PHYSICAL REVIEW B

VOLUME 45, NUMBER 5

Raman spectrum of zirconia-hafnia

FEBRUARY 1992-I

mixed crystals

Cosmo Carlone
Departement

de Physique and Centre de Recherche sur la Physique du Solide,

Universite de Sherbrooke, Sherbrooke, Quebec, Canada JIK2RI
(Received 9 July 1991)

Monoclinic crystals of Zr, Hf, 02 were grown by heating the layered structures Zr Hf, S& in a
pure oxygen atmosphere at 800'C for 2 h (x =0, 0. 1, 0. 25, 0. 5, 0. 75, 0. 9, and 1.0). Their Raman spectra were recorded at 15 and 300 K. The 18 modes predicted by group theory were identified in Zr02 and
their evolution with x was determined. At 15 K, seven phonons show distinct two-mode behavior, while
others are characterized by discontinuities, either at x =0.6 or x =0.3. This latter observation is reminiscent of percolation-type phenomena.

I.

INTRODUCTION

'

Zirconia and hafnia are similar in many respects.

At
room temperature, they are both monoclinic, with four
formula units per unit cell. They both transform to a
tetragonal phase, the former between 1250 and 1450 K,
the latter at approximately 600'C higher. ' Various techniques including x rays,
high pressure, ' and Raman
have been used to investigate
these
spectroscopy
different phases. As these materials are important ceramics, their high-temperature properties are being studied in
great detail. For example, the Raman spectrum from 300
to 1600 K has been published; however, Raman data at
low temperatures
are somewhat scarce. Anastassakis,
roomand
Asher
Papanicolaou,
have
published
temperature Raman data, and they state that, except for
the small usual frequency shifts, no change in the Raman
spectrum occurs in going from room temperature to
liquid-nitrogen temperature.
The analysis given in Ref. 2 is the most thorough of the
works on Raman spectroscopy, but the situation is not
entirely satisfactory. An unresolved issue is the number
of modes. Group theory predicts 18, but Anastassakis,
Papanicolaou, and Asher give only 17 peaks as due to
the Raman spectrum of Zr02. They list 20 peaks, but
one was attributed to a second-order spectrum and two
others to the high-temperature
tetragonal phase, which
supposedly persists even at room temperature. They actually observed 17 transitions, but excluded three, as explained. To remedy the situation, they hypothesized that
two peaks are doublets and assumed an unobserved structure to arrive at 17 modes. The authors also investigated
Hf02 powders and list 17 first-order transitions.
A second unresolved issue concerns the mixed crystals
Zr Hf
02, where there is much less agreement with
published Raman data. Krebs and Condrate have analyzed the high-frequency modes, for which they state that
the frequency dependence is linear with x, suggesting
single-mode behavior. They also mention that some lowone in
frequency modes, in particular the 189-cm
Zr02, show continuous but nonlinear change with Hf02
content. They observed only 15 phonons. In another
work by Ignat'ev et al. , the second-lowest frequency

'

&

45

phonon splits into three components for 0. 2&x &0.7.

further
without
the
attribute,
comment,
They
phenomenon to two-mode behavior. The data suggest
rather a phase transition, but this possibility was not discussed. It is fortuitous that they also observed only 15
modes.
The unsatisfactory situation in the Raman data of
Zr Hf
02 mixed crystals has led us to re-examine the
spectrum. By working with crystals and by obtaining the
spectra at 15 K, we have been able to identify 18 modes
in the case of Zr02, and we were able to follow the x
dependence of these phonons both at room temperature
and at 15 K. We could not exactly reproduce the results
of Ignat'ev et al. , but we do confirm the speculation
made in that work that mixed-mode behavior does occur
in Zr, Hf&
02. Similarly, we could not reproduce the
data of Krebs and Condrate because we find mixedmode behavior even for some high-frequency
modes.
Our data for the parent crystals is very similar to that of
Anastassakis, Papanicolaou, and Asher, but our observation of mixed-mode behavior in the mixed crystals has
led to a change in the identity and correlation of some of
the modes. In fact, it is the mixed-mode behavior of
several phonons that has led to considerable confusion in
the interpretation of the Raman spectrum of the parent
crystals.
Although the data presented in this work permit us to
resolve some puzzles concerning the mode behavior in
the family Zr, Hf,
02, two problems still remain. (1)
We observe broad transitions in the case of Zr02 and 24
transitions in the case of Hf02, at 15 K. We attribute
this to our inability to reach x =0.00 or 1.00 (Zr is an impurity in Hf02 and Hf is an impurity in Zr02) and to the
two-mode behavior of some of the modes. Further work
in materials purification may be necessary.
(2) The
mixed-mode behavior of the phonons is unexplained.
Our data are reminiscent of percolation phenomenon, but
a detailed theory is lacking.
&

II. CRYSTAL GROWTH

Our starting point was the synthesis of the mixed crystals Zr Hf,
S2, which were grown by the iodine trans2079

1992

The American Physical Society

COSMO CARLONE

2080

From stoichiometric mixing, x was

port method.
chosen to be 0, 0. 1, 0.25, 0.5, 0.75, 0.9, and 1.0. For a
given crystal, i.e. , for a fixed x, we placed it in an oven
filled with pure oxygen and then heated it to 800'C for 2
h. The crystals had changed color from dark red to ivory
white. The x-ray analysis, using the Debye-Schirrer
monoclinic
method, confirmed their room-temperature
structure.
Despite the polycrystalline nature of the samples, their Raman spectrum proved to be of very good
quality. We also grew equally good quality crystals of
Zr Hf& 02 by starting with Zr Hf, S3 and, as described, by boiling off the sulfur in a pure oxygen atmosphere.

III. GROUP THEORETICAL

Vl

45

10

Z r Op

IV. SOME PROPERTIES OF MIXED CRYSTALS

Although Zr02 and Hf02 belong to the same space
group, an additional feature is added when mixed crystals
Zr Hf& 02 are synthesized. Disorder in chemical cornposition is introduced at the microscopic scale. Consequently, the potential is no longer periodic and the properties of the crystal depend on x. For the case of phonons,
with x (single
the frequency may vary continuously
(two-mode behavior).
The
mode) or discontinuously
theory is not suSciently advanced that one can predict
the mode behavior in a given crystal. Nevertheless, by
supposing that the disordered state is a linear combination of all possible ordered states, it can be shown that
the electrons can wander through the crystal most easily
for certain values of x. For a classical three-dimensional
system at T=O K, x =0.3 and 0.7. It is expected that
this percolation-type phenomenon persists to higher temperatures and even if quantum mechanics is applied. '

V. EXPERIMENTAL

The Raman spectra were obtained using several lines of

the argon-ion laser and the results were independent of
excitation energy. Considering the dielectric nature of
these materials, these observations were expected. A
Jobin- Yvon HG2S Ramanor monochromator, equipped
with standard electronics and a photon counting system,
was used to record the spectra. The low-temperature
spectra were obtained with the help of a CTI cryogenics
refrigerator.

VI. RESULTS
The room-temperature
Raman spectrum of Zr02 is
shown in Fig. 1. The continuous background signal of
about 20%%uo is due to the polycrystalline nature of the
crystals.
The room-temperature
Raman spectra of
ZrHf&
02 solutions are shown in Fig. 2, while those at

500 K )

lA

CD

234
0

50

125

5 6 78 9,10

200

275

phonon

ANALYSIS

The group theoretical analysis has been given by Anastassakis, Papanicolaou, and Asher. Since there are four
formula units per unit cell, one expects a total of 36
modes, of which three are acoustic. The low symmetry of
the crystal structure, monoclinic, results, at the I point,
in 18 Raman-active modes of symmetry A or B .

12

II
I

350 425

frequency

1314

500

650

575

(crn '

18-

15 16 17

725

800

FIG. 1. The room-temperature Raman spectrum of the crystal Zr02. The 18 modes predicted by group theory are indicated. The constant background signal is due to the polycrystalline
nature of the samples.
15 K are shown in Fig. 3. In Figs. 2 and 3, the constant
background is not shown. In order to compare our results with previously published data, we list in Table I the
room-temperature
frequencies of the Zr02 modes, as
given by Anastassakis, Papanicolaou, and Asher; their
results on HfOz powder are included in Table II. The 15
K values of the frequencies of the modes of the parent

V)

CD

E
O
CC

50

phonon

800

425

frequency

(crn

FIG 2 The room temperature Raman spectrum of the

mixed crystals ZrHf, 0&, as a function of frequency, in cm
The value of x is 1.0, 0.9, 0.75, 0.5, 0.25, 0. 1, and 0.0 going from
top to bottom.

RAMAN SPECTRUM OF ZIRCONIA-HAFNIA

45

MIXED CRYSTALS

2081

crystals are given in Table III, but the evolution of these

frequencies as a function of x is shown in Fig. 4 (300 K)
and in Fig. 5 (15 K).

VII. DISCUSSION
A. The Raman spectrum of Zr02 and Hf02 at 300 K.

C/l

E
O

According to group theory, the Raman spectra of both

materials at 300 K should consist of 18 peaks. We list in
Tables I and II what we judge to be the 18 phonons of
zirconia and hafnia. Although our results are very similar to those of Anastassakis, Papanicolaou, and Asher,
we do, however, disagree on the interpretation of some
modes. These differences are the following.
(1) Anastassakis, Papanicolaou, and Asher observed
that the lowest-frequency mode, at 101 cm ' in Zr02 and
112 cm ' in Hf02, is broad and suggested it to be a doublet. We also observe the broad character of this mode.
Its x dependence shows a discontinuity, indicating twomode behavior. In Hf02, the mode is broad at 300 K,
but it is clearly a doublet at 15 K. See Fig. 3.
(2) We do not observe a weak broad structure at 148
cm ' in Zr02. This peak was attributed to the tetragonal
phase, but we cannot discount it because we do observe
this structure in the mixed crystals for x 0.5. We believe that the second-lowest phonon also shows two-mode
behavior.
' in
(3) We do not attribute the phonon at 266 cm
Zr02 to the tetragonal Zr02 phase. This peak is barely
visible in our 300-K spectra, but we can follow it for
several values of x studied. It appears very strongly in
Hf02 at 15 K, and it corresponds to the 248-cm ' pho-

800

425

50

phonon

frequency

(cm

FIG. 3. The 15-K Raman spectrum of the mixed crystals

ZrHf, 02, as a function of frequency, in cm '. The value of
x is 1.0, 0.9, 0.75, 0.5, 0.25, 0. 1, and 0.0 going from top to bottom.

TABLE I. Zr02 Raman-active modes (cm ') at 300 K.

Mode
number

Present
work

Mode
number

331
343

9
10
11
12
13
14
15

16
17
18

376
376
473
498
534
557
613
633
705
780

Comment of
Anastassakis,
Papanicolaou, and Asher

92
101
148
177
189
222
266
306

observed

observed

9
10

315
335
347
355

11
12
13
14
15

382
476
502
537
559

16
17

616

99
177
189
222
270
305

Anastassakis,
Papanicolaou, and Asher

6
7
8

ambiguous

tetragonal

phase

tetragonal

phase

unobserved

ambiguous

suggested

637
764

second order

45

COSMO CARLONE

2082

TABLE II. Hf02 Raman-active modes (cm ') at 300 K.

Mode
number

Present
work'

Comment

Mode
number

104.8
2
3

133.8
164.4

195
250
276. 5

Anastassakis,
Papanicolaou, and Asher
(using powders)

112
116
140
153
170

2
3

taken from Fig. 2

taken from Fig. 2

331.3

7
8

10

335.8
379.3
392.8

9
10
11

248
261
322
342
388
403

11
12

464
511

13
14
15
16
17
18

548
574.6

12
13
14
15
16
17

504
527
557
588
647
680

6
7
8

taken from Fig. 2

taken from Fig. 2

641.8
671.8
708.9
787.3

'Transitions that are sharp or well resolved are measured to 0. 1 crn ', otherwise to

non in Hf02. This mode, which we label 5, is also two

mode. Anastassakis, Papanicolaou, and Asher had correlated the 248-cm ' mode in Hf02 to the 306-cm ' mode
in Zr02. We do not confirm this correlation.
(4) Anastassakis, Papanieolaou, and Asher suggest a
mode at 355 cm ' in ZrOz. They proposed it in order to
complete the correspondence between ZrOz and Hf02.
In fact, they proposed that this mode corresponds to the
388-cm ' phonon in HfOz. From our work, the 388-

cm

cm ' mode in Hf02 corresponds to the 380-cm ' phonon in ZrOz. See Figs. 3 and 4. Thus we do not need to
postulate a phonon at 355 cm ' in Zr02.
(5) Anastassakis, Papanicolaou, and Asher attribute
the broad structure at 780 cm ' in ZrOz to a secondorder spectrum. We observe other structures in this region. See Figs. 1 and 2. By plotting their frequencies as a
function of x, we discern discontinuities; in the first-order
are much less prospectrum, these discontinuities

TABLE III. Rarnan-active modes of Zr02 and Hf02 at 15

'
and otherwise to 1 cm
resolved are measured to 0. 1 cm

K. Transitions that are

sharp or we11

Mode
number
1

Zr02
101
177

189.5

4
5

222. 5
270

6
7

310.5
331.6

348. 1
378
384.9
474. 1
501.1
537.5
556.3
614.4
635.0
673

9
10
11
12
13
14
15

16
17
18

Comment

745

Hf02

Comment

108

The assignment
is suggested
by Fig. 5.

133.6
165.5
195

241.3
272.7
329
Unresolved
at 300 K

336.1
379.9
400. 8
475

519.4
548.0
579.1
639.9
668.9
706

789.9

IA-H
IA-HAFNIA MIXED CRY
YSTALS
RAMAN SPECTRUM OF ZIRCONIA-H

45

bl,

id
d

is temperature
tern

order spectrum
the fe

to th

15K

relative to the first-

, w h en they appear,

Zrx

))

Hf( x O~

(BROOK)

'ti(IF AK

YERY

inde en

go

ZrH

400-

Qe

~e

Qe

~e

o'

-'

We

~e

Ve

~e

Ue

ew at

-0=

Oe

400-

o servathey are at 300 K. These ob

t'ions have led us t o reinterpret thee structures at hiig h fre-

v(cm ')

v(cm ')

h'an

2083

Qe

30

200- 3

20

Pe~

2~ ---0

100{'

IOO(

(a)

(a)
I

0.9 0.8 0.7 06 Q5 0. 4 0.3 0. 2

v(cm ')

()------O---

700-

&

0.5 Q4 0.3 0.2

~)

(300K

{ b)
18

v(cm
rx Hfi x Oa

800-

O. I

O.

Zrx Hfi x Op ((5K)

800
--O---O--O l8

n,

17

) l8
700-

17

Qe

17

l&

16

16

15

600

600-

8-0

O
O

Q- 14

~-

Qo

13

Qi- 12

IP

VERY

WEAK

4OG

ll

lo

.7 0.6 0.5 0.4 03 0.

, l

QI

O----

IO

FIG. 4. T e correlation
b

Y Eq.V.

t
0.6 0.5 0.4 03 0.2
I

O. I

ve rno es
he correlation, at 1S K of
FIG. S. The
and
ue
range 0-400 cm
. (a) Freequency

2084

45

COSMO CARLONE

quencies as a first-order spectrum, whose breadth depends in part, on the two-mode character of the phonons.
(6) The region between 130 and 200 cm ' in HfOz is
particularly difficult to analyze. The peaks are very
broad and their large breadth persists from x=0.5 0 (at
300 K). For x 0.5, three sharp phonons are observed,
5. If, indeed,
but there appear to be at least four for x
there are four structures for x =0 but only three for x = 1,
then Hf02 has one more phonon than ZrOz. We recall
that Ignat'ev et al. had observed that this phonon is single for x 0.5 and that it splits into three modes at x approaching 0. We do observe discontinuities in the phonon frequencies and suspect that mixed mode behavior is
The spectra at
responsible for some of the phenomena.
15 K is more revealing and is discussed in Sec. VII B.

(0.

B. Mixed-mode

behavior

The x dependence of the modes is shown in Fig. 4 (300

K) and in Fig. 5 (15 K). There is a discontinuity at
x=0.6 for phonons labeled 1, 2, 3, 4, 5, 9, and 10 and at
0.3 for those labeled 6, 7, 8, 13, 14, and 15 in Fig. 5.
Some phonons show nonlinear behavior, e.g. , 11 and 18.
To complicate matters, there is in Zr, Hf, 02 both
single-mode and two-mode behavior. The peaks labeled
1, 2, 5, 10, 11, 17, and 18 are two mode. The two-mode
behavior of some of the phonons is also evident from line
At the region of discontinuity,
strength considerations.
there is a tendency for the intensity to drop and the half
width to increase. We suspect that the discontinuities observed are a subtler manifestation of two-mode behavior.
This mixed-mode behavior, though interesting in itdoes not help in sorting out the symmetry of the
self,
crystal through Raman spectra. Nevertheless, our proposed correspondence of the modes is shown in Figs. 4

"

'R. Ruh

and

P. W. Corfield, J. Am. Ceram. Soc. 53(3), 126

(1970).
2E. Anastassakis,

B. Papanicolaou, and I. M. Asher, J. Phys.

Chem. Solids 36, 667 (1975).
3J. D. McCullough and K. N. Trueblood, Acta Crystallogr. 12,
507 (1959).
4M. Ishagame and T. Sakurai, J. Am. Ceram. Soc. 60(7-8), 367
(1977).
5H. Arashi and M. Ishigame, Phys. Status Solidi 71, 313 (1982).
L. C. Ming and M. H. Manghaxni, in Solid State Physics: Recent Advances with Anuil Devices, edited by S. Minomura
(KTK Scientific, Tokyo, 1985), p. 135.
7M. A. Krebs and R. A. Condrate, Sr. , J. Am. Ceram. Soc. 65,

C-144 (1982).

and 5. It is interesting that in Zr Hf& Sz the phonons

show single-mode behavior' and in Zr Hf,
S3 both sin' To date, theory
gle and mixed modes are observed.
cannot predict the behavior of the modes in these Zr-Hf
compounds. We wish to point out that discontinuities at
x=0.6 and 0.3 is reminiscent of percolation phenome-

na.

"

C. The Raman spectrum of the parent crystals

The Raman spectrum of the mixed crystals shows both
single- and two-mode behavior. Let us pay particular attention to the parent crystals Zr02 and Hf02, where the
spectra should be the simplest. According to Table I, we
in fact observe 18 modes for ZrOz, but the peak numbered 1 is relatively broad. The situation in Hf02 is
worse, for we observe 24 peaks at 15 K. We attribute this
observation of broadening and of too many phonons to
the two-mode behavior of some modes. We postulate
that neither Zr nor Hf is pure enough that we could synthesize pure ZrOz or Hf02. We suspect that the smallest
and largest x values obtained in our experiments are of
the order of 0.01 and 0.99, respectively, and the impurity
is sufficient to bring out the two-mode behavior of some
modes. It seems that Hf contains more of Zr as an impurity than vice versa. More work on materials preparation is necessary to clear up this point.

ACKNOWLEDGMENTS

I wish to thank Robert Gagnon for expert crystal

growing and Franqois Malouin for assistance in recording the Raman spectra. This work was supported by the
National Research Council of Canada.

B. V. Ignat'ev, V. F. Kalabukhova,

V. V. Osiko, and A. A.
Sobol, Fiz. Tverd. Tela (Leningrad) 22, 1524 (1980) [Sov.
Phys. Solid State 22, 890 (1980)j.
L. Roubi and C. Carlone, Phys. Rev. B 37, 6808 (1988).
' D. Stauff'er, Introduction
to Percolation Theory (Taylor 4
Francis, London, 1985).
' J. M. Lopez Castillo and A. M. J. Tremblay, Phys. Rev. B 34,
8482 (1986).
'2C. Carlone, L. Roubi, and A. Beliveau, in Proceedings of the
XIth AIRAPT International Conference, Kieu, 1989, edited by
N. V. Novikov (Kiev Naukova, Dumka, 1989), Vol. 2, p. 348.
'3G. Nouvel, A. Zwich, M. A. Renucci, and A. Kjekshees,
Phys. Rev. B 32, 1165 (1985).