ARTICLE IN PRESS

Physica B 404 (2009) 3035–3037

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Physica B
journal homepage: www.elsevier.com/locate/physb

The g-value of Er3þ doped unfilled skutterudite CoSb3 (Th ) reveals the
existence of an additional sixth order term in the crystal field Hamiltonian
J.M. Vargas a, F.A. Garcia a, C. Rettori a,, D.J. Garcia b, B. Sales c, P. Schlottmann d, S.B. Oseroff e
a
Instituto de Fı́sica ‘‘Gleb Wataghin’’, UNICAMP, Campinas-SP 13083-970, Brazil
b
Consejo Nacional de Investigaciones Cientı́ficas y Tecnicas & Centro Atómico Bariloche, S.C. de Bariloche, RN, Argentina
c
Oak Ridge National Laboratory, Oak Ridge, TN 37831, USA
d
Department of Physics, Florida State University, Tallahassee, FL 32306, USA
e
San Diego State University, San Diego, CA 92182, USA

a r t i c l e in fo abstract

Electron spin resonance (ESR) experiments have been carried out in single crystals of the unfilled
PACS: skutterudite CoSb3 doped with Er ions. The X- (9.5 GHz) and Q- (34.4 GHz) band spectra obtained at low
75.20.En temperature (4–20 K) shown a temperature independent g-value of 6.21(5). This g-value can only be
75.20.Hr explained with the addition of a second sixth order Bt6 ðO26  O66 Þ term to the usual cubic crystal field
76.30.v Hamiltonian. The ESR of Er3þ show the typical temperature dependence of the line-shape and line-
76.30.Kg width expected for insulating host.
& 2009 Elsevier B.V. All rights reserved.
Keywords:
Filled skutterudite
Antimonides
CoSb3
Rare-earth metal

1. Introduction thermal conductors [1]. Although in the existing literature there is

detailed information about the macroscopic response of the
The study of the unfilled skutterudites CoSb3 doped with rare- filled–unfilled rare-earths ions located in the oversized skutter-
earth (RE) ions have attracted the attention of the scientific udites cages, there is a limited knowledge about the microscopic
community due to their interesting thermoelectric properties that local crystal field (CF) at the rare-earths site. Electron spin
make them attractive for potential thermoelectric energy con- resonance (ESR) can provide, even when the compound is not
verting devises [1]. Besides, these systems may provide a paramagnetic, useful information by doping the matrix with a
3þ
canonical illustration of the Einstein model, because the RE ions small amount of paramagnetic ions such as Gd , Dy3þ , Er3þ and
3þ
are located in oversized cages that are believed to ‘‘rattle’’ Yb . The ESR spectra of the impurities allow not only to learn
independently of each other and of the neighboring atoms making about their magnetic state, but also to study the properties of the
up the cage [2]. The RE-doped antimony skutterudite are nice host lattice. In this work, we present an ESR study of the ground
examples of phonon glass and a electron crystal, with the state of Er3þ doped in the unfilled CoSb3 skutterudite.
simultaneous requirement of low thermal conductivity and high
electrical conductivity that characterize a disordered (glassy)
material and a crystalline material, respectively [3]. The unfilled 2. Experimental
antimony skutterudite, CoSb3 , crystallizes in a body-centered-
cubic phase with a unit-cell parameter of 9:037 A [4]. The unfilled Single crystals of CoSb3 doped with 1000 ppm of Er, were
˚
skutterudites can be filled up to one atom/formula by introducing grown in a molten Sb flux according to the method described in
a RE in the dodecahedral void formed by twelve antimony and Ref. [5]. The dc magnetic measurements were taken in a quantum
eight cobalt atoms. Thus, one may obtain different systems with a design MPMS SQUID magnetometer. The crystals used were about
great variety of metallic, semiconducting and insulating proper- 2  2  2 mm3 with perfect natural crystallographic grown faces.
ties. These properties make them versatile and tunable electrical- The cubic structure (space group Im3) and phase purity were
checked by X-ray powder diffraction. The ESR spectra were taken
in Bruker X- (9.48 GHz) and Q- (34.4 GHz) band spectrometers
 Corresponding author. using appropriated resonators coupled to a T-controller of a
E-mail address: rettori@ifi.unicamp.br (C. Rettori). helium gas flux system for 4:2tTt300 K.

0921-4526/$ - see front matter & 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.physb.2009.07.012
 ARTICLE IN PRESS
3036 J.M. Vargas et al. / Physica B 404 (2009) 3035–3037

3. Results and discussion expected for insulating hosts; (ii) the Q-band line-width data is
similar to the X-band one, therefore, no inhomogeneous
Fig. 1 shows the X-band ESR spectrum at T ¼ 4:2 K, with the broadening is observed; and (iii) an exponential increase of DH
typical resolved hyperfine structure of Er3þ . The resonances at high-T is observed. The homogeneous line broadening results
correspond to the 166 Er3þ (I ¼ 0) and 167 Er3þ (I ¼ 72) isotopes [6]. from a phonon spin-lattice relaxation process involving excited CF
The Lorentzian line-shapes are expected for insulating hosts and levels. In this case the T-dependence of the line-width can be
the hyperfine structure corresponds to a hyperfine parameter of written as
A ¼ 78:5ð5Þ Oe. The g-value of 6.21(5) at T ¼ 4:2 K is quite different
D3
than those expected for isolated G7 (gG7 ¼ 6:80) and G6 DH ¼ a þ c ; ð1Þ
(gG6 ¼ 6:00) doublets in the usual Oh cubic symmetry. Besides, ½eD=kT  1
this value is smaller than that measured for the Er3þ in the semi- where a is the residual line-width, c is a constant and D is the
metallic skutterudite CeFe4 P12 , g ¼ 6:408ð3Þ [7]. The g-value is energy separation between the ground and first excited state.
found to be T-independent between 4.2 and 20 K and Q-band From the fitting of the line-width using Eq. (1), we obtain
experiments gives also a g-value of 6.21(5). The T-dependence of a ¼ 5:4ð4Þ Oe, c ¼ 0:0009ð1Þ Oe=K3 , and D ¼ 84ð15Þ K. It is
the ESR intensity follows approximately the Curie–Weiss behavior interesting to mention that the D value is similar to the one
(not showed), indicating that the resonance arise from a Kramers reported for the Er3þ ions doped into the filled skutterudite
doublet ground state of the CF split J-multiplet of Er3þ (J ¼ 15 2 ). CeFe4 P12 . Therefore, the crystal field environment is probably
Fig. 2 shows the T-dependence of the line-width, DH, at X- and similar for Er3þ in both, unfilled CoSb3 (insulator) and filled
Q-band between 4.2 and 20 K. These results shows that: (i) a CeFe4 P12 (semiconductor) skutterudite systems.
linear T-term (Korringa relaxation) is negligible at low-T, as Fig. 3 shows the magnetization loop (750 kOe) at T ¼ 2 K, after
substraction of the sample holder and host CoSb3 diamagnetic
contributions. From the low-field magnetic susceptibility we
estimate an Er3þ concentration of 1000 ppm. The
magnetization loops show that: (i) there is no saturation up to
H ¼ 750 kOe; and (ii) it is magnetically reversible with no
hysteresis effects, indicating the absence of strong interactions
between the localized 4fEr3þ ions.
The striking large g-shift measured for the Er3þ resonance
could only be explained by the absence of two symmetry
operations in the T and Th groups, namely C4 and C20 rotations
[8]. Takegahara et al. noticed that due to the absence of these
symmetry operations [9], the CF Hamiltonian (HCF ) should include
an additional sixth order terms with an extra crystal field
parameter (CFP), Bt6 . Therefore, for Th symmetry, in terms of
Steven’s operators [10], the HCF should be written as

HCF ¼ Bc4 ðO04 þ 5O44 Þ þ Bc6 ðO06  21O46 Þ þ Bt6 ðO26  O66 Þ; ð2Þ
where the last term is absent in the ordinary cubic symmetry Oh.
We now add the Zeeman term gJ mB H  J to Eq. (2), where gJ is the
Lande g-factor, mB the Bohr magneton, J the total angular
momentum for Er3þ ion and H is the external magnetic field.
Fig. 1. ESR spectrum of Er3þ in CoSb3 measured at T ¼ 4:2 K. Following Lea, Leask and Wolf (LLW) [11] the Hamiltonian can be

Fig. 3. Magnetization loops for Er3þ measured at T ¼ 2 K. The contribution of the

Fig. 2. T-dependence of DH of X- and Q-band ESR for Er3þ in CoSb3 . The solid line sample holder and host lattice to the measured magnetization has been
is fit to Eq. (1) leading the value for the energy gap D ¼ 84ð15Þ K. subtracted.
 ARTICLE IN PRESS
J.M. Vargas et al. / Physica B 404 (2009) 3035–3037 3037

1 7 4. Conclusions

6 Although in the existing literature there is detailed information

0.8
5 about the macroscopic response of the filled–unfilled rare-earths
ions located in the oversized skutterudites cages, there is a limited
0.6 4 knowledge about the microscopic local CF at the rare-earths site.
yB

In this work we studied, by ESR, the ground state of Er3þ in the

0.4 3
unfilled CoSb3 skutterudites. The samples were doped with Er
2 concentrations at 1000 ppm. The X- and Q-band ESR spectra
0.2 measured at low-T (4–20 K) show a T-independent g-value of
1 6.21(5). This g-value can only be explained with the addition of a
0 0 second sixth order Bt6 ðO26  O66 Þ term to the usual cubic CF
-1 -0.5 0 0.5 1 Hamiltonian. The Er3þ resonance show the typical T-dependence
of the line-shape and line-width expected for insulating host. The
xB
exponential T-dependence of DH allowed us to determine an
Fig. 4. Ground state g-values for Er3þ (J ¼ 15 6 energy separation of D ¼ 84ð15Þ K for the first CF excited state.
2 ; gJ ¼ 5) as a function of (x; y). The blue
dashed line indicates the set of (x; y) values corresponding to g ¼ 6:21. (For
interpretation of the references to color in this figure legend, the reader is referred
to the web version of this article.) Acknowledgments

The work at UNICAMP was supported by FAPESP and CNPq,

Brazil. Research at ORNL sponsored by the Division of Materials
Sciences and Engineering, Office of Basic Energy Sciences, U.S.
parameterized as
Department of Energy.
( " # )
Oc4 Oc6 Ot6
HCFZ ¼ W ð1  jyjÞ x þ ð1  jxjÞ þ y þ gJ mB H  J; ð3Þ References
F40 F60 F62

where we denoted O04 þ 5O44 by Oc4 and similarly the sixth order [1] H. Sato, D. Kikuchi, K. Tanaka, M. Ueda, H. Aoki, T. Ikeno, S. Tatsuoka, K.
terms by Oc6 and Ot6 , respectively. The coefficients of Eq. (2) are Kuwahara, Y. Aoki, M. Kohgi, H. Sugawara, K. Iwasa, H. Harima, in:
Proceedings of the International Conference on New Quantum Phenomena
rewritten as Bc4 ¼ ð1  jyjÞxW=F40 , Bc6 ¼ ð1  jyjÞð1  jxjÞW=F60 and in Skutterudite and Related Systems (Skutterudite 2007) J. Phys. Soc. Japan.
Bt6 ¼ yW=F62 . The coefficients Fnm are tabulated in Ref. [12] for 77 (Suppl. A) (2008) 1–6.
various values of J. The above is a generalization of the LLW [2] R.P. Hermann, F. Grandjean, G.J. Long, Amer. J. Phys. 73 (2005) 110.
[3] A. Ohno, S. Sasaki, E. Nishibori, S. Aoyagi, M. Sakata, B.B. Iversen, Phys. Rev. B
Hamiltonian that includes the Ot6 -term [8,11]. Now, the entire 76 (2007) 064119.
range of the CF parameters are accounted for within the finite [4] B.C. Chakoumakos, B.C. Sales, J. Alloy Compd. 407 (2006) 87.
intervals ð1rxr1Þ and ð1ryr1Þ, where y ¼ 0 correspond to [5] G.P. Meisner, M.S. Torikachvili, K.N. Yang, M.B. Maple, R.P. Guertin, J. Appl.
Phys. 57 (1985) 3073.
the Oh symmetry and ya0 to a generic Th symmetry. Fig. 4 shows [6] R.N. Mesquita, G.E. Barberis, C. Rettori, M.S. Torikachvili, M.B. Maple, Solid
the x and y dependence of the g-value for the ground state of Er3þ State Comm. 74 (1990) 1047.
(J ¼ 15 6
2 ; gJ ¼ 5; W40) in a color scale (from g ¼ 0 in black to g ¼
[7] D.J. Garcia, F.A. Garcia, J.G.S. Duque, P.G. Pagliuso, C. Rettori, P. Schlottmann,
M.S. Torikachvili, S.B. Oseroff, Phys. Rev. B 78 (2008) 174428.
6:8 in yellow). The white region in Fig. 4 corresponds to the
[8] K. Takegahara, H. Harima, A. Yanase, J. Phys. Soc. Japan 70 (2001) 1190.
quadruplet ground states. A g-value of 6:2 corresponds neither to [9] T. Inui, Y. Tanabe, Y. Onodera, Group Theory and its Applications in Physics,
a G6 (gG6 ¼ 6:000) nor to a G7 (gG7 ¼ 6:800). For ya0 the g-value Springer, Berlin, 1966.
[10] A. Abragam, B. Bleaney, EPR of Transition Ions, Clarendon Press, Oxford, 1970.
decreases and approaches to zero for large values of y (black
[11] K.R. Lea, M.J.M. Leask, W.P. Wolf, J. Phys. Chem. Solids 23 (1962) 1381.
region). Hence, the measured g-value of 6:2 for Er3þ corresponds [12] M.T. Hutchings, Solid State Phys. 16 (1964) 227.
to a Kramers doublet ground state with ya0. Such a g-value is [13] From the (x; y) dependence of the g-value, in the case of ya0, the calculated g-
obtained for the set of (x; y) values indicated by the dashed blue shift is always negative, i.e., for ya0 the g-value is reduced respect to that of
y ¼ 0. Considered the measured g-value of 6.21(5) for Er3þ in our sample and
line in Fig. 4, and correspond to the G15 ground state arising from the g-values of gG7 ¼ 6:80 and gG6 ¼ 6:00 for isolated Er3þ ions (y ¼ 0), the G15
the G7 [13]. These results do not depend on the sign of y. ground state (ya0) with a g-value of 6.21 can only arise from a G7 .