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Inverse Spinel Structure
Inverse Spinel Structure
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Powder ZnAl2O4 (gahnite) samples doped with 0–100 at% Co were obtained by a sol-gel technique.
X-ray powder diffraction was used to characterize the samples. Gahnite samples are cubic with the
normal spinel structure, space group Fd3m. Cobalt doping caused a nonuniform increase of unit-cell
parameter. The structure of the gahnite samples was refined by the Rietveld method. The location of
Co2+ was determined by EPR spectroscopy. Cobalt doping of gahnite induces the inverse spinel structure
at only 4 at% Co, and the inversion parameter increases with Co2+ doping level. Metal-oxide distances
in the (Al,Co)O6 octahedra dominantly influence the unit-cell parameter of Co-doped gahnite.
Keywords: Co-doped gahnite, spinel structure, X-ray powder diffraction, Rietveld method
part of Co2+ substitutes for Zn2+ on tetrahedral cation sites, and centration of Co2+ centers. The amount of splitting between these
the remaining Co2+ substitutes for Al3+ on octahedral cation sites lines is 11.5 mT (insert in Fig. 2) and corresponds to eight lines
in the ZnAl2O4 lattice, causing the increase of unit-cell parameter of hyperfine splitting of 59Co nuclear spin (I = 7/2). The effec-
(ionic radii of octahedrally coordinated Al3+ and high-spin Co2+ tive g value of this spectral component is g = 7.79. To elucidate
being 0.535 and 0.745 Å, respectively). A nonuniform increase a possible character of the obtained EPR spectra, the additional
of unit-cell parameter with increase of Co-doping level (Fig. 1) spectra for sample S1 were taken at 35 and 70 K (Fig. 3). With
suggests a nonuniform Co2+ substitution mechanism. the increase in temperature, the intensity of EPR components
decreased. At 70 K, the spectrum became dominated by two
EPR spectroscopy broad components at g = 5.30 and g = 2.0 indicating that these
EPR spectra of the samples S1, S2, and S3 collected at 10 K components had a slightly slower relaxation than other spectrum
are shown in Figure 2. The spectra display a typical distorted axial components seen at lower temperatures. This evidently showed
pattern for high-spin Co2+ centers with three major resonance that the EPR spectra of Co-doped gahnite have the composite
features. These spectra are in agreement with expectation for character. The components can be identified as contributions to
molecules with S = 3/2 subjected to zero-field splitting where the spectra from Co2+ cations in more than one local environment.
only the (±1/2) Kramer’s doublet, identified from the effective Indeed, in accord with the previous EPR studies (Sellin et al.
g values, is resonant (Weil et al. 1994). An additional multiple 1983) the values g = 7.79, g = 2.22, and g = 1.84 and hyperfine
splitting with low intensity is incorporated in the broad low-field splitting are consistent with Co2+ center on distorted octahedral
resonance signal, as clearly seen for the sample with lowest con- cation site. On the other hand, the spectral components at g =
5.30 and g = 2.0 are characteristic of Co2+ centered on the tet-
rahedral cation site (Pountney and Vašak 1992). Based on these
results, a general formula for Co-doped gahnite can be written
as IV[Zn1–xCox–δAlδ] VI[Al2–δCoδ] O4, where x represents the level
of incorporated Co2+ cations in the gahnite structure, and δ is the
inversion parameter of the spinel structure.
FigurE 3. EPR spectra of sample S1 taken at 10, 35, and 70 K. FigurE 4. Result of the Rietveld refinement for samples S0 and S4.
774 POPOVIć ET Al.: INVERSE SPINEl STRUCTURE IN Co-DOPED GAHNITE
Table 2. Results of Rietveld refinements: Structural parameters and their standard deviations for samples S0, S1, S2, S3, S4, S6, S8, and S10
Sample δ Rwp Atom site Wyck. position Occupancy x=y=z Biso (Å2)
S0 0 0.059 IV
A 8a 1 Zn 0.125 0.97(2)
VI
B 16d 1 Al 0.5 0.29(3)
O 32e 1O 0.2644(1)* 0.53(5)
S1 0.037(4) 0.068 A
IV
8a 0.003 Co + 0.96 Zn + 0.037 Al 0.125 0.90(1)
B
VI
16d 0.0185 Co + 0.9815 Al 0.5 0.45(2)
O 32e 1O 0.2640(1) 0.48(3)
S2 0.051(3) 0.072 A
IV
8a 0.029 Co + 0.92 Zn + 0.051 Al 0.125 0.90(2)
B
VI
16d 0.0255 Co + 0.9745 Al 0.5 0.47(2)
O 32e 1O 0.2636(1) 0.51(3)
S3 0.055(4) 0.057 A
IV
8a 0.065 Co + 0.88 Zn + 0.055 Al 0.125 0.90(2)
B
VI
16d 0.0275 Co + 0.9725 Al 0.5 0.44(1)
O 32e 1O 0.2634(9) 0.43(3)
S4 0.070(3) 0.054 A
IV
8a 0.18 Co + 0.75 Zn + 0.07 Al 0.125 1.06(6)
B
VI
16d 0.035 Co + 0.965 Al 0.5 0.48(1)
O 32e 1O 0.2631(8) 0.55(2)
S6 0.095(4) 0.056 A
IV
8a 0.405 Co + 0.5 Zn + 0.095 Al 0.125 0.94(3)
B
VI
16d 0.0475 Co+0.9525 Al 0.5 0.64(2)
O 32e 1O 0.2629(1) 0.63(3)
S8 0.150(4) 0.059 A
IV
8a 0.6 Co + 0.25 Zn + 0.15 Al 0.125 0.58(2)
B
VI
16d 0.075 Co + 0.925 Al 0.5 0.68(2)
O 32e 1O 0.2625(1) 0.67(3)
Inversion parameter δ
FigurE 6. Metal-oxygen distances in tetrahedra and octahedra of
gahnite with inversion parameter δ.
caused by Co doping (Fig. 7b) has the same trend as the change
of unit-cell parameter of gahnite (Fig. 1). This is quite under-
standable since the metal-oxygen bonds in octahedra, Moct-O, are
almost parallel to the [100], [010], and [001] axes. The change
of interatomic distances in tetrahedra has much smaller impact
on the unit-cell parameter of gahnite because Mtetr-O bonds make
an angle of ~53° with the [100], [010], and [001] axes. Besides,
in the spinel-type structure there are twice as many structural
octahedra as tetrahedra.
The nonuniform increase in the unit-cell parameter of gahnite
with increasing Co content may be explained by the results of
the Rietveld structure refinements as follows. In doping, a por-
tion of the Co content occupies tetrahedral sites of the gahnite
structure (substituting for Zn), and a portion occupies octahedral
sites (substituting for Al). The portion of Co that occupies the
octahedral sites is given by the ratio of inversion parameter (δ)
FigurE 7. Metal-oxygen distances in (a) structural tetrahedra and and total Co content (x), namely δ/x. Figure 8 presents the de-
(b) structural octahedra as a function of Co content in gahnite. pendence of δ/x on Co content, x, in doped gahnite samples. For
the examined doped gahnite samples, δ/x has a minimum at Co
ously increase almost linearly. The same type of dependence on content x = 0.5, as seen in Figure 8. According to this, at a low
inversion parameter of the metal-oxygen distances was noted for Co-doping level the portion of Co on octahedral sites is a large
CoAl2O4 samples that suffered an increase of structure inversion part of total Co content (almost 93% of total Co content at x =
on annealing (Nakatsuka et al. 2003). 0.04). This induces a pronounced increase of unit-cell parameter
Changes in metal-oxygen distances in structural tetrahedra for low doping levels. In further doping, the portion of Co on
and octahedra of gahnite as a function of Co-doping level are octahedral sites decreases until it reaches 19% of total Co content
shown in Figure 7. Metal-oxygen distances in tetrahedra decrease for doping level x = 0.5, causing a slower increase of unit-cell
with doping level (Fig. 7a), while metal-oxygen distances in parameter with saturation at x = 0.5. After the doping level of
octahedra increase (Fig. 7b). It is obvious that the change of 0.5, the portion of Co on octahedral sites increases, which causes
metal-oxygen distance in the structural octahedra of gahnite a renewed faster increase of unit-cell parameter at x > 0.5.
776 POPOVIć ET Al.: INVERSE SPINEl STRUCTURE IN Co-DOPED GAHNITE