Spectra, energy levels, and symmetry assignments for Stark components

of Eu
3
(4f
6
) in gadolinium gallium garnet (Gd
3
Ga
5
O
12
)
John B. Gruber
a
, Uygun V. Valiev
b
, Gary W. Burdick
c
, Sharof A. Rakhimov
b
,
Madhab Pokhrel
a
, Dhiraj K. Sardar
a,n
a
Department of Physics and Astronomy, The University of Texas at San Antonio, San Antonio, TX 78249, USA
b
Faculty of Physics, National University of Uzbekistan, Vuzgorodok, Tashkent 100174, Uzbekistan
c
Department of Physics, Andrews University, Berrien Springs, MI 49104, USA
a r t i c l e i n f o
Article history:
Received 9 November 2010
Received in revised form
17 March 2011
Accepted 24 March 2011
Available online 14 April 2011
Keywords:
Stark components
Magneto-optical spectrum
Crystal eld parameters
Zeeman components
Fluorescence spectrum
Absorption spectra
a b s t r a c t
Absorption and uorescence spectra observed between 450 and 750 nm at 85 K and room temperature
(300 K) are reported for Eu
3
(4f
6
) in single-crystal Czochralski-grown garnet, Gd
3
Ga
5
O
12
(GGG). The
spectra represent transitions between the
2S1
L
J
multiplets of the 4f
6
electronic conguration of Eu
3
split by the crystal eld of the garnet. In absorption, Eu
3
transitions are observed from the ground
state,
7
F
0
, and the rst excited multiplet,
7
F
1
, to multiplet manifolds
5
D
0
,
5
D
1
, and
5
D
2
. The Stark
splitting of the
7
F
J
multiplets (J 06) was determined by analyzing the uorescence transitions from
5
D
0
,
5
D
1
, and
5
D
2
to
7
F
J
. The Eu
3
ions replace Gd
3
ions in sites of D
2
symmetry in the lattice during
crystal growth. Associated with each multiplet manifold are 2J 1 non-degenerate Stark levels
characterized by one of four possible irreducible representations (irreps) assigned by an algorithm
based on the selection rules for electric-dipole (ED) and magnetic-dipole (MD) transitions between
Stark levels in D
2
symmetry. The quasi-doublet in
5
D
1
was characterized by an analysis of the magneto-
optical spectra obtained from the transitions observed between
5
D
1
and
7
F
1
. A parameterized
Hamiltonian dened to operate within the entire 4f
6
electronic conguration of Eu
3
was used to
model the experimental Stark levels and their irreps. The crystal-eld parameters were determined
through use of a Monte-Carlo method in which nine independent crystal-eld parameters, B
k
q
, were
given random starting values and optimized using standard least-squares tting between calculated
and experimental levels. The nal tting standard deviation between 57 calculated-to-experimental
Stark levels is 5.9 cm
1
. The choice of coordinate system, in which the nine B
k
q
are real and the crystal-
eld z-axis is parallel to the [0 0 1] crystal axis and perpendicular to the xy plane, is identical to the
choice we used previously in analyzing the spectra of Er
3
and Ho
3
garnets.
& 2011 Elsevier B.V. All rights reserved.
1. Introduction
For decades trivalent europium (Eu
3
) has been used as an
optical probe, providing spectroscopic information regarding the
local site symmetry and environment within the host [111]. The
emission cross sections and relatively long uorescence lifetimes
associated with the Eu
3
(4f
6
) transitions from the
5
D
0,1,2
levels to
the ground-state multiplets
7
F
J
have made it possible to develop
components for numerous photonic devices and optical displays
[1223]. Reviews of earlier work on the spectroscopic analysis of
the crystal-eld splitting of the energy levels of Eu
3
(4f
6
) doped
into single-crystal cubic garnets have been reported by several
groups of Refs. [912]. The Eu
3
ion substitutes for Gd
3
in the
D
2
sites of cubic gadolinium gallium garnet Gd
3
Ga
5
O
12
[2426].
The crystal-eld splitting of the
7
F
J
multiplets of Eu
3
in
Eu
3
Ga
5
O
12
(EuGG) was determined by Boal et al. [20] from
analysis of the light scattering (electronic Raman spectra),
uorescence and absorption spectra. The crystal-eld splitting
analysis of Eu
3
in Y
3
Al
5
O
12
(YAG) reported by Gross et al. [21]
involved site-selective polarized spectroscopy to identify
both the energy and irreducible representation (irrep) for
individual Stark levels. More recently, Binnemans and G orller-
Walrand [22,27,28] analyzed the absorption spectra and
magnetic circular dichroism (MCD) spectra, and modeled
the crystal-eld splitting of Eu
3
doped into single-crystal
Y
3
Ga
5
O
12
(YGG). Advances by Burdick et al. [29,30] and Rudo-
wicz et al. [31,32] have provided insight into the crystal eld
theory used to analyze these spectroscopic data. The present
experimental spectroscopic and magneto-optical analyses of
Eu
3
in GGG extend our earlier work on this host to include
additional assignments in a crystal that we are presently investigating
for possible down-conversion or quantum cutting.
Contents lists available at ScienceDirect
journal homepage: www.elsevier.com/locate/jlumin
Journal of Luminescence
0022-2313/$ - see front matter & 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.jlumin.2011.03.057
n
Corresponding author. Tel.: 1 210 458 4578.
E-mail address: dsardar@utsa.edu (D.K. Sardar).
Journal of Luminescence 131 (2011) 19451952
We report the absorption and uorescence spectra and analy-
sis of Eu
3
in GGG between 450 and 750 nm, and the magneto-
optical spectra and analysis of transitions between levels of the
5
D
1
multiplet, which includes a quasi-doublet and singlet, and the
three singlet Stark components of the
7
F
1
manifold. Quasi-doub-
lets are singlets (non-degenerate) Stark levels closely spaced so
that magneto-optical spectroscopy is needed to identify the
energies and irreps of these singlets [3335]. The irrep assign-
ments obtained for
5
D
1
and
7
F
1
allow us to use an algorithm to
make irrep assignments to Stark levels in other multiplet mani-
folds, identied through analyses of the 300 K absorption and
uorescence spectra. A parameterized Hamiltonian dened to
operate within the entire 4f
6
electronic conguration of Eu
3
was
used to model the experimental Stark levels and their irreps. Nine
independent crystal-eld parameters, B
k
q
, were given random
starting values and optimized by using standard least-squares
tting between calculated and experimental levels. The nal
tting standard deviation between 57 calculated-to-experimental
levels is 5.9 cm
1
. The choice of the coordinate system, in which
all nine B
k
q
are real and the crystal-eld z-axis is parallel to the
[0 0 1] crystal axis and perpendicular to the xy plane, is identical
to the choice used recently to analyze the crystal-eld splitting of
the energy levels of Er
3
and Ho
3
in garnet hosts [30,35].
2. Experimental details
Single crystals of Gd
3
Ga
5
O
12
(GGG) doped with Eu
3
were grown
using a high-temperature Czochralski furnace by B.V. Mill at Moscow
State University. The growth direction of the crystal was along the
[1 1 1] axis of the garnet. Small amounts of Sm
3
and Tb
3
were
found in the sample as well. In terms of atomic weight %, the
concentration of each ion is: Eu
3
(0.05), Sm
3
(0.01), and Tb
3
(0.015) determined by atomic emission spectroscopy methods. The
ultra violet (UV) absorption spectrum of the crystal is intense due to
overlapping transitions from the ground state to a dense distribution
of excited levels unique to each ion. Upon excitation of the crystal,
energy is transferred through the lattice to each ion (Eu
3
, Sm
3
, and
Tb
3
). However, the uorescence is easy to separate since each ion
has distinct groupings of uorescence bands associated with the
crystal-eld splitting for that ion. Consequently, the spectra of all
three ions were analyzed as part of an on-going investigation into
possible down-conversion or quantum-cutting phenomena in the
crystal. The uorescence from Sm
3
(
4
G(4)
5/2
-
6
H
J
,
6
F
J
) and the
uorescence from Tb
3
(
5
D(3)
4
-
7
F
J
) are similar to the detailed
crystal-eld splitting analyses we reported earlier for Sm
3
in
Y
3
Al
5
O
12
(YAG) and Tb
3
Y
3
Ga
5
O
12
(YGG) [3638]. By concentrating
on the details of the Eu
3
spectra in the present study, we identied
the uorescence spectra representing transitions from
5
D
0,1,2
to the
7
F
J
multiplets.
The absorption and uorescence spectra were obtained with a
high resolution diffraction monochromator MDR Model 23 (LOMO,
Russian), and a Steady State and Lifetime Fluorescence Spectrometer
FSL 920 (Edinburgh Instruments Ltd., U.K.). The wavelength range
covered in both emission and absorption experiments was approxi-
mately 450760 nm with an average instrumental resolution of
0.03 nm for the absorption spectra and 0.05 nm for the uorescence
measurements. Excitation of the sample was carried out using an
Hgxenon discharge lamp and narrow-band pass lters designed to
exclude the Sm
3
and Tb
3
emission. Detection of the absorption
spectra was made using photomultiplier tubes sensitized by a
technique described earlier that stabilizes the average photomulti-
plier current at a constant level while scanning over a given line
shape [34,38]. Spectra were recorded at 300 K (room temperature).
For low temperature measurements the crystal was placed
between two quartz light guides and attached to the cold nger of
a conduction Dewar lled with liquid nitrogen (78 K). The actual
crystal temperature in this arrangement was approximately 85 K.
For magneto-optical measurements both the MCD and the
magnetic circular polarization of luminescence spectra (MCPL)
were obtained at 300 K in a magnetic eld, H, up to 10 kOe with
the sample oriented along the [1 1 1] direction of the crystal.
A sensitive modulation method for measuring the degree of
circularity, P, for the partially polarized emitted MCPL and for
transmitting MCD light has been described earlier in Ref. [34]. The
excitation spectrum for luminescence of Eu:GGG is compared
with the ultra violet (UV) absorption spectrum of the GGG crystal
in Fig. 1. The preferred wavelength range for effective excitation
of luminescence is around 280 nm. In particular, 274 nm excita-
tion results in a well-resolved red and infrared spectra of
Eu
3
in GGG at both 300 and 85 K. Between 270 and 284 nm the
sharp-line absorption obtained at 85 K in Fig. 1 is due to the
6
I
J
and
6
P
J
energy levels of Gd
3
(4f
7
). A survey spectrum of the 300 K
uorescence spectrum observed between 550 and 720 nm is
given in Fig. 2. A superposition of the uorescence and absorption
spectra of the
7
F
1
manifold at 300 K is shown in Fig. 3. A listing of
the Eu
3
uorescence spectrum is given in Table 1 and analyzed
in the following section. The calculated energy (Stark) levels
obtained from modeling the crystal-eld splitting are reported
Wavelength (nm)
240 260 280 300 320
A
b
s
o
r
p
t
i
o
n

(
a
.
u
)
0
20
40
60
80
100
120
6
I
17/2
6
I
9/2
6
I
7/2
6
P
3/2
6
P
5/26
P
7/2
Fig. 1. Absorption spectrum of Eu
3
in GGG obtained between 240 and 320 nm at
85 K. The sharp-line absorption spectrum between 280 and 320 nm is due to
Gd
3
. Inset: spectrum of excitation of luminescence in GGG at 300 K. Wavelength
of observation at l591 nm.
Wavelength (nm)
560 580 600 620 640 660 680 700 720
F
l
u
o
r
e
s
c
e
n
c
e

I
n
t
e
n
s
i
t
y

(
a
.
u
)
0
20
40
60
80
100
5
D
1
7
F
2
5
D
0
7
F
1
5
D
0
F
5
D
1
7
F
4
5
D
0
7
F
3
5
D
1
7
F
5
5
D
0
7
F
4
5
D
1
7
F
6
Fig. 2. Fluorescence spectrum of Eu
3
in GGG obtained at 300 K between 550 and
720 nm while the sample was excited at l
exc
274 nm.
J.B. Gruber et al. / Journal of Luminescence 131 (2011) 19451952 1946
in Table 2. The atomic and crystal-eld energy parameters (in
cm
1
) that predict the splitting are given in Table 3, and are used
to interpret the magneto-optical spectra given in Figs. 4 and 5.
3. Analysis of the Eu
3
spectra in GGG
Each Stark level is non-degenerate and is characterized by one
of four symmetry labels, namely G
1
(A), G
2
(B
1
), G
3
(B
2
), and G
4
(B
3
). In D
2
symmetry, the electric-dipole (ED) and magnetic-dipole
(MD) selection rules for transitions between Stark components
preclude transitions between levels having the same symmetry
label. Lacking polarized spectroscopic data, an algorithm method
was used instead to establish the irreps in a manner similar to the
approach used in analyzing the spectra of other non-Kramers ions
such as Pr
3
, Tm
3
, and Ho
3
in garnets [35,39,40]. The method is
satisfactory when individual Stark levels are sufciently separated
in energy so that the spectra representing transitions between
these levels are resolved. When quasi-doublets, or closely spaced
Stark levels are involved, an analysis of the magneto-optical
spectroscopy must be carried out to identify the transitions.
Selection rules (either ED or MD) preclude uorescence from
5
D
0
to
7
F
0
, since both have the same irrep, namely G
1
. However,
Stark levels of the
7
F
1
manifold (306, 331, and 415 cm
1
) are
sufciently populated at RT so that absorption transitions to
5
D
0
(G
1
) are allowed from all three Stark levels of
7
F
1
(G
3
, G
2
, and G
4
).
The splitting of
7
F
1
is conrmed from an analysis of the RT
uorescence from
5
D
1
to
7
F
1
(Table 1). Both sets of data place
the energy of
5
D
0
at 17,233 cm
1
(see Fig. 3 and Table 2). In
absorption, transitions from both
7
F
0
and
7
F
1
to
5
D
1
allow us to
establish the energy of a quasi-doublet and a singlet in the
5
D
1
manifold given in Table 2. Analysis of the magneto-optical
experiments presented in the following study indicates the
quasi-doublet in
5
D
1
consists of two nearly degenerate Stark
levels having irreps G
4
and G
3
(Table 2). Therefore, the singlet
in
5
D
1
has an irrep of G
2
, approximately 34 cm
1
above the quasi-
doublet and also populated at RT. These levels are designated as
B
1,2
(quasi-doublet) and B
3
(singlet) in Table 1. We use Set 1 values
in Table 2 for all irrep assignments in our analysis, though the
algorithm method works exactly the same for each set, simply
with G
2
, G
3
, and G
4
irrep labels permuted. Fluorescence transi-
tions from the
5
D
1
quasi-doublet are observed to all 2J 1 Stark
levels in the manifolds of
7
F
J
. However, based on the algorithm,
uorescence is not observed from
5
D
0
(G
1
) to other G
1
Stark levels
in
7
F
J
nor is uorescence observed from the G
2
Stark level in
5
D
1
to other G
2
Stark levels in
7
F
J
.
Different uorescence patterns can be observed from the two
lowest-energy Stark components of the
5
D
2
multiplet manifold
observed in RT absorption at 21,402 and 21,425 cm
1
. In a J 2
manifold (2 G
1
, G
2
, G
3
, G
4
) we can expect to observe in the
absorption spectrum three transitions to this multiplet from
7
F
0
(G
1
), and four from G
2
in
7
F
1
at 415 cm
1
. Analysis of the
absorption data indicates that the lowest-energy Stark compo-
nent in
5
D
2
(21,402 cm
1
) has an irrep of G
1
since it is observed in
7
F
1
to
5
D
2
absorption, but not in
7
F
0
to
5
D
2
absorption. Consistent
uorescence patterns from the second level approximately
23 cm
1
higher in energy than the rst indicate the irrep for this
level is G
3
. Other Stark levels and their irreps were also identied
from a combined analysis of absorption and uorescence spectra
of
5
D
2
and are reported in Table 2 as 21,458 cm
1
(G
2
) and
21,480 cm
1
(G
4
). A fth expected Stark level could not be
established in the manifold from the experimental data, and
may indicate the presence of a quasi-doublet.
4. Modeling the crystal-eld splitting
The experimental energy levels analyzed in this study include
57 of the 58 Stark energy levels expected to be split out of the
7
F
J
(J06) and
5
D
0,1,2
multiplet manifolds. The electronic energy
level structure of Eu:GGG is analyzed by means of a model
Hamiltonian dened to operate within the 4f
6
electronic cong-
uration of Eu
3
. All parts of the Hamiltonian that depend upon
4f-electron radial coordinates or describe intermixing from excited
congurations are represented as variable parameters. The model
Hamiltonian is expressed according to standard practice as [41,42]
H E
avg

X
k
F
k
f
k
aLL1 bGG
2
gGR
7

X
i
T
i
t
i
B
so
A
so

X
k
P
k
p
k

X
j
M
j
m
j

X
k,q
B
k
q
C
k
q
1
where k2, 4, 6; i 2, 3, 4, 6, 7, 8; j0, 2, 4; and 9q9rk is
constrained by the site symmetry of the lanthanide ion. The B
k
q
parameters contain radially dependent parts of the one-electron
crystal-eld interactions and the C
k
q
are many-electron spherical
tensor operators acting within the 4f
6
conguration. The B
k
q
parameters with 7q terms are constrained by the expression,
B
k
q
1
kq
B
k
q
, which, for D
2
site symmetry, yields 9 independent
crystal-eld parameters: B
2
0
, B
2
2
, B
4
0
, B
4
2
, B
4
4
, B
6
0
, B
6
2
, B
6
4
, and B
6
6
.
For lanthanide systems having low site symmetry, different
crystal-eld parameter sets can yield identical calculated energy
levels, due to different possible orientations of the crystal-eld
axes [43,44]. For the D
2
symmetry system examined here, the
crystal-eld z-axis may be chosen parallel to any one of three
orthogonal C
2
symmetry axes. Additionally, for each of these
three z-axis orientations, there exist two orientations of the x and
y axes along the two remaining C
2
symmetry axes, resulting in six
alternative sets of crystal-eld parameters for which only the nine
crystal-eld parameters listed above are non-zero [45]. These six
parameter sets correspond to the six possible permutations of the
orthogonal crystallographic a, b, and c axes. However, it is not
possible from the optical data presented here to uniquely identify
which parameterization corresponds to which permutation of the
crystallographic axes.
Transformations between these six equivalent parameter sets
involve 901 rotations about the x, y, and z axes, and have been
investigated by Morrison and Leavitt [9], and Rudowicz and
Bramley [46]. These transformations provide an effective way to
determine the other ve equivalent parameter sets once an initial
set is realized. For completeness, and in order to facilitate
comparison with previous publications, we present all six sets
of crystal-eld parameters in Table 3. Sets 13 (upper and lower
Wavelength (nm)
590 591 592 593 594 595 596
I
n
t
e
n
s
i
t
y

(
a
.
u
.
)
20
40
60
80
100
120
5
D
0
7
F
1
Fluorescence at 300 K
7
F
1
5
D
0
Absorption at 300 K
A
1





Y
1
A
1






Y
2
A
1
Y
3
Fig. 3. Fluorescence (dotted) and absorption (solid line) spectra of Eu
3
in GGG at
300 K showing the transitions between the
5
D
0
and
7
F
1
multiplet manifolds
between 590 to 596 nm while the sample was excited at 274 nm.
J.B. Gruber et al. / Journal of Luminescence 131 (2011) 19451952 1947
signs) are given in modied Morrison and Leavitt notation, where
the signs on the q2, 6 terms of Set 2 are reversed in order to
facilitate transformation between sets [30].
Crystal-eld energy level parameters were determined using a
Monte-Carlo method of random starting parameters [47,48],
where each of the nine crystal-eld parameters are randomly
varied between 71000 cm
1
to create multiple sets of starting
parameters which are then optimized using a standard least-
squares tting between experimental and calculated energy
levels. When many of these calculations are done, the local
minima on the parameter error space are mapped out, along with
the six-fold global minimum. Each local minimum also has a six-
fold solution, and represents a different ordering of the Stark
component energy level states.
Table 3 presents the Hamiltonian parameters (in cm
1
) for the
best-t analysis of 57 experimentally determined energy levels.
The left two columns of this table give the atomic parameters
dened by Eq. (1) with statistical uncertainties given in
Table1
Fluorescence from
5
D
0
and
5
D
1
to
7
F
J
(Eu
3
:GGG).
5
D
0
5
D
1
EuGG
a
2S1
L
J l (nm) E (cm
1
) Transition E
f
(cm
1
) l (nm) E (cm
1
) Transition E
f
(cm
1
) E (cm
1
)
7
F
0
17,233 0 526.70 18,982 B
3
-Z
1
0 0
527.67 18,948 B
1,2
-Z
1
0 0
7
F
1
590.63 16,927 A
1
-Y
1
306 536.31 18,642 B
1,2
-Y
1
306 306
591.51 16,902 A
1
-Y
2
331 537.05 18,617 B
1,2
-Y
2
331 328
594.45 16,818 A
1
-Y
3
415 539.46 18,533 B
1,2
-Y
3
415 409
7
F
2
609.08 16,414 A
1
-X
1
819 551.48 18,129 B
1,2
-X
1
819 819
609.53 16,402 A
1
-X
2
831 551.81 18,118 B
1,2
-X
2
830 832
552.63 18,091 B
1,2
-X
3
857 857
627.35 15,936 A
1
-X
4
1297 566.47 17,649 B
1,2
-X
4
1299 1323
567.08 17,630 B
1,2
-X
5
1318 1342
7
F
3
649.39 15,395 A
1
-W
1
1838 584.31 17,110 B
1,2
-W
1
1838 1830
650.32 15,373 A
1
-W
2
1860 585.17 17,085 B
1,2
-W
2
1863 1853
652.10 15,331 A
1
-W
3
1902 586.51 17,046 B
1,2
-W
3
1902 1896
653.50 15,298 A
1
-W
4
1935 587.64 17,013 B
1,2
-W
4
1935 1924
655.17 15,259 A
1
-W
5
1974 589.3 16,965 B
1,2
-W
5
1983 1974
589.41 16,962 B
1,2
-W
6
1986 1983
663.26 15,073 A
1
-W
7
2160 595.62 16,785 B
1,2
-W
7
2163 2146
7
F
4
605.84 16,502 B
1,2
-V
1
2446 2448
693.81 14,409 A
1
-V
2
2824 620.03 16,124 B
1,2
-V
2
2824 2830
694.68 14,391 A
1
-V
3
2842 620.73 16,106 B
1,2
-V
3
2842
699.0 14,302 A
1
-V
4
2931 624.14 16,017 B
1,2
-V
4
2931 2925
629.56 15,880 B
1,2
-V
5
3068 3070
706.96 14,141 A
1
-V
6
3092 630.55 15,855 B
1,2
-V
6
3093 3088
707.56 14,129 A
1
-V
7
3104 631.03 15,843 B
1,2
-V
7
3105 3097
632.47 15,807 B
1,2
-V
8
3141 3142
712.14 14,038 A
1
-V
9
3195 634.63 15,753 B
1,2
-V
9
3195 3199
7
F
5
742.0 13,473 A
1
-U
1
3760 658.20 15,189 B
1,2
-U
1
3759 3766
743.21 13,451 A
1
-U
2
3782 659.20 15,166 B
1,2
-U
2
3782
661.0 15,125 B
1,2
-U
3
3823 3823
752.84 13,279 A
1
-U
4
3954 666.55 14,998 B
1,2
-U
4
3950 3956
755.80 13,227 A
1
-U
5
4006 669.16 14,940 B
1,2
-U
5
4008 4012
757.86 13,191 A
1
-U
6
4042 670.70 14,906 B
1,2
-U
6
4042 4018
763.70 13,090 A
1
-U
7
4143 675.26 14,805 B
1,2
-U
7
4143 4155
765.16 13,065 A
1
-U
8
4168 676.40 14,780 B
1,2
-U
8
4168 4165
765.93 13,052 A
1
-U
9
4181 677.0 14,767 B
1,2
-U
9
4181 4183
678.56 14,733 B
1,2
-U
10
4215 4215
768.80 13,003 A
1
-U
11
4230 679.25 14,718 B
1,2
-U
11
4230 4232
7
F
6
713.60 14,010 B
1,2
-T
1
4938 4939
715.93 13,964 B
1,2
-T
2
4984 4958
716.25
b
13,958 B
1,2
-T
3
4990 4990
716.25
b
13,958 B
1,2
-T
4
4990 4990
717.25 13,938 B
1,2
-T
5
5010 5009
721.35 13,859 B
1,2
-T
6
5089 5089
721.74 13,852 B
1,2
-T
7
5096 5101
727.30
b
13,746 B
1,2
-T
8
5202 5204
727.30
b
13,746 B
1,2
-T
9
5202 5204
729.55
b
13,703 B
1,2
-T
10
5245 5240
729.70
b
13,701 B
1,2
-T
11
5247
731.55
b
13,666 B
1,2
-T
12
5282 5282
731.6
b
13,664 B
1,2
-T
13
5284
a
Experimental energy levels taken from Ref. [20].
b
Band with structure.
J.B. Gruber et al. / Journal of Luminescence 131 (2011) 19451952 1948
Table 2
Experimental and calculated energy levels, and predicted irreps for Eu
3
in GGG.
Level no. Set 1 Set 2 Set 3 Energy (cm
1
)
2S1
L
J
Irrep (G
n
) M
J
Irrep (G
n
) M
J
Irrep (G
n
) M
J
E
expt
E
calc DE
7
F
0
1 1 0 1 0 1 0 0 12 12
s12.2
7
F
1
2 4 71 2 0 3 71 306 305 1
3 3 71 4 71 2 0 331 332 1
4 2 0 3 71 4 71 415 421 6
s3.5
7
F
2
5 2 72 3 71 4 71 819 819 0
6 4 71 2 72 3 71 830 828 2
7 1 0 1 0 1 72 857 857 0
8 3 71 4 71 2 72 1299 1293 6
9 1 72 1 72 1 0 1318 1313 5
s3.8
7
F
3
10 2 72 3 71 4 73 1838 1839 1
11 3 73 4 71 2 0 1863 1869 6
12 4 71 2 72 3 73 1902 1910 8
13 4 73 2 0 3 71 1935 1944 9
14 2 0 3 73 4 71 1983 1984 1
15 1 72 1 72 1 72 1986 1987 1
16 3 71 4 73 2 72 2163 2172 9
s6.2
7
F
4
17 1 72 1 72 1 0 2446 2441 5
18 2 74 3 73 4 71 2824 2828 4
19 3 71 4 71 2 74 2842 2846 4
20 4 73 2 74 3 71 2931 2936 5
21 1 74 1 0 1 74 3068 3077 9
22 4 71 2 72 3 73 3093 3094 1
23 2 72 3 71 4 73 3105 3103 2
24 1 0 1 74 1 72 3141 3141 0
25 3 73 4 73 2 72 3195 3200 5
s4.5
7
F
5
26 2 0 3 71 4 75 3759 3752 7
27 4 71 2 0 3 75 3782 3778 4
28 1 74 1 74 1 72 3823 3822 1
29 2 74 3 73 4 73 3950 3942 8
30 4 73 2 74 3 71 4008 4004 4
31 3 75 4 75 2 0 4042 4036 6
32 3 71 4 75 2 72 4143 4133 10
33 2 72 3 75 4 73 4168 4162 6
34 4 75 2 0 3 73 4181 4174 7
35 1 72 1 72 1 74 4215 4210 5
36 3 73 4 71 2 74 4230 4224 6
s6.4
7
F
6
37 1 0 1 76 1 74 4938 4945 7
38 4 71 2 72 3 75 4984 4989 5
39 2 72 3 73 4 75 4990 4991 1
40 3 73 4 75 2 74 4990 4993 3
41 4 73 2 76 3 73 5010 5013 3
42 1 74 1 76 1 72 5089 5094 5
43 2 72 3 75 4 73 5096 5097 1
44 1 0 1 72 1 76 5202 5201 1
45 3 71 4 71 2 76 5202 5202 0
46 4 75 2 74 3 71 5245 5247 2
47 3 75 4 75 2 72 5247 5251 4
48 1 76 1 74 1 0 5282 5281 1
49 2 76 3 73 4 71 5284 5283 1
s3.3
5
D
0
50 1 0 1 0 1 0 17,233 17,232 1
s0.9
5
D
1
51 4 71 2 0 3 71 18,948 18,946 2
52 3 71 4 71 2 0 18,948 18,950 2
53 2 0 3 71 4 71 18,982 18,985 3
s2.4
5
D
2
54 1 72 1 72 1 0 21,402 21,412 10
55 3 71 4 71 2 72 21,425 21,422 3
56 2 72 3 71 4 71 21,458 21,455 3
57 1 0 1 0 1 72 21,464
58 4 71 2 72 3 71 21,480 21,474 6
s6.1
J.B. Gruber et al. / Journal of Luminescence 131 (2011) 19451952 1949
parenthesis after the parameter values. Due to the small number
of multiplets examined, all except six of the 20 atomic parameters
were held xed at pre-determined values. This results in a good
tting of barycenters for each
7
F
J
and
5
D
J
multiplet, but care
should be taken in extrapolating the calculation to higher-energy
multiplets, due to the lack of information regarding the values of
the remaining atomic parameters.
The six different sets of crystal-eld parameters corresponding
to the six axes orientations are presented in the three right-hand
columns of Table 3, identied as Sets #13 in modied Morrison
and Leavitt notation. Each column presents two possible sets of
parameter values, indicated by the top and bottom symbols of the
7 signs on the q2, 6 parameters. It should be noted that Set 1b
(lower sign) parameters represent the standardized parameter
set promoted by Rudowicz [31], based on the rhombicity ratio
k B
2
2
=B
2
0
being in the standard range (0,

6
p
), even though the
original Morrison and Leavitt parameters for Nd:YAG used to
dene Sets 1 to 3 have Set 1a (upper sign) in standardized
notation. The reason for this discrepancy can be seen in the small
value of the B
2
2
parameter (577 cm
1
), which has changed sign
between these two systems. This change in sign for the small B
2
2
parameter has been observed previously for Ho:YGG [35].
Calculated energy levels are invariant with respect to para-
meter set selection. However, each of the six sets of parameters
gives differing wave functions and irrep identication for each of
the energy levels. For example, Set 1 (upper sign) parameters
yield an irrep ordering of {G
4
, G
3
, G
2
} for the
7
F
1
multiplet, with
wavefunctions given by an antisymmetric combination of
M
J
71, a symmetric combination of M
J
71, and M
J
0, respec-
tively. Set 1 (lower sign) parameters yield an irrep ordering of
{G
3
, G
4
, G
2
} for the same
7
F
1
multiplet, with wavefunctions given
Table 3
Atomic and crystal-eld energy parameters (in cm
1
) for Eu:GGG. Six alternative crystal-eld parameter sets are presented using modied Morrison and Leavitt notation.
Atomic parameter Value Crystal-eld parameter Value Set 1 Value Set 2 Value Set 3
E
avg
76,311 (19) B
2
0
321 (12) 167 (13) 155 (8)
F
2
113,453 (46) B
2
2
85 (7) 8194 (6) 7199 (9)
F
4
65,605 (87) B
4
0
13 (23) 495 (25) 2050 (17)
F
6
42,207 (53) B
4
2
81610 (15) 71305 (15) 7305 (22)
a [20.16] B
4
4
748 (18) 1152 (16) 978 (14)
b [566.9] B
6
0
1526 (31) 867 (28) 1079 (26)
g [1500] B
6
2
8568 (21) 7542 (20) 8254 (19)
T
2
[300] B
6
4
529 (19) 705 (23) 1225 (18)
T
3
[40] B
6
6
8641 (18) 71006 (18) 8176 (24)
T
4
[60]
T
6
[300]
T
7
[370]
T
8
[320]
z 1342 (2)
M
0
3.76 (0.08)
M
2
[0.56M
0
]
M
4
[0.48M
0
]
P
2
[360]
P
4
[0.50P
2
]
P
6
[0.10P
2
]
535 536 537 538 539 540

D
e
g
r
e
e

o
f

M
C
P
L

(
a
.
u
.
)
100
0

7
F
1
5
D
1
Wavelength (nm)
4
3
2
1
-100
Fig. 4. Luminescence (dotted line) and MCPL spectrum in an external eld
H9.0 kOe (solid line), recorded without smoothing at T300 K on the transition
from
5
D
1
to
7
F
1
uorescence band in Eu
3
:GGG. Inset: scheme of the magneto-
optically active radiative transitions between the Stark sublevels of the
5
D
1
and
7
F
1
manifolds. Along side each Stark level is the corresponding irrep and its energy
(in cm
1
) above the ground state
7
F
0
.
526.5 527.0 527.5 528.0
-60
-40
-20
0
20
40
60
80
100

1
2
(18986)
(18962)
(415)
(331)
(306)
(0)

7
F
0
7
F
1
5
D
1
2
1
M
C
D

(
a
.
u
)
Wavelength (nm)
Fig. 5. Spectral dependence of the optical absorption (dotted line) and the MCD
spectrum (solid line) for EuGG. Inset: scheme of the magneto-optically active
transitions between Stark levels of the
5
D
1
and mixed by an external magnetic
eld the Stark singlet states from the
7
F
0
and
7
F
1
multiplet manifolds.
J.B. Gruber et al. / Journal of Luminescence 131 (2011) 19451952 1950
by a symmetric combination of M
J
71, an antisymmetric com-
bination of M
J
71, and M
J
0, respectively. Similarly, Set 2
(upper sign) parameters yield an irrep ordering of {G
2
, G
4
, G
3
}
and Set 3 (upper sign) parameters yield an irrep ordering of {G
3
,
G
2
, G
4
}. Each of these sets is optically indistinguishable.
Experimental and calculated energies are presented in Table 2,
along with irrep assignments and the largest M
J
components for
each energy level. Irreps given in this table for Sets 13 correspond
to the upper sign on the q2, 6 parameters given in Table 3.
Changing the sign on the q2, 6 parameters to the bottom sign
leaves the G
1
and G
2
states and wave functions invariant, but
results in the swapping of G
3
and G
4
irreps, changing symmetric
combinations of the M
J
(Jodd) with antisymmetric combinations.
As can be seen from this table, for the six possible axis orientations
of the crystal eld, the G
1
states remain invariant, and the other
states take on every possible permutation of G
2
, G
3
, and G
4
.
5. Analysis of the magneto-optical spectra
The complete removal of the degeneracy of the Stark levels of
non-Kramers RE
3
ions like Eu
3
in D
2
sites, provides little
opportunity for the paramagnetic (C-term [49,50]) and diamag-
netic (A-term [49,50]) to contribute to the magneto-optical
activity (MOA) observed in these compounds [51]. Consequently,
the mixing of the wave functions through the interaction with
the external magnetic eld H of two closely spaced (13 cm
1
)
non-degenerate Stark sublevels that form a quasi-doublet state is
the primary means by which we observe MOA [34,38,51]. In the
present study, the observed MCPL and MCD have been brought
about by the optical transitions between the quasi-doublet Stark
levels in
5
D
1
and the relatively separated singlets in other multi-
plet manifolds (
7
F
1
and
7
F
2
).
Using the symmetry selection rules for the matrix elements of
the operators of the ED and MD moments in the A
0
-and C
0
-terms of
MCD or MCPL described in Refs. [33,4951], we can determine
directly the symmetry of one state if we know the symmetry of the
second state that is joined by the transition, whether it is a quasi-
doublet-singlet or singlet-quasi-doublet transition [38]. In
Fig. 4 the spectral dependence of the degree of MCPL on a
luminescence line has a simpler shape than the spectral depen-
dence of the MCD on the absorption line (Fig. 5) [34,49]. This
dependence is linear and is shifted from zero (the center of the
luminescent line) by the value of the amplitude of the C
0
-term [34],
whereas the slope of the linear dependence is determined by the
A
0
-term of the degree of the MCPL [38]. In Fig. 4 the degree of MCPL
in arbitrary units is shown as a function of wavelength for
transition 4 in emission from
5
D
1
to
7
F
1
at 300 K in a magnetic
eld H of 9.0 kOe. The four transitions observed in uorescence are
plotted as dotted lines and show the quasi-doublet-singlet
magneto-optically active transition as 4. The energy level/transi-
tion scheme with irreps given on the right in Fig. 4 is in agreement
with the experimental values reported in Table 2. The symmetry of
the quasi-doublet state at approximately 18,948 cm
1
is dictated
by the symmetry of the
7
F
1
Stark level at 415 cm
1
. Selection rules
for the C
0
-terms of MCPL [34] do not allow the appearance of MOA
on the other observed luminescent transitions.
The MCD spectrum shown in Fig. 5 was obtained between 526
and 528 nm along the [1 1 1] direction of the crystal in a magnetic
eld H of 5.0 kOe at 300 K. The sample in this case was the pure Eu
garnet (EuGG). A slight shift in the spectrum is observed due to the
Eu
3
concentration difference between the two crystals, but the
MOA details and the energy-level scheme is essentially the same.
The dominant MCD feature labeled 2 in the gure has the char-
acteristic S-like shape, similar to the rst derivative of an absorption
curve and represents a singlet to quasi-doublet magneto-optically
active transition from the ground-state
7
F
0
(G
1
) to the quasi-doublet
G
3
, G
4
in
5
D
1
[51]. The MCD feature having the shape of an
absorption line (labeled 1 in Fig. 5) is due to the Van Vleck mixing
between
7
F
0
and
7
F
1
in the presence of the external magnetic eld.
Following the selection rules [34,38] and results from Ref. [50], we
determine this magneto-optical transition to be from the combined
state of G
1
(
7
F
0
), G
4
(
7
F
1
) to the singlet state G
2
in
5
D
1
.
6. Summary
Fluorescence and absorption spectra are reported for Eu
3
(4f
6
)
in Gd
3
Ga
5
O
12
(GGG) between 450 and 760 nm at 85 K and RT. In
absorption, transitions are observed from the ground state,
7
F
0
,
and the rst excited state,
7
F
1
, to excited states
5
D
0
,
5
D
1
, and
5
D
2
.
Fluorescence is observed from
5
D
0
,
5
D
1
, and
5
D
2
to all
7
F
J
multi-
plets. Magneto-optical spectra, including MPCL and MCD, were
analyzed for the energies and irreps for the Stark levels of
5
D
1
and
7
F
1
. Using the assignments obtained for the Stark levels in these
manifolds, an algorithm was used to assign the irreps of Stark
levels in the other multiplet manifolds.
A total of 57 of the 58 Stark energy levels expected were
modeled using a Hamiltonian dened to operate within the 4f
6
electronic conguration of Eu
3
. The choice of crystal-eld axes
used in the present study is identical to that used previously in
analyzing the spectra of Er
3
and Ho
3
garnets [30,35]. Crystal-
eld energy level parameters were determined using a Monte-
Carlo method of random starting parameters, where each of the
nine B
k
q
parameters are randomly varied to create multiple sets of
starting parameters which are then optimized using a standard
least-squares tting between experimental and calculated levels.
Following a global minimization procedure, we obtain a nal rms
deviation of 5.9 cm
1
between the experimental and calculated
levels with all experimentally assigned irreps in agreement with
those predicted by the nal calculation.
Acknowledgments
One of the authors (UVV) gratefully acknowledges Nankai
University (Peoples Republic of China) for nancial support
through Project B07013 for part of his work performed in TEDA
Applied Physics School, and to Dr. Z. Wang for technical assis-
tance. This research was also supported by the National Science
Foundation (NSF) Partnerships for Research and Education in
Materials (PREM) Grant number DMR0934218.
References
[1] G.H. Dieke, Spectra and Energy Levels of Rare Earth Ions in Crystals,
Interscience, NewYork, 1968.
[2] H.M. Crosswhite, H.W. Moos, Optical Properties of Ions in Crystals, Inter-
science, NewYork, 1967.
[3] J.A. Koningstein, Phys. Rev. 136 (1964) A717.
[4] J.A. Koningstein, J. Chem. Phys. 42 (1965) 3195.
[5] C. Brecher, H. Samelson, R. Riley, A. Lempicki, J. Chem. Phys. 49 (1968) 3303.
[6] O.J. Sovers, T. Yoshioka, J. Chem. Phys. 51 (1969) 5330.
[7] R.L. Cone, R. Faulhaber, J. Chem. Phys. 55 (1971) 5198.
[8] P. Porcher, P. Caro, J. Chem. Phys. 65 (1976) 89.
[9] C.A. Morrison, R.P. Leavitt, in: K.A. Gschneidner Jr., L. Eyring (Eds.), Handbook
on the Physics and Chemistry of Rare Earths, vol. 5, North-Holland, Amster-
dam, 1982, p. 489.
[10] C. G orller-Walrand, K. Binnemans, in: K.A. Gschneidner Jr., L. Eyring (Eds.),
Handbook on the Physics and Chemistry of Rare Earths, vol. 25, North-
Holland, Amsterdam, 1998, p. 101.
[11] D.J. Newman, B. Ng, Crystal Field Handbook, Cambridge University Press,
England, 2000.
[12] A.A. Kaminskii, Crystalline Lasers: Physical Processes and Operating Schemes,
CRC, NewYork, 1996.
[13] H. Peng, C.-W. Lee, H.O. Everitt, C. Munasinghe, D.S. Lee, A.J. Steckl, J. Appl.
Phys. 102 (2007) 073520.
J.B. Gruber et al. / Journal of Luminescence 131 (2011) 19451952 1951
[14] R.P. Leavitt, J.B. Gruber, N.C. Chang, C.A. Morrison, J. Chem. Phys. 76 (1982)
4775.
[15] W. Koecher, Solid State Laser Engineering, Springer, New York, 1996.
[16] D.K. Williams, H. Yuan, B.M. Tissue, J. Lumin. 8384 (1999) 297.
[17] U.V. Kumar, D.R. Rao, P. Venkateswarlu, J. Chem. Phys. 66 (1977) 2019.
[18] E. Lippert, G. Rustad, K. Stenersen, Advanced Solid-State Photonics, OSA
Trends in Optics and Photonics, vol. 3, OSA, Washington, D C, 2003.
[19] H.H. Caspers, H.E. Rast, J.L. Fry, J. Chem. Phys. 47 (1967) 4505.
[20] D. Boal, P. Grunberg, J.A. Koningstein, Phys. Rev. B 7 (1973) 4757.
[21] H. Gross, J. Neukum, J. Heber, D. Mateika, T. Xiao, Phys. Rev. B 48 (1993) 9264.
[22] K. Binnemans, C. G orller-Walrand, J. Phys.: Condens. Matter 9 (1997) 1637.
[23] J.B. Gruber, D.K. Sardar, B. Zandi, J.A. Hutchison, C.W. Trussell, J. Appl. Phys.
93 (2001) 3137.
[24] S. Geller, Z. Krist. 125 (1967) 1.
[25] F. Euler, J.A. Bruce, Acta Crystallogr. 19 (1965) 971.
[26] C.D. Brandle, R.L. Barnes, J. Cryst. Growth 20 (1973) 1.
[27] K. Binnemans, C. G orller-Walrand, J. Rare Earths 16 (1998) 204.
[28] K. Binnemans, C. G orller-Walrand, J. Chem. Soc., Faraday Trans. 92 (1996)
2487.
[29] G.W. Burdick, J.B. Gruber, K.L. Nash, S. Chandra, D.K. Sardar, J. Alloys Compd.
488 (2009) 632.
[30] G.W. Burdick, J.B. Gruber, K.L. Nash, S. Chandra, D.K. Sardar, Spectrosc. Lett.
43 (2010) 406.
[31] C. Rudowicz, M. Chua, M.F. Reid, Physica B 291 (2000) 327.
[32] C. Rudowicz, P. Gnutek, Physica B 405 (2010) 113.
[33] A.K. Zvezdin, V.M. Matveev, A.A. Mukhin, A.I. Popov, Rare Earth Ions in
Magnetically Ordered Crystals, Mir, Moscow, 1985.
[34] U.V. Valiev, S.A. Rakhimov, N.I. Juraeva, R.R. Rupp, L. Zhao, Z. Wang, Z.Y. Zhai,
J.B. Gruber, G.W. Burdick, Phys. Status Solidi (b) 245 (2009) 429.
[35] J.B. Gruber, G.W. Burdick, U.V. Valiev, K.L. Nash, N.I. Juraeva, S.A. Rakhimov,
D.K. Sardar, J. Appl. Phys. 106 (2009) 113110.
[36] J.B. Gruber, B. Zandi, M.F. Reid, Phys. Rev. B 60 (1999) 15643.
[37] J.B. Gruber, B. Zandi, U.V. Valiev, S.A. Rakhimov, Phys. Rev. B 69 (2004)
115103.
[38] J.B. Gruber, D.K. Sardar, R.M. Yow, U.V. Valiev, A.K. Mukhammadiev,
V.Y. Sokolov, I. Amin, K. Lengyel, I.S. Kachur, V.G. Piryatinskaya, B. Zandi,
J. Appl. Phys. 101 (2007) 023108.
[39] J.B. Gruber, M.E. Hills, R.M. Macfarlane, C.A. Morrison, G.A. Turner,
G.J. Quarles, G.J. Kintz, L. Esterowitz, Phys. Rev. B 40 (1989) 9464.
[40] J.B. Gruber, M.E. Hills, R.M. Macfarlane, C.A. Morrison, G.A. Turner, Chem.
Phys. 134 (1989) 241.
[41] W.T. Carnall, G.L. Goodman, K. Rajnak, R.S. Rana, J. Chem. Phys. 90 (1989)
3443.
[42] C.A. Morrison, Angular Momentum Theory Applied to Interactions in Solids,
Springer, NewYork, 1988.
[43] C. Rudowicz, J. Qin, J. Lumin. 110 (2004) 39.
[44] G.W. Burdick, M.F. Reid, Mol. Phys. 102 (2004) 1141.
[45] C.A. Morrison, D.E. Wortman, N. Karayianis, J. Phys. C: Solid State Phys.
9 (1976) L191.
[46] C. Rudowicz, R. Bramley, J. Chem. Phys. 83 (1985) 5192.
[47] J.B. Gruber, K.L. Nash, R.M. Yow, D.K. Sardar, U.V. Valiev, A.A. Uzokov,
G.W. Burdick, J. Lumin. 128 (2008) 1271.
[48] J.B. Gruber, S. Chandra, D.K. Sardar, U.V. Valiev, N.I. Juraeva, G.W. Burdick,
J. Appl. Phys. 105 (2009) 023112.
[49] A.K. Zvezdin, A.V. Kotov, Modern Magneto-Optics and Magnetooptical
Materials, IOP Publishing, Bristol and Philadelphia, 1997, p. 386.
[50] U.V. Valiev, A.K. Zvezdin, G.S. Krinchik, R.Z. Levitin, K.M. Mukimov, A.I. Popov,
Sov. Phys.: JETP 58 (1) (1983) 181.
[51] P.J. Stephens, Adv. Chem. Phys. 35 (1976) 197.
J.B. Gruber et al. / Journal of Luminescence 131 (2011) 19451952 1952