres I, et al. Photon
dosimetry methods outside the target volume in radiation
therapy: Optically stimulated luminescence (OSL),
Acknowledgements  thermoluminescence (TL) and radiophotoluminescence
(RPL) dosimetry. Radiat Meas 2013, 57: 9–18.
S. S. Pedro, M. A. F. M. da Silva, A. López, and L. P. [8] Dong G, Wu B, Zhang F, et al. Broadband near-infrared
Sosman acknowledge FAPERJ and FINEP for financial luminescence and tunable optical amplification around
support. The authors also acknowledge the Centro 1.55 µm and 1.33 µm of PbS quantum dots in glasses.
J Alloys Compd 2011, 509: 9335–9339.
Brasileiro de Pesquisas Físicas (CBPF) for the X-ray
[9] Henderson B, Bartram RH. Crystal-Field Engineering of
diffraction experiments and Waste Analysis Laboratory Solid-State Laser Materials. Cambridge, UK: Cambridge
(UERJ) for the FTIR measurements. University Press, 2000.
[10] Kuleshov NV, Mikhailov VP, Scherbitsky VG, et al.
Open  Access: This article is distributed under the terms Absorption and luminescence of tetrahedral Co2+ ion in
MgA12O4. J Lumin 1993, 55: 265–269.
of the Creative Commons Attribution License which
[11] Husain S, Alkhtaby LA, Bhat I, et al. Study of cobalt
permits any use, distribution, and reproduction in any doping on structural and luminescence properties of
medium, provided the original author(s) and the source nanocrystalline ZnO. J Lumin 2014, 154: 430–436.
are credited. [12] Radlinski AP, Liro Z. Infrared luminescence excitation
spectroscopy of cobalt impurity in GaP. J Phys C: Solid
State Phys 1985, 18: 6481.
References  [13] Sosman LP, Abrita T. Optical spectroscopy of MgGa2O4:
Co2+. Solid State Commun 1992, 82: 801–803.
[1] Li J, Pan Y, Zeng Y, et al. The history, development, and [14] Sosman LP, Abritta T, Pereira AC, et al. Photoacoustic
future prospects for laser ceramics: A review. Int J Refrac spectroscopy of Co2+ in ZnGa2O4 and MgGa2O4. Chem
Met H 2013, 39: 44–52. Phys Lett 1994, 227: 485–489.
[2] Boulon G. Fifty years of advances in solid-state laser [15] Roisnel T, Rodriguez-Carvajal J. FullProf Suite Program
materials. Opt Mater 2012, 34: 499–512. FullProf.2k V. 4.80 Laboratoire Léon Brillouin (CEA-
[3] Kück S. Laser-related spectroscopy of ion-doped crystals CNRS). 2010. Available at http://www.ill.eu/sites/fullprof/
for tunable solid-state lasers. Appl Phys B 2001, 72: index.html.
515–562. [16] Martin JE, Shea-Rower LE. Lifetime determination of
[4] Feldmann C, Jüstel T, Ronda CR, et al. Inorganic materials that exhibit a stretched exponential luminescent
luminescent materials: 100 years of research and decay. J Lumin 2006, 121: 573–587.
application. Adv Funct Mater 2003, 13: 511–516.

www.springer.com/journal/40145