Transactions

of theJapan Institute
of Metals,Vol.24,No. 6 (1983),pp. 443 to 449

Substitutional Disorder in a Trirutile-type

MgSb2O6 Crystal Studied by 1 My High-Resolution
Transmission Electron Microscopy

By Shigeo Horiuchi*, Kenji Uchida* and Takeshi Kikuchi*

Structureimagesof a trirutile-type
MgSb2O6 crystaltaken by 1 MV high-resolution transmis-
sionelectronmicroscopyrevealthatthe nearestneighbouringMg and Sb atoms are mutuallysub-
stitutedand the structurebecomes slightly disordered.The substitution
siteisrandom and the
substitution
probabilityisestimatedto be lessthan 10% by comparing the realimage and the cal-
culatedone forrelatively
thickcrystalsof about 10 nm. Four cationclusters
are necessarily
formed
by the substitution
and exciteweak diffusescatteringalong<110>.
(Received
January
22,1983)
Keyrwords: substitutional
disorder,trirutile-type
magnesium antimonate,1 MV high-
resolution
electronmicroscopy,structureimages,calculated
images,substitution
pro-
bability,
cationcluster,
diffuse
scattering

of powdered MgSb2O6(4) and 4 g of Na2B4O6

Ⅰ. Introduction were mixed and heated in a Pt-crucible at

1373 K (1100℃) for 4 h, followed by cooling

The existence of many crystals with trirutile- through 1023 K (750℃) at a rate of 4K/h.

type structure has so far been reported(1). A Transparent crystals smaller than 0.3 mm

magnesium antimonate, MgSb2O6, belongs to grew in the flux. Their X-ray powder diffrac-
such a group. The peak intensity in the X-ray togram identified them as MgSb2O6, which

powder diffraction pattern, however, slightly has a tetragonal symmetry with lattice parame-

deviates from the calculated intensity, de- ters a=0.465 and c=0.923 nm.

pending on the method of crystal preparation(2).

This suggests that the crystals include lattice
imperfections. In the present study we try to

clarify the character of the imperfections in a

MgSb2O6 crystal, which has been prepared

by a flux method, by means of 1 MV high-

resolution transmission electron microscopy

(HRTEM).
Figure 1 shows the crystal structure of

MgSb2O6(3). It is composed of three subcells

of rutile-type structure. The position of oxygen

atoms is the same as that in the rutile-type

structure. Mg and Sb are arranged in a long-

range order, i.e. Mg atoms tend to be apart

from each other as far as possible.

Ⅱ. Experimental

Fig. 1 Unit-cell of trirutile-type MgSb2O6 crystal.

The crystal preparation is as follows: 0.4 g
Open circles represent O, dark small ones Mg and
dark large ones Sb atoms. The structure istetragonal
* National Institutefor Researches in Inorganic with lattice parameters a=0.465 and c=0.923 nm.
Materials,Sakura-mura, Niihari-gun,Ibaraki 305, The nearest neighbouring cations are at the sites
Japan. 1 and 2 or 1 and 3.
 444 Shigeo Horiuchi, Kenji Uchida and Takeshi Kikuchi

The crystals were crushed in an agate mortar.

Fragments obtained were examined by a high-

voltage electron microscope (H-1250 type)

operated at 1 MV. The optical conditions of

the microscope are the same as described in a

previous paper(5).

Ⅲ. Experimental Results and

Interpretation

1. Electron diffraction

Series of electron diffraction patterns were

taken from several fragments by tilting them

inside the microscope. Okl reflexions (k+l=2n)

are excited in accordance with the space group

Fig.3 1 MV HRTEM image of MgSb2O6 under
of P42/mnm(3). It is found in some of diffrac-
the[001]zoneaxisillumination.
The figure
inserted
tion patterns that weak, broad diffuse scattering showstheprojectionofcationrows.a=0.465nm
appears along the <110> directions. An example
is shown in Fig. 2. thephotograph.Itisnoticedthateach projected
siteis imaged as dark dot. The image contrast
2. Structure images
seems locallyinhomogeneous. This is due to
Figure 3 is a 1 MV HRTEM image taken at the damage produced by the electronirradia-
about 70 nm underfocus, which is in the range tion,which rapidlyproceedsin the crystalwith
of the optimum defocus for getting crystal this orientation.
structure images(5). Electrons are incident along Figure 4(a) is an image from a different
the [001] direction. As is known from Fig. 1, crystal,in which electronsare incidentalong
both Mg and Sb atoms are included in each the [110]direction.In thiscase the crystalis
cation row along this direction. The projection rather stableagainstthe electronirradiation.
of cation rows -Mg-Sb-Sb-Mg-is inserted in Dark lines elongate parallelto the c axis.
Fig. 3 with the same magnification as that of A thin area at the edge of the fragment is
enlarged in (b),in which the arrangement of
dark and brightsitesis irregular; the contrast
is darker at the parts marked by upward ar-
rows, while brighter at downward ones. In
the inner, thickerarea, on the other hand,
thecontrastmakes a regularpattern,as noticed
in an enlargedphotograph in (c).
In order to interpretthe above contrast
anomaly in the thin area,we have performed
acomputer simulation.In the [110]projection,
Mg and Sb atoms are arrayedin different rows,
unlessthere are latticeimperfections, and the
projectedsitesof Mg atom rows show a slightly
dark contrast,while those of the two adjoining
Sb atom rows givean elongateddark contrast
(Fig.5(a)).In the calculation,the dynamical
Fig.2 Electron diffractionpattern of MgSb2O6. interactionamong 140 waves are taken into
Electrons are incident nearly parallelto the [001] account according to the multi-slice method.
direction.Diffuse scatteringappears along <110>. The sphericalaberration coefficientof the
Substitutional Disorder in MgSb2O6 Studied by 1 MV High-Resolution Transmission Electron Microscopy 445

Fig.4 (a) 1 MV HRTEM image of a wedge-form MgSb2O6 crystalunder the [110]zone axis
illumination.The thinand thickareas are enlarged in (b)and (c),respectively.
c=0.923 nm

objective lens is taken as 10 mm, the mean and some of the resultsare shown in Fig.5(b)
fluctuation of defocus due to chromatic aberra- and (c).In (b) one of the three cations are
tion as 20 nm and the beam convergence as assumed to be substituted
in thewhole thickness
8×10-4 rad(5)(6). The thickness of crystal is of 1.97nm. The site1,which has been occupied
assumed to be 1.97 nm (6 slices) by Mg in the idealstructure, is slightly
dark-
A possible origin of the contrast anomaly ened, whilethe site2,which has been occupied
is that Mg and Sb atoms are locally sub- by Sb, brightened.In (c) two of the three
stituted between the nearest neighbouring cationsare substituted. It is noticed that the
cation sites like 1 and 2 or 1 and 3 in Fig. 1. image contrastchanges clearlydepending on
It should be noted that even after this sub- the fraction of substitution.Although the
stitution two Mg atoms never adjoin at the calculationisperformed on a simplified model,
nearest cation sites. First we assume for a we may say that the contrastanomaly in the
thin fragment that the substitution occurs only thin area is related to the substitutionof
between the sites 1 and 2. The change in the canons.
contrast due to the substitution is calculated, In realitythe substitutionmust be possible
 446 Shigeo Horiuchi, Kenji Uchida and Takeshi Kikuchi

Fig. 5 Calculated images of MgSb2O6 under the

[110] zone illumination. Frameworks correspond
to those in Fig. 4(b) and (c). Dark circles and
figures in (a) have the same meaning as in Fig. 1.
The thickness of crystal is 1.97 and 8.88 nm for
(a) to (c) and (d) to (f), respectively.

at any cation sites. In the calculation for a

thicker area like in Fig. 4(c) we may assume

that the site of the substitution is at random,

since the image contrast is apparently regular.

The calculation has been performed on this

assumption with changing value of the sub-

stitution probability a and crystal thickness.

For examples, Fig. 5(d) to (f) are obtained for

α=0.05, 0.15 and 0.33, respectively, with the

crystal thickness of 8.88 nm. The image (d)

well fits the real image in Fig. 4(c). In the

range of higher probability ((e) and (f)) the

calculated image contrast no longer coincides

with the real one. In (f) it is composed of the

contrast of three rutile-type subcells, which Fig.6 Intensity

(a)and phase(b)of main diffracted
are mutually identical. Similar images to (d)
waves vs crystal
thickness.1 MV electronsare
incident
alongthe [110]zone axisof MgSb2O6.
are obtained in the thickness range between 7
The calculation
isperformedfortheidealstructure
and 12 nm unless α exceeds 0.1. Based on these shown inFig.1.A:000, B:001,C:003, D:110,
results we may conclude that the substitution E:111 and F:113.
occurs with the probability less than 0.1. In
thiscalculation
the probability
isintroduced relatively
small amount at the thicknessaround
through the challgein the scattering
amplitude 10 nm. This is reason why the image contrast
for phase grating. seems identicalin a wide range of thickness
Figure 6(a) and (b) show the thickness mentioned above. It isinteresting
to note that
dependence of the diffractionintensityand for the crystalthinnerthan 2 nm the phase of
phase, respectively. Both the intensityand the diffractedwaves, which are kinematically
phase of these scatteringwaves change in a absent (waves B and C in the figures)or
 Substitutional Disorder in MgSb2O6 Studied by 1 MV High-Resolution Transmission Electron Microscopy 447

kinematically very weak (E), is largely deviated

from that of the strongly scattered waves

(D and F). This must be due to that the former

waves are excited mainly by the double dif-
fraction effect.

The crystal with the [100] zone axis orienta-

tion is so sensitive to electron irradiation that

any clear structure image can not be obtained.

Ⅳ. Discussion

1. Possible lattice imperfections

In order to explain the contrast anomaly

in the 1 MV HRTEM images, we have proposed Fig.8 Diffraction
pattern
showingthestreaks
along
the substitution between the nearest neighbour- [110].Electrons
areincideht
hearlynormalto the
ing Mg and Sb atoms. The occurrence of this (110)planeofMgSb2O6.
type of lattice imperfection seems reasonable

from the viewpoint of free energy; it is clear canons are most denselypacked, allthe canons
from Fig. 1 that in the trirutile-type structure in a region A are shiftedby c/3 in the [001]
the pairs of nearest neighbouring Mg and Sb direction.An adjoining region B keeps the
atoms tend to be as large as possible in number. originalstructure.Both the regionsA and B
On the occurrence of the substitution the become mutually in the anti-phaserelation.
number of the pairs is unchanged. This means The atom plane in the regionA forms a stack-
that the charge neutrality is kept in local, ing faultin the directionnormal to the (110)
small areas and the mechanical strain does not plane.If the faultwould take placefrequently,
become large; i.e. the enthalpy of crystal is the diffractionstreaksshould be excitedalong
kept substantially unchanged. the directionnormal to (110).It should be
From the viewpoint of free energy, another noted that two Mg atoms adjoin, although
type of lattice imperfection as shown in Fig. 7 locallyalong the anti-phaseboundary.
seems probable; in the {110} plane, where Figure 8 isa diffractionpattem, found with
very low frequency.Weak but sharp diffraction
streaksrun along [110],suggestingthe forma-
tion of the faultsdiscussedabove. The crystals
giving this type of streak are, however, so
sensitiveto electronirradiationthat no clear
structureimage have been obtained.

2. Clustersgivingthe <110> diffusescat-

tering
The substitution between the nearestneigh-
bouring Mg and Sb atoms causes each (001)
plane to include two speciesof cations.This
necessarilyresultsin the formation of clusters,
as schematicallyshown in Fig. 9; each cluster
Fig. 7 Model of stacking fault, whose plane is is composed of 4 cations.The clustersexcite
paralielto (110) of MgSb2O6. Only the cation the diffuse scattering(7)(8), whose intensity
sitesare shown. Open circlesrepresentMg atoms
locus is defined by
and dark ones Sb. Areas A and B are mutually in
the anti-phase relation,and their boundary is f(g)=Σlωiexp(-2πig・rl)=0, (1)
shown by the broken lines.
 448 Shigeo Horiuchi, Kenji Uchida and Takeshi Kikuchi

Fig. 9 Model of 4 cation cluster, which can explain

the origin of diffuse scattering along <110>. All the
cation sites in the (001) plane of MgSb2O6 are
shown.

where r and g are the vector in real and recipro-

cal space, respectively, and cot the cluster pa-

rameter. For the present clusters with ω10=

Fig. 10 Reconstructed image of a thin crystal of
ω10=1 and ω01=ω01=-1
MgSb2O6 under the [110] zone axis illumination.
sinπ(h+k)sinπ(h-k)=0. (1)' Random occurrence of the substitution is assumed
to take place with α=0.1.
Then, we have

cupied by Mg. When it is between 0 and α,

h±k=m, (2)
we examine another random number. If the
where m is an integer. The eq. (2) explains the value is between 0 and 1/3, the site is still
origin of the diffuse scattering along <110> occupied by Mg. If it is between 1/3 and 1,
found in Fig. 2. on the other hand, the site must be substituted
The cluster relation(7) is by Sb. From a series of such calculation we

obtain the modified structure with one atom

σ10+σ10-(σ01+σ01)=0, (3)
thickness in the direction normal to the (110)

where σj is the Flinn operator. For the (001) plane. We then reconstruct an image contrast

plane, which has been composed only of Mg by allocating the intensity, which has been

atoms in the ideal structure and includes a calculated for the ideal structure in Fig. 5(a),

small amount of Sb after the substitution, σj to each cation site of the modified structure.

has a value of -α for the site occupied by Mg, Some reconstructed images obtained in the

while 1-α for the site by Sb. same way as above are superposed on one
another to get a final image. An example of the

3. Contrast simulation for thin crystals result is shown in Fig. 10, where α is taken as

0.1 and the number of superposed images is

We can simulate the image contrast in the 6 corresponding to the crystal thickness of

thin crystal as follows; we consider the modi- 1.97 nm. The pattern of Fig. 10 is irregular
fication of each cation site from the ideal and the contrastfeatureis essentially
similar
structure due to the substitution. The sub- to thatof therealimage in Fig.4(b).
stitution probability discussed above is related

to the random number, which can be generated

Acknowledgments
directly in the computer according to the The authors wish to expresstheir deep
program incorporated. For the site originally gratitude
to Dr. A. Watanabe and Dr. N.D.
occupied by Mg, as an example, if the value Zakharov for discussion
and to Mr. Y. Seki-
of random number obtained is between α and kawa forassistance
in theexperiment.
1, the site is not modified, i.e. the site is oc-
Substitutional Disorder in MgSb2O6 Studied by 1 MV High-Resolution Transmission Electron Microscopy 449

(5)S. Horiuchi: Ultramicroscopy, 10 (1982),229.

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