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Journal of Non-Crystalline Solids 354 (2008) 3343–3347

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Optical properties of Cr3+ ion in lithium metasilicate Li2O  SiO2

transparent glass–ceramics
Shigeki Morimoto a,*, Sasithorn Khonthon a, Yasutake Ohishi b
a
School of Ceramic Engineering, Institute of Engineering, Suranaree University of Technology, 111 University Avenue,
Muang District, Nakhon Ratchasima 30000, Thailand
b
Research Center for Advanced Photon Technology, Toyota Technological Institute, 2-12-1 Hisakata, Tempaku, Nagoya 468-8511, Japan

Received 15 August 2007; received in revised form 14 January 2008

Available online 20 March 2008

Abstract

The optical properties of Cr3+ ions in lithium metasilicate (Li2O  SiO2) transparent glass–ceramics were investigated. The main crys-
talline phase precipitated was the lithium metasilicate (Li2O  SiO2) crystal. The percent crystallinity and crystalline size were ranging 65–
75% and 20–35 nm, respectively. The color changes drastically to deep pink from emerald green upon crystallization. New and strong
absorption bands appeared and the absorption intensity increases by about 10 times that in glass. These new absorption bands are found
to be derived from Cr3+ ions in octahedral sites in the lithium metasilicate crystal lattice. Cr3+ ions substitute for three Li+ ions and
occupy the distorted octahedral site between single [SiO4]n chains of lithium metasilicate crystal. The ligand field parameters can be esti-
mated: 10Dq = 13 088 cm1, B = 453 cm1, Dq/B = 2.89 and C = 2036 cm1. The near-infrared luminescence centered at 1250 nm was
not detected in the deep pink glass–ceramics unlike emerald green glass.
Ó 2008 Elsevier B.V. All rights reserved.

PACS: 42.70.C; 78.40; 78.55; 78.60; 78.66.J

Keywords: Glass–ceramics; Optical spectroscopy; Nanocrystals; Nanoparticles; Absorption; Luminescence; Alkali silicates; Electron spin resonance

1. Introduction (700 nm) under excitation by shorter wavelengths of

Much research on color generation and luminescent
behavior of Cr3+ ions in glasses and single crystals have
been examined in terms of the transition metal coordina-
tion number [1–5]. These results have been interpreted
based on ligand field theory. It is well known that the
Cr3+ ions preferentially occupy octahedral sites in glasses
and crystals as indicated by their large site stabilizing
energy [6]. The color and the positions of absorption bands
change depending on the ligand field parameters.
In the case of ruby crystals (Cr3+:Al2O3) [2,6] and spinel
crystals (Cr3+:MgAlO4) [3], the absorption bands shift to
shorter wavelengths and they emit a characteristic red line
*
Corresponding author. Tel.: +66 44 22 4475; fax: +66 44 22 4612.
E-mail address: shigeki@sut.ac.th (S. Morimoto).
light. In this case, Cr3+ is located in a strong ligand field.
On the other hand, recently, Cr3+ ions located in weak
ligand field were reported in a Zn(Mg)-doped LiNbO3:Cr3+
single crystal [7–9]. Usually, crystal hosts enhance the
ligand field strength, but this crystal showed the opposite
result.
Glass–ceramics are two-phase systems consisting of a
base glass within which crystals are grown by heat treat-
ment. Transparent glass–ceramics, in which nano-scale
crystals are precipitated, can be obtained by controlling
base glass composition and heat treatment condition.
Transparent glass–ceramics are currently being considered
as hosts for luminescent ions because of the possibilities
afforded by crystal site control.
In this paper the optical properties of the Cr ion in
Li2O  SiO2 transparent glass–ceramics were investigated.

0022-3093/$ - see front matter Ó 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.jnoncrysol.2008.01.025
3344 S. Morimoto et al. / Journal of Non-Crystalline Solids 354 (2008) 3343–3347

It was found that the Cr3+ ion is present in the weak octa- where k is the wavelength of X-ray radiation (1.54 Å), b the
hedral ligand field of lithium metasilicate nano-crystal. true half width (radian) and h the diffraction angle (degree).
True half width was determined by Jones method [12], and
2. Experimental methods a-Quartz was used as a standard.
In order to confirm the presence of Cr3+ ion, electron
2.1. Sample preparation spin resonance (ESR) spectra were measured using JEOL
JES RE-2X at room temperature.
The base glass composition was 65SiO2  5Al2O3 
26Li2O  4K2O (wt%), and 0.2 wt% of Cr2O3 and 1.0 wt% 2.4. 4. Optical absorption and emission spectra
of Sb2O3 were added to 100 g of glass by excess. In this
glass the addition of Sb2O3 reduced Cr ion to the 3+ state The absorption spectra were measured with Varian Cary
and eliminated the charge transfer absorption of Cr6+ [10]. 5E UV–VIS–NIR Spectrophotometer in the range of 300–
High purity silica sand, alumina and reagent grade of 2000 nm at room temperature.
chemicals of Li2CO3, K2CO3, Cr2O3 and Sb2O3 were used The emission spectra in near-infrared (NIR) region
as raw materials. Batch corresponding to 25 g of glass was (1000–1700 nm) were also measured under the excitation
mixed thoroughly, and then melted in a 50 ml Pt/Rh10 cru- of 974 nm laser diode at room temperature. Emission from
cible at 1300 °C for 1 h in an electric furnace in air. The samples was dispersed by a single monochromator (blaze,
molten glass was poured onto iron plate and pressed 1.0 lm: grating, 600 grooves/mm: resolution, 3 nm) and
quickly by another iron plate to avoid crystallization. detected by an InGaAs photodiode.
The glass was annealed at 450 °C for 30 min to remove
stresses and cooled slowly to room temperature in the 3. Results
furnace, and then they were heat treated under conditions
of 650 °C – 5 h, 700 °C – 1.5 h and 700 °C – 5 h for 3.1. Properties of glass–ceramics
crystallization.
The glass and glass–ceramics were cut and polished The glass–ceramics appeared to be transparent after the
optically into about 1 mm in thickness for optical heat treatment below 800 °C. In these conditions, only lith-
measurement. ium metasilicate (Li2O  SiO2, hereafter LS) crystal (JCPDS
00-029-0829) was detected. Table 1 shows appearance,
2.2. Preparation of polycrystalline Li2O  SiO2:Cr crystalline phases, percent crystallinity and crystal size of
transparent glass–ceramics. The percent crystallinity and
The polycrystalline Li2O  SiO2:Cr was prepared by a the crystallite size were ranging 65–75 wt% and 25–
solid state reaction to investigate whether Cr3+ ion exists 35 nm, respectively. Both the percent crystallinity and the
or not in this crystal. A mixture of high purity silica sand, crystallite size increased with increase in heating tempera-
Li2CO3 and Cr2O3 (1 wt% by excess) corresponding to ture and time. If all of Li2O (26 wt%) would be spent for
Li2O  SiO2 composition was heated at 1100 °C for 40 h the crystallization of LS crystal, the amount of LS crystal
in air. would be about 78 wt%, and hence the measured values
may be reasonable.
2.3. XRD and ESR
3.2. Absorption spectra
Crystalline phases, amount of crystal and crystalline size
were examined by powder X-ray diffraction (XRD) (Bru- The color changes drastically from pale emerald green to
ker, AXS Model D5005) under the condition of Cu-Ka deep pink upon crystallization and the pink color becomes
radiation, 40 kV–40 mA, 0.01° step, 1 s/step. Amount of deeper with increasing heating temperature and time. Fig. 1
crystal was determined using Ohlberg and Strickler’s
method [11], and was calculated by
Table 1
100x ½I g  I x =½I g  I c  ¼ percent crystallinityð%CÞ; Crystalline phase, percent crystallinity and crystallite size of transparent
glass–ceramics
where Ig is the background intensity of glass, Ix that of Heat Appearance Crystalline Percent Crystallite
specimens and Ic that of a-Quartz at 2h = 23°. The calibra- treatment phase crystallinity size (nm)
tion curve was obtained using parent glass and a-Quartz at (°C – h) (%C, by wt)
various ratios, and showed good linearity. The percent Glass Transparent pale – – –
crystallinity can be obtained by wt%. emerald green
The crystal size was calculated using Scherrer’s 600–5 Transparent deep pink Li2O  SiO2a 65 ± 5 20 ± 5
700–1.5 Transparent deep pink Li2O  SiO2a 70 ± 5 25 ± 5
equation. 700–5 Transparent deep pink Li2O  SiO2a 75 ± 5 35 ± 5
d ¼ 0:9  k=b  Cosh a
JCPDS 00-029-0829.
 S. Morimoto et al. / Journal of Non-Crystalline Solids 354 (2008) 3343–3347 3345

Cr-Diffuse.emf (3991x2867x16M)
a 25
100
VIS

20 700˚C-5h
Glass-ceramics(700-5)
Optical density

80

15

Reflectance/%
60

10 700˚C-1.5h Synthesized LS :Cr crystal

40
5
650˚C-5h

Glass
20
0
300 400 500 600 700 800
Wavelength/nm 0
400 600 800 1000 1200 1400 1600 1800 2000
Wavelength/nm
b NIR
Fig. 2. Diffuse reflectance spectra of glass–ceramics and synthesized
5
polycrystalline Li2O  SiO2:Cr at room temperature. Glass–ceramics:
700 °C – 5 h.
Optical density

700˚C-5h
3
360 nm, 530 nm and 750 nm, and the broad bands at
2 700˚C-1.5h
around 950 nm and 1150 nm are also observed in NIR
region. Furthermore, the weak absorption band at around
650˚C-5h 420 nm appears. This indicates that the Cr ion was
1
incorporated into Li2O  SiO2 crystal lattice in glass–
Glass
ceramics.
800 1000 1200 1400 1600 1800 2000
Wavelength/nm 3.3. Emission spectra
Fig. 1. Absorption spectra of glass and glass–ceramics at room temper-
ature. Inset denotes heat treatment condition for crystallization (°C – h). Fig. 3 shows the emission spectra of glass and glass–
ceramics in NIR region under the excitation of 974 nm,
and no emission was observed in glass–ceramics. On the
shows the absorption spectra of glass and glass–ceramics. contrary, the broad emission centered at around 1250 nm
In the glass the weak absorption bands appear at around was observed in glass. This emission might be due to
4
450 and 650 nm and are due to d–d transition of Cr3+ T2 ? 4A2 transition of Cr3+ in octahedral coordination.
ion in octahedral site, and they can be assigned to
4
A2 ? 4T1 (450 nm) and 4A2 ? 4T2 (650 nm) transi-
tions [1]. No absorption band was observed in NIR region.
On the contrary, in glass–ceramics, the new and strong LS3NIR.emf (4683x3183x16M)
absorption bands appear at around 370, 530 and 10
750 nm in VIS region, and the broad bands at around Ex=974 nm
Glass
950 nm and 1150 nm are observed in NIR region. 8
Furthermore, the weak absorption band at around
Intensity/a.u.

420 nm is also found. It should be noted that the absorp- 6

tion intensity of new absorption bands in glass–ceramics
increases with increase in heating temperature and time,
4
and is about 10 times greater than that in glass (700 °C
5 h glass–ceramics). This suggests that Cr3+ ion enters into
LS nano-crystals in glass–ceramics. 2
The polycrystalline Li2O  SiO2:Cr appeared to be pink
Glass-ceramics(700˚C-5h)
in color, and XRD showed only Li2O  SiO2 phase (JCPDS 0
00-029-0289). Fig. 2 shows the diffuse reflectance spectra 1000 1100 1200 1300 1400 1500 1600 1700
of polycrystalline Li2O  SiO2:Cr. The spectral pattern of Wavelength/nm
polycrystalline Li2O  SiO2:Cr is almost the same as Fig. 3. NIR emission spectra of glass and glass–ceramics under the
that of glass–ceramics. The absorption bands appear at excitation of 974 nm laser diode at room temperature.
3346 S. Morimoto et al. / Journal of Non-Crystalline Solids 354 (2008) 3343–3347

4. Discussion As shown in Fig. 1, the absorption spectra in visible

4.1. Assignment and coordination number of Cr3+ ion in LS
crystal
It was found that Cr3+ ion in octahedral site is present in
glass by optical absorption spectra. In order to confirm the
valence state and ligand field of Cr ion (Cr3+) in glass–
ceramics, ESR measurement was carried out. Fig. 4 shows
ESR spectra of glass and glass–ceramics. The ESR signals
were detected at g  4.3 and g  1.9 in both glass and
glass–ceramics, and these signals become more clear and
the signal intensity increases upon crystallization, espe-
cially g  1.9 signal. Generally it was reported that ESR
signal at g  4.3 is due to isolated Cr3+ ion in octahedral
site and the signal at g  1.9 is due to exchange coupled
pairs of Cr3+ ion in octahedral site [13]. Furthermore, the
ESR signal at g  1.9 was found in Zn co-doped LiN-
bO3:Cr3+ single crystal [14], and this signal is interpreted
to be due to Cr3+ ion occupying Nb5+ site (octahedral site)
in that crystal [7–9]. Thus, it was confirmed that Cr3+ ion in
octahedral site is present in glass and glass–ceramics by
ESR measurement.
It is well known that Cr3+ ion occupies preferentially
octahedral site in crystals and glasses. The color and
absorption bands change with the ligand field strength
[1]. Here, the assignment of absorption bands will be dis-
cussed bellow based on octahedral symmetry.
The energy diagram (Tanabe–Sugano diagram) in octa-
hedral symmetry predicts that the spectrum of Cr3+ will
consist essentially of three bands corresponding to the
spin-allowed transitions 4A2g ? 4T1g, 4A2g ? 4T2g and
4
A2g ? 4T1g(P) together with several weak lines and bands
corresponding to spin-forbidden transition. The ligand
field parameters were analyzed by multi-peak fitting
method with Gaussian distribution, and results are summa-
rized in Table 2. The examples of another crystal are also
listed in this table for comparison.
region of glass–ceramics are quite similar to that of pink
Zn co-doped LiNbO3:Cr3+ single crystal [7–9] in which
Cr3+ ion occupies octahedral Nb5+ site, and its ligand field
parameters were given, 10Dq = 13 420 cm1, B = 646 cm1
and Dq/B = 2.1 [14]. By assuming that three absorption
bands, 370 nm, 520 and 750 nm in glass–ceramics
observed here, would be assigned to 4A2g ? 4T1g(P),
4
A2g ? 4T1g and 4A2g ? 4T2g transitions, the ligand field
parameters can be estimated, 10Dq = 13 088 cm1, B =
453 cm1, C = 2036 cm1, Dq/B = 2.89 and C/B = 4.50.
The agreement between observed spectra and predicted
taking above values is reasonable (Table 2). These values
are also quite similar to those of Cr3+doped LiNbO3 single
crystal and CrCl3 crystal [1]. In Cr3+doped lithium metasi-
licate (LS) glass–ceramics discussed here, the absorption
bands shift to longer wavelength (red shift) unlike Cr3+
ion-doped ruby and spinel crystals [2,3]. Usually crystal
hosts enhance the ligand field strength, but this result
shows opposite feature. In this glass–ceramics, the absorp-
tion due to the spin-forbidden transition 4A2g ? 2A2g
(420 nm) also appeared, and this indicates the large dis-
tortion of octahedral symmetry.
4.2. Cr3+ site in LS crystal
Lithium metasilicate (LS) crystal belongs to base cen-
tered orthorhombic symmetry with Cmc21 space group,
and the LS crystal has a single chain structure in which
each [SiO4] tetrahedron shares two vertices [15]. In the crys-
tal the parallel chains pack so as to provide suitable
environment for the cations, e.g. 6-coordination of Li+
(0.68 A) and Mg2+(0.66A). Cr3+ ion (0.63 A) is slightly
smaller than Li+ and Mg2+ ions and hence Li+ ion might
be substituted by Cr3+ ion, in this case however, three
Table 2
Ligand field parameters of Cr3+ ion in glass and glass–ceramics using
Gaussian distribution

LS4ESR1.emf (3141x2135x16M) Cr3+ ion Transition Observed Predicted

bands (cm1) bands (cm1)
4
3000 Glass (octahedral) A2g ? 2E2g(G) 14 220 14 705
4
A2g ? 4T2g 15 761 15 554
4
g=4.26305 A2g ? 4T1g 22 615 22 114
2000 10Dq = 15 761 cm1, B = 707 cm1,
Intensity/a.u.

Glass-ceramics C = 3112 cm1, Dq/B = 2.23, C/B = 4.40

(700˚C-5h) g=1.93063
4
1000 Glass–ceramics A2g ? 2E2g(G) 8849 9422
4
(700 °C – 5 h) A2g ? 2T2g(G) 10 802 10 186
4
(octahedral) A2g ? 4T2g 13 088 13 110
0 4
A2g ? 4T1g 18 854 18 120
g=1.88834
g=4.34955 Glass 4
A2g ? 4T1g(P) 27 206 27 252
-1000 10Dq = 13 088 cm1, B = 453 cm1,
C = 2036 cm1, Dq/B = 2.89, C/B = 4.50
0 100 200 300 400 Zn-LiNbO3 [14] 10Dq = 13 420 cm1, B = 646 cm1,
Magnetic field/mT (octahedral) C = 3022 cm1, Dq/B = 2.1, C/B = 4.68
CrCl3 [1] (octahedral) 10Dq = 13 600 cm1, B = 510 cm1,
Fig. 4. ESR spectra of Cr3+ ion in glass and glass–ceramics at room
Dq/B = 2.66
temperature.
 S. Morimoto et al. / Journal of Non-Crystalline Solids 354 (2008) 3343–3347
Li+ ions should be replaced by one Cr3+ ion in order to
neutralize the electrical charge. NIR luminescence disap-
peared and few spin-forbidden transitions appeared upon
crystallization. Usually these phenomena can be observed
when the symmetry of ligand polyhedra is lacking or
decreases. As mentioned above, three Li+ ions should be
replaced by one Cr3+ ion to neutralize the electrical charge,
and hence it seems that the ligand polyhedra of Cr3+ ion
might be distorted.
Generally, the polarizable ligand induces the dramatic
decrease in Dq and B, and further the absorption intensity
tends to increase according to spectrochemical series.
Therefore, this indicates that mixing of electron between
central cation and ligands increases. The absorption inten-
sity in glass–ceramics increases drastically.
5. Conclusion
The optical properties of Cr3+ ions in lithium metasili-
cate (Li2O  SiO2) transparent glass–ceramics were investi-
gated. The only crystalline phase precipitated was the
lithium metasilicate (Li2O  SiO2) crystal. The percent crys-
tallinity and crystalline size ranged from 60–70% and 20–
35 nm, respectively. Polycrystalline Li2O  SiO2:Cr3+ was
also prepared and its optical absorption was compared
with that of the transparent glass–ceramics.
The color changes drastically to deep pink from emerald
green upon crystallization. New and strong absorption
bands appeared and the absorption intensity increases by
about 10 times that in the glass. The same absorption
spectra can be obtained in both polycrystalline Li2O 
SiO2:Cr3+ and in the glass–ceramics. These new absorption
bands are found to be derived from Cr3+ ions in octahedral
sites in the lithium metasilicate crystal lattice. Cr3+ ions
substitute for three Li+ ions and occupy the distorted octa-
hedral sites between single [SiO4]n chains of the lithium
metasilicate crystal. The ligand field parameters can be esti-
mated: 10Dq = 13 088 cm1, B = 453 cm1, Dq/B = 2.89
and C = 2036 cm1, respectively. Near-infrared lumines-
3347
cence was not detected in deep pink glass–ceramics unlike
emerald green glass.
Thus, while crystal hosts usually enhance ligand field
strength, the lithium metasilicate crystal provides the oppo-
site result.
Acknowledgements
This study was supported by Special Coordination Fund
of Suranaree University of Technology, to which the
author indebted. The author also would like to thank Dr
Sathorn Suwan, STREC, Chulalongkorn University, Thai-
land, for helpful discussion on ESR measurement.
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