Spectrochimica

Acta,Vol.34A,pp.50510514.
@ Pergamon Press Ltd., Printed in Great Britain

Vibrational spectra of bismuth oxide and the sillenite-structure

bismuth oxide derivatives*
REGIS J. BEXCH and WILLIAM B. WHITER
Materials Research Laboratory, The Pennsylvania State University,
University Park, Pennsylvania 16802, U.S.A.

(Received 20 April 1977)

Abstract-Bismuth oxide is monoclinic, space group P2Jc. The sillenite compounds are impurity stabilized
derivatives with general formula MO, *6Bi,03, body-centered cubic with space group 123. Far i.r. and
Raman spectra have been measured on polycrystaliine Bi203 and on sillenite structures in which the
stabilizing oxide is SiO,, GeO,, TiO,. Ga,O>. ZnO. or PbO. About half the oredicted 24 i.r. bands
and Ran& bands are observed-for the sille&e’structures. Low frequency Raman bands are very sharp,
but high frequency bands are greatly broadened. This is interpreted in terms of an orientational disorder
of the lone-pair non-bonding orbital of Bi3+ m the bismuth-xygen framework. Although an isolated
regular tetrahedron, M04, exists in the structure, internal modes from the tetrahedron are not identifiable,
indicating a strong coupling with the framework. A cluster of relatively narrow bands in the i.r. spectra
in the range of 400-65Ocm-’ can be correlated with the various Bi- 0 bonds in the highly distorted
polyhedra that make up the bismuth-oxygen framework.

INTRODUCTION history, two metastable forms may appear, one tetra-

Bismuth oxide occurs in at least four polymorphs, one gonal (/IBizO,) and one body-centered cubic (yBi,03).
of which is stabilized by the introduction of small No detailed structural data appear to be available for
quantities of a large variety of other cations. The any of these other polymorphs. The phases are
stabilized YBi203, sillenite structure, is a rare example tabulated in Table 1 and a schematic diagram of the
of an optically active cubic crystal and therefore has stability relationships is shown in Fig. 1.
been of interest as an electro-optic material. Optical The refinement of the crystal structure of ctBizOJ [ 131
activity [I], optical rotation [2,3], Faraday rotation indicates that there are two kinds of bismuth atoms
[3],andelasto-optic properties [4] have been measured. both on the 4(e) general positions and three kinds of
The compounds BilZSi020 and Bi12Ge020 have oxygen atoms, also all on general positions. The Bi(1)
been of most interest, in part because these materials polyhedron is S-coordinated, rather like a distorted
can be prepared as single crystals [S, 71. Raman spectra pyramid with the apical Bi-0 bond an exceptionally
have been reported for these compounds [8,9], includ- short 208 pm while the bonds to the base of the pyramid
ing a very detailed study of the polarized spectra consist of two of shorter than nominal length, 217 and
obtained from single crystals [lo] and the effect of 221 pm and two that are rather long, 254 and 263 pm.
uniaxial stress on the Raman scattering [ll]. The Bi(2) polyhedron is more or less octahedral but
There appear to be no previous measurements on very distorted with bond lengths varying from 214 to
the Raman spectra of other sillenite structure com- 280 pm. The oxygens, in fact, can be regarded as sheets
pounds or of aBi203. In this paper we present i.r. and parallel to (001) giving the material a characteristic
Raman spectra of powder materials of six sillenite platy cleavage.
structure compounds. The spectra of the Si and Ge Most early attempts to determine the stability rela-
compounds are included for comparison with previous tions of the bismuth oxides were frustrated by the
single crystal work. continuing appearance of a body-centered cubic phase.
It later developed that this phase was, in fact, stabilized
by the presence of small amounts of a wide variety of
CRYSTAL CHEMISTRY OF THE BISMUTH OXIDES
impurities giving a compound with the general formula
The polymorphism of Biz03 has been the subject of MO;6Bi203, where M could be metals as diverse as
an extensive literature which is summarized by LEVIN Zn, Pb, Si, Ge, Ti, Ga, and many others. A compre-
and ROTH [12]. The low temperature form is mono- hensive investigation of many bismuth oxide-other
clinic (aBiZ03). At 730°C the monoclinic form inverts metal oxide systems [14] revealed at least ten oxides
to a cubic structure (8Bi203) that remains stable up to that would form a stable compound with roughly this
the melting point, 825°C. Depending on the cooling composition and there appear to be many more.
The unit cell of the body-centered cubic compound
* This work was supported by the Air Force Cambridge and the X-ray diffraction powder pattern are very
Research Laboratories under Contract F19628-71-C-0232. similar to those for metastable YBi203 and it has been
t Also afiliated with the Dept. of Geosciences. customary to refer to these compounds as yBizOs
505
506 REGIS J. BETSCH and WILLIAM B. WHITE

Table 1. The polymorphs of BilOJ

Phase Structure Unit Cell Reference

aBi203 Monoclinic a - 5.8486 &) [131

b - 8.1661
(bismite) P2llC c = 7.5097
8 = 113.00°
2=4

BBi,C, Tetragonal a = 10.93 [I21

? c = 5.63

YBi203 Cubic a - 10.268 [121

(slllenite) 123

6Bi203 Cubic a = 5.66 [121

?

structures. The mineral sillenite is described as yBi203
although the natural material is almost certainly
stabilized by one or more other metallic constituents.
It therefore seems more appropriate to refer to these
compounds as “sillenite” structures since the detailed
structure of pure yBi203 itself is still unknown.
A detailed crystal structure refinement is available
for one sillenite-structure compound, BilzGeOzo [lS].
The compound belongs to the polar space group 123.
The crystals are strongly piezoelectric and have a large
optical rotatory power, a property to be considered
when measuring single crystal Raman spectra. The
structure contains a single kind of Bi-0 polyhedron,
7-coordinated and of a peculiar bi-pyramidal con-
figuration. The base of the pyramid is like the poly-
hedron in uBiz03 with two shorter bonds, 222.0 and
222.8 pm and two longer bonds, 262.3 and 264.0 pm,
all more or less co-planar. The apex of the pyramid
is an exceptionally short bond, 207.8 pm. Below the
base are two additional oxygen ions at distances of
308.2 and 317.0 pm. This peculiar arrangement obtains
because of the non-bonding lone-pair of 6s’ electrons
on the Bi3+ ion which are oriented between the
extremely long bonds. The stabilizing foreign metal ion,
Ge in this case, forms a perfect tetrahedron (point
symmetry 7’) located at the center of the cubic unit
cell. Whether all of the great variety of ions which
stabilize this structure are also cl-coordinated is not
known, but similarities in X-ray diffraction data and
similarities in vibrational spectra imply that the struc-
tures must be very similar.
Phase diagrams [14] for three systems between
bismuth oxide and a tetravalent oxide show the
existence of a sillenite-structure compound, Bi12M020,
of narrow compositional range that melts congruently
near 900°C. Solid solution of the tetrahedral cation
in either of the stable polymorphs of Biz03 is un-
detectably small. A similar situation obtains with
Ga203, which forms a congruently melting compound,
Bil sGa024. The phase diagrams when a divalent cation
is used to stabilize the sillenite structure are quite
different. Lead oxide forms a compound, Bi12Pb019r
witha narrow composition range melting incongruently
at about 730°C. ZnO stabilizes the sillenite structure.
The compound BilzZnO19 has only a narrow com-
position range and melts congruently at about 800°C.
Nearly unique among the divalent cations, Nizt de-
stabilizes the sillenite structure and the phase diagram
shows only the coexistence of NiO with the two bismuth
oxide polymorphs. This is expected from the large
octahedral site preference energy of NiZt if only the
tetrahedral site is available.

EXPERIMENTAL METHODS

The compositions MO,. 6BiZ03 were prepared in which

MO, was SiO*, Ge02, TiOz, NiO, ZnO, and PbO. The Ga
400 500 600 700 800 9ot
compound was made up at the ratio GaZOs - 15Bi203
TEMPERATURE WI following the suggested composition of LEVIN and ROTH
Fig. 1. Schematic diagram showing the stability relations [ 141. There is some disagreement in the literature concerning
of the various polymorphs of Bi203. Adapted from [12]. the stoichiometry of this compound and the Zn compound.
 Vibrational spectra of bismuth oxide and the sillenite-structure bismuth oxide derivatives 507

SAFRONOV et al. [16,17] claim Ga208 *24Bi203 and band contours and produce an unknown amount of
ZnO*24Bi20,. The compositions used in the present work distortion in the spectra.
led to single phase materials so far as could be determined Raman spectra were measured with a Spex Model 1401
by X-ray powder diffraction and from the spectra themselves. spectrometer using photon counting electronics and a cooled
The end member oxides were mixed in proper ratios and RCA 31034 photomultiplier. The spectra reported were
ground intimately in an agate mortar. The resulting mixtures excited with an RCA ionized argon laser with an output
were fired under an oxygen-hydrogen torch in a carbon power of 300 mW at 488 nm and 250 mW at 514.5 nm. Most
crucible so that a puddle supported by a layer of unmelted spectra were measured with both excitation lines using a
starting material was formed. The liquid was maintained for spectral slit width of 2cm-‘. The samples were measured
only about 10 s and then allowed to cool in air to room as powders pressed into compact pellets and broken to
temperature. This technique proved superior to various expose a fresh powder surface. Line width measurements
sintered pellet techniques because of the greatly enhanced were made on spectra excited by a 15mW HeeNe laser
reaction kinetics. Maintaining a melt in a furnace for an used to reduce local heating effects.
extended period of time was not feasible because of loss of
BiaOs as a vapor phase. The resulting materials were ground,
RESULTS
pressed into pellets, and heated at 700°C for 24 h. The
additional annealing time was to insure that reactions were Infrared spectra for the six sillenite compounds,
complete and that the materials were well crystallized. A ctBi*O, and the hypothetical Bir2Ni0r9, are shown in
measurable improvement in crystallinity was obtained only
for the Bi12Ti020 compound. Sillenite-structure compounds Figs. 2 and 3. The spectra are shown as four segments
were obtained with all oxides except NiO. at four different wavenumber scales because of the use
Infrared spectra in the range of 4ooO-300 cm-’ were of four different gratings on the spectrometer. The per-
measured on a Perkin-Elmer Model 621 spectrometer with cent transmission scales are relative. Quantitative com-
samples vacuum cold-pressed into KBr discs. Far i.r. spectra
parison of band intensities between spectra cannot be
were measured from 700 to 33 cm- ’ using a Beckman IR-11
spectrometer. Samples for far ir. measurement were ground made because of the varying thicknesses of the mineral
to a fine powder under acetone, mixed with mineral oil oil films. The spectra confirm the phase diagram for
(Nujol) to form a mull and painted onto a polyethylene the NiO-Bip03 system. The i.r. spectrum of the nickel
slab for mechanical support. Only the far ir. spectra, which
containing composition is essentially identical to that
contain all features of interest, are reported here. These
spectra are subject to the same restrictions that plague all
of pure cc-BizOa.
attempts to measure powder i.r. spectra of polar compounds: The spectra of the six sillenite-structure compounds
particle size effects and Frohlich surface mode effects modify are generally similar to each other but differ in small

Fig. 2. Infrared spectra of sillenite-structure oxides containing tetravalent and trivalent cations.
 REGIS J. BETSCH and WILLIAM B. WHITE

WAVENUMBER

Fig. 3. Infrared spectra of rBi203 and sillenite-structure oxides containing divalent cations.

details.At the high frequency end of the spectrum is
a group of intense bands (3 bands in the Ti, Ga, Zn,
and Pb compounds; 4 in the Si and Ge compounds)
with the highest frequency component near 600 cm-‘.
The divalent cation compounds have in addition a
shoulder near 630 cm- ‘. In all compounds the highest
frequency i.r. mode is somewhat higher in frequency
than the corresponding mode in tlBi203.
The Raman spectrum of aBi203 is shown in Fig. 4
and the Raman spectra of the sillenite-structure com-
pounds are shown in Figs. 5-7. The spectra of all
compounds separate into two distinct parts: bands

a-Ei,O, 298” K

WAVENUMBER

Fig. 4. Raman spectra of aBi203 taken at 298 and at 78 K.

 Vibrational spectra of bismuth oxide and the sillenite-structure bismuth oxide derivatives 509

cations. The bands are narrower in the sillenite com-

pounds containing tetravalent cations but the line-
widths are still at least a factor of three larger than
Bi,,TiO, the linewidths of the low frequency bands. The highest
B frequency Raman mode in aBiz03 occurs at 445 cm-‘.
The main bands in the sillenite-structure compounds
occur near 525-550 cm- 1 and in the compounds con-
taining tetravalent cations there are weak Raman bands
at frequencies above 700 cm- ‘.

DISCUSSION

Theoretical analysis
Although the availability of only powder data limits
the extent to which assignments can be made, a factor
group analysis at least permits an inventory of the
number of predicted modes (Tables 2 and 3). A sum-
mary of the mathematical methods involved may be
found in the review paper of DEANGELIS et al. [18].
The monoclinic form of Bi203 belongs to space
group P2,/c(C&,). There are 4 Bi203 per unit cell. Since
Bi,,Ge O,, all atoms lie on general positions [ 131, the sixty degrees
t
of freedom of the twenty atoms in the cell are distri-
buted uniformly over the four irreducible representa-
tions of CZh. Factor group analysis (Table 2) predicts
a total of twenty-seven i.r. active modes and thirty
Raman active modes. Because of the centrosymmetric
cell there are no coincidences between the i.r. and
Ran-tan active vibrations.
700 600 500 400 XK) 100 The sillenite structure belongs to the polar cubic
WAVENUMBER
group I23 (T3) with two formula units in the body-
Fig. 5. Raman spectra of sillenite-structure oxides with
tetravalent cations. centered cell. The distribution of atoms over the equi-
points of the space group is
above 200 cm- ’ and bands below 200 cm-‘. The bands 2M on 2(a) T
below 200 cm- ’ are all very sharp. Those of the six
24 Bi on 24 (f) Ct
sillenite-structure compounds are very similar to each
24 O(1) on 24 (f) C1
other. The bands above 200 cm- ’ are quite broad in
the room temperature spectra of n-Biz03 and the 8 O(2) on g (c) c3

sillenite compounds containing divalent and trivalent 8 O(3) on g (c) C3

Bi,, GaO,,

t 1-1 I I I I I I I I I I I I I II
900 600 700 600 500 400 300 200 100
WAVENUMBER

Fig. 6. Raman spectrum of Bi15Ga02+

510 REGISJ. BETSCHand WILLIAMB. WHITE

Bi,,ZnO,,

Fig. 7. Raman spectra of sillenite-structure oxides with divalent cations.

Factor group analysis based on this distribution of
atoms (Table 3) predicts twenty-four i.r. active vibra-
tions and forty Raman active vibrations. Modes belong-
ing to irreducible representation, T, are both i.r. and
Raman active and thus the twenty-four i.r. active modes
should also appear in the Raman spectra. The remain-
ing sixteen Raman modes will be unique. The modes
that classify in the same irreducible representation as
the dipole moment vector will be split by the long range
polarization field into longitudinal and transverse com-
ponents. This effect may be responsible for broadening
the i.r. bands as observed on the spectra of powders
but the longitudinal modes themselves do not appear
in the i.r. However, the longitudinal components of
those modes that are a1so.i.r. active are permitted in
the Raman effect and thus there is the possibility of a
Table 2. Factor group analysis of a-Biz03
--
Total Selection
'2h Acoustic Vibrations
Modes Rules
doubling of each of the twenty-four T-type modes in
the Raman spectra.
The stabilizing cation in the sillenite structure
occupies a regular tetrahedron at the center of the unit
cell. The point symmetry is also T, the same as the
factor group. If this part of the structure is regarded
as a tetrahedral molecule, the internal modes can be
classified separately and this has been done in Table 3.
The remaining modes have simply been listed as lattice
modes and were not separated into translatory and
rotatory types. The descent of symmetry from the
molecular point group Td to the site symmetry T is
There is no site group splitting and because there is
only one tetrahedron in the primitive unit cell there is
no factor group splitting either.
Comparison of observed spectra with theoretical
predictions and with single crystal spectra

A 15 15 R&MWll The i.r. spectrum of crBizOX (Fig. 3) exhibits sixteen

R bands, slightly more than half the number predicted
B 15 15 R~llKSl
g in Table 2. The Raman spectrum (Fig. 4) contains
A 15 z 14 IR, R/lb fifteen bands at 298 K and twenty-two bands at 78 K.
IL
This situation has been observed in the powder spectra
B 15 X*Y 13 IR, R&
u of other compounds with low symmetry. If the struc-
tures are more or less homogeneously bonded in all
 Vibrational spectra of bismuth oxide and the sillenite-structure bismuth oxide derivatives
Table 3. Factor group analysis of the sillenite structure
Total Acoustic Tetrahedral
T
Modes Modes Modes
A 8 v1
E 8 v2
T 25 (X,Y,Z) v3 + v
directions the vibrational frequencies in different
polarization directions do not differ much, although
their polarization properties are different. The observed
powder spectra, being a superposition of the polarized
spectra, reflect the overlapping of similar modes as
single bands.
It is also instructive to compare the i.r. with the
Raman spectra. xBi203 is centro-symmetric so no
strict coincidences are permitted. The 39 cm- ’ i.r. band
has no Raman counterpart. The group of three sharp
bands at 53, 59 and 67 cm- ’ in the Raman can be
matched against a set at 58, 62 and 67 cm- 1 in the i.r.
The next doublet of Raman lines at 83 and 93cm-i
have no i.r. counterparts but the Raman lines at 101,
118 and 139 are close to the i.r. bands at 100, 116
and 132 cm- ‘. The higher frequency parts of the spectra
are less similar, in particular, the highest frequency
modes occur in the i.r. as the group of strong bands
from 380 to 595 cm-‘. Most of these have no bands of
similar frequency in the Raman spectrum.
Spectra of the sillenite-structure compounds may be
compared both with factor group predictions and with
the single crystal Raman data on the Si and Ge com-
pounds published by VENUGOPALANand RAMDAS[lo].
About half the predicted 24 i.r. bands were observed,
the number varying somewhat from one compound to
the next. Between ten and seventeen of the predicted
forty Raman bands were observed. The Raman spectra
taken on powders at 300 K (Fig. 5) are in good agree-
ment with VENUGOPALAN and RAMDAS’ unpolarized
single crystal measurements at 300 K, in which approxi-
mately the same number of bands were observed. The
numerical agreement is within 1-2 cm-’ for most
bands. At liquid helium temperature the single crystal
spectra are better resolved and other weak bands
appear for a total of twenty-nine of the predicted forty
Raman bands.
The dominant lines in the powder Raman spectra
appear to be the A modes. There is a reasonable
agreement between the i.r. bands and the weak Raman
bands which the single crystal data indicate should be
T modes. The exceptions are the 272 and 236 cm- ’
i.r. bands in the Ge compound and the 240 cm- 1 i.r.
band in the Si compound, which have no corresponding
bands of the T type in the Raman spectrum.
The strong cmster of bands between 400 and 650
511
Lattice Selection
Vibrations Rules
7 Raman
7 Raman
22 IR + Raman
4
cm-’ in the i.r. spectra must be of the T type. They
are the strongest bands in the i.r. spectra whereas the
corresponding bands in the Raman spectra, where
observed at all, are very weak.
Tetrahedral modes
The only difference between the six compounds with
the sillenite structure is the mass and valence of the
tetrahedral cation. This is manifested in the spectra by
the great similarity in band shape and frequency.
Distinct differences in the i.r. spectra occur mainly in
the intermediate frequency group of bands. The most
distinct differences in the Raman spectra occur at high
frequency where the compounds containing tetravalent
ions exhibit a few weak modes in the range of 650-
800 cm-‘.
It is apparent from the spectra that the tetrahedral
group does not behave as an isolated molecule. There
would be expected a very intense i.r. active asymmetric
stretching mode in the range of 850-900 cm-’ in the
Si compound and at about 750 cm- ’ in the Ge com-
pound. No such bands were observed. Instead the
highest frequency i.r. bands are nearly the same for all
compounds regardless of the charge or mass of the
tetrahedral cation.
In the Raman spectra, on the other hand, the highest
frequency bands observed 717cm-’ in the Ge com-
pound 722 cm- ’ in the Ti compound and 817 cm- ’
(observed by VENUGOPALAN and RAMDAS) in the Si
compound are at about the right frequency to corre
spond to the M-O symmetric stretch. The intensity
of these modes is, however, greatly reduced from the
expected intensity of a tetrahedral molecule. The sym-
metric stretching mode is usually the most intense band
in the Raman spectrum.
The structure of Bii2GeOZo [15] shows that the
O(3) ions coordinating Ge are also corner-shared with
the 7-coordinated bismuth polyhedron. It is not valid,
therefore, to analyze the spectrum in terms of an
isolated tetrahedral molecular group. The great
similarity of the i.r. spectra of all compounds, regard-
less of size and valence of the tetrahedral cation,
combined with the weak high frequency Raman bands,
suggests that the spectrum is better regarded as that
of a bismuth-oxygen framework with an isolated im-
purity atom in a tetrahedral cage.
512 REGIS J. BETSCHand WILLIAMB. WHITE

The bismuth-oxygenframework
The 40@600 cm- ’ region of the i.r. is occupied by
an intense broad band envelope broken into a number
of sharper bands. The intensity of the envelope and its
mean wavenumber values suggest that these bands are
predominantly stretching modes of the bismuth-
oxygen framework.
ABRAHAMS’[15] structural determination
Bir2Ge02c reveals a single type of bismuthoxygen
polyhedron, 7-coordinated, with bond lengths ranging
from 207.6 to 317 pm. However, except for the
shortest bond, the other Bi-0 bonds occur in pairs
with similar but not identical lengths, there being
effectively only four distinctly different bonds in the
Bi-0 coordination polyhedron. The high frequency
envelope for BirlGeO1s contains four bands and if
the band wavenumbers are plotted against the bond
lengths (Fig. 8) a linear relationship results.
The structure of ctBiz03 is more complex [13]. There
are two distinct Bi-0 polyhedra, each effectively 6-
coordinated but highly distorted with bond lengths
ranging from 208 to 325 pm. These are plotted on the
bottom of Fig. 8. The i.r. absorption envelope of
aBiz03 (Fig. 3) is broader and although six bands can
be distinguished the fine structure is less distinct than
is found in the i.r. spectra of the sillenite compounds.
Nevertheless, if one attempts to correlate the observed
fine structure bands between 380 and 595 cm- ’ with
the clusters of similar bond lengths the results shown
in Fig. 8 are obtained.
The two low wavenumber bands of the i.r. stretching
group appear at almost the same wavenumber values
for all six sillenite-structure compounds, suggesting
that the arrangement of the long bonds in the B-O
polyhedra are very similar in all these compounds. The
two higher wavenumber bands merge into one for the
Ti analogs and a band with a poorly defined shoulder
in the Ga, Zn and Pb analogs. This implies that the
relative lengths of the very short (208 pm) apical bond
and the two normal bonds (222 and 223 pm) are likely
to be less distinct in these compounds.
for VENUGOPALAN and RAMDAS[lo] found from their
single ,crystal measurements that the separation be-
tween the transverse and longitudinal optic modes was
small, in the order of 2-IOcm-’ and that the longi-
tudinal components were weak. There is no evidence
that the longitudinal optic modes appear in the room
temperature spectra of any of the other sillenite-
structure compounds either. The small mode separa-
tion suggests that the bismuth-oxygen bonds are rather
highlycovalentiftherelationship between longitudinal-
transverse mode separation and effective charge pro-
posed by MITRA and MARSHALL[19] is accepted. This
result appears in spite of the overall polar character
of the entire structure. The small longitudinal-trans-
verse mode separation may also account for the
relatively narrow i.r. bands. A broad envelope in the
metal-oxygen stretching region in the i.r. spectrum of
a powdered material would normally be associated
with highly polar bonds and a large longitudinal-
transverse mode separation. In the case of aBi203 and
the sillenite-structure materials, the large distortion of
the Bi-0 polyhedra separates the Bi-0 stretching
modes into more localized and narrow-line vibrations.
Something similar is observed in ZrOz where the highly
distorted monoclinic polymorph has a number of
relatively narrow bands in the powder i.r. spectrum,
whereas the spectrum of the cubic form contains only
a broad envelope [20,21].

Raman line widths and structural order

The Raman bands of both aBi20j and the sillenite-
I BOND LENGTHS IN ai,,GeO,, I structure derivatives are all exceptionally broad. The
line widths are also a sensitive function of temperature
(Fig. 4 and [lo]), sharpening by more than an order
of magnitude between room temperature and 78 K.
The low frequency Raman bands are relatively sharp
but the line width increases with frequency reaching a
maximum in the band near 300 cm-r in all compounds
(Fig. 9) and then decreasing somewhat for the highest
frequency modes.
The band widths of QBi203, which exhibits a large
number of Raman bands, seem to follow a smooth
d
function of the band frequency which reaches a maxi-
400- mum near 3OOcm- 1 (Fig. 9). The line widths of
BOND LENGTHS IN a&O,
Li - _ \-
Bi12Ge02e follow the same trend but fit less well to a
smooth function. The number of bands observed for
350.
I I I I BiIsGaOz4 and Bi12PbO19 are too few to define a
200 225 250 275 300 325
BISMUTH-OXYGEN DISTANCE (Picomaters)
curve. The line widths for these and all other sillenite
compoundswith divalent stabilizing elements are larger
Fig. 8. Plot of the components of the intense high frequency than the line widths of the compounds stabilized by
group of i.r. bands against interatomic distances in the
aBizOJ and sillenite structures. Each point represents an
4-valent elements.
average of the clusters of bond lengths shown by the long Both the band widths and their temperature de-
bars at the top and bottom of the diagram. pendences require an explanation. The most commonly
 Vibrational spectra of bismuth oxide and the sillenite-structure bismuth oxide derivatives 513

1 I I I1 0 1 I I,
D
l a Bi20,
50- 0 Bi,aGa OK) *

A Bi,,GaOz,
0 Bl,ePb 0,9
i -
5 40-

Fig. 10. The bismuth-oxygen polyhedron for Bi12GeOZ,,

(adapted from [ 151) showing the two possible orientations
of the non-bonding lone-pair orbital.

between the two long bonds. It can take on either of

BANDPOSITION
(cm-‘)
Fig. 9. Variation in Raman band width as a function of
band frequency. The curve for Bi203 is simply drawn
through the points to show the smooth variation. Data
points for the sillenite compounds show the widths of
individual bands but have not been connected with curves.
proposed hypothesis is that large line widths result
from structural disorder. Disorder, such as in glasses
[22,23] or in crystals with large concentrations
defects [24], results in the breakdown of the transla-
tional invariance of the structure and this in turn causes
a breakdown of the k = 0 selection rule. Mixing of
phonon states from different regions of the Brillouin
zone results in broadening of the Raman bands. Line
broadening also occurs in the spectra of materials that
undergo positional disorder of molecular units. Rather
detailed studies have been carried out for the am-
two positions which are sterically of nearly equal
energy. At finite temperatures the distribution of lone-
pair orbitals between two possible positions is random.
As the temperature is lowered the orbitals begin to
preferentially orient (although one cannot say from the
structural data alone which position this would be). As
the structure orders the Raman band widths decrease.
This model, which is discussed in more detail else-
where [27], provides an example of temperature-
dependent disorder that occurs in well crystallized,
of stoichiometric compounds that do not contain mole-
cular entities and in which the structural disorder is
not implicitly associated with phase transitions.
REFERENCES
[l] P. V. LENZO, E. G. SPENCERand A. A. BALLMAN,
Appl. Opt. 5, 1688 (1966).
[2] G.-F. MOORE, P. V. LENZO, E. G. SPENCERand A. A.
BALLMAN,J. ADDI.Phvs. 40.2361 (1969). I

mo&m halides in which there may be either random [3] A. FELDMAN, w. S. BROWER Jr. and D. HOROWITZ,
positioning of the NH: ion over several possible Appl. Phys. Len. 16, 201 (1970).
[4] E. L. VENTURINI,E. G. SPENCERand A. A. BALLMAN,
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W(P)34 NO.5-D
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