Nanolaminate films with a nominal 5 nm HfO2–4 nm TiO2 bilayer architecture are sputter deposited on unheated fused silica and Au-coated glass substrates. Films on fused silica are postdeposition annealed from 573 to 1273 K and characterized by x-ray diffraction, scanning electron microscopy, Raman microscopy, and UV-visible-near IR spectrophotometry. The films show weak but progressive crystallization into orthorhombic (o)HfTiO4 when annealed up to 973 K. o-HfTiO4 is expected to form under bulk thermodynamic equilibrium conditions in the case of complete mixing of the bilayer components. Annealing above 973 K produces a crystallization sequence that is not predicted by bulk thermodynamics, ultimately involving o-HfTiO4 demixing to form monoclinic HfO2 doped with Ti and rutile TiO2 doped with Hf. These phases have a higher atomic density than o-HfTiO4 and segregate into discrete mesoscopic features. The authors propose that o-HfTiO4 demixing into higher density phases is a mechanism for thermal stress relief at high temperature. Demixing results in a major loss of optical transparency in the visible and ultraviolet spectral regions.

1.
R.
Ruh
,
G. W.
Hollenberg
,
E. G.
Charles
, and
V. A.
Patel
,
J. Am. Ceram. Soc.
59
,
495
(
1976
).
2.
L’Octet
Franco-Canadien
,
High Temp. - High Press.
13
,
97
(
1981
).
3.
R. W.
Lynch
and
B.
Morosin
,
J. Am. Ceram. Soc.
55
,
409
(
1972
).
4.
G. A.
Carlson
,
J. L.
Anderson
,
R. A.
Briesmeister
,
S. R.
Skaggs
, and
R.
Ruh
,
J. Am. Ceram. Soc.
60
,
508
(
1977
).
5.
See, for example, the review,
R. M.
Wallace
and
G. D.
Wilk
,
CRC Crit. Rev. Solid State Mater. Sci.
28
,
231
(
2003
).
6.
G.
Tilloca
,
J. Mater. Sci.
27
,
5671
(
1992
).
7.
M.
Li
,
Z.
Zhang
,
S. A.
Campbell
,
H. -J.
Li
, and
J. J.
Peterson
,
J. Appl. Phys.
101
,
044509
(
2007
).
8.
M.
Li
,
Z.
Zhang
,
S. A.
Campbell
,
W. L.
Gladfelter
,
M. P.
Agustin
,
D. O.
Klenov
, and
S.
Stemmer
,
J. Appl. Phys.
98
,
054506
(
2005
).
9.
K.
Honda
,
A.
Sakai
,
M.
Sakashita
,
H.
Ikeda
,
S.
Zaima
, and
Y.
Yasuda
,
Jpn. J. Appl. Phys., Part 1
43
,
1571
(
2004
).
10.
F.
Chen
,
X.
Bin
,
C.
Hella
,
X.
Shi
,
W. L.
Gladfelter
, and
S. A.
Campbell
,
Microelectron. Eng.
72
,
263
(
2004
).
11.
D. H.
Triyoso
 et al.,
J. Appl. Phys.
98
,
054104
(
2005
).
12.
C. R.
Aita
,
J. Phys.: Condens. Matter
20
,
264006
(
2008
).
13.
J. P.
Coutures
and
J.
Coutures
,
J. Am. Ceram. Soc.
70
,
383
(
1987
).
14.
M. C.
Cisneros-Morales
and
C. R.
Aita
,
Appl. Phys. Lett.
93
,
021915
(
2008
).
15.
E. E.
Hoppe
,
C. R.
Aita
, and
M.
Gajdardziska-Josifovska
,
Appl. Phys. Lett.
91
,
203105
(
2007
);
E. E.
Hoppe
,
C. R.
Aita
, and
M.
Gajdardziska-Josifovska
,
Appl. Phys. Lett.
92
,
109903
(
2008
).
16.
R. C.
Weast
,
Handbook of Chemistry and Physics
, 51st ed. (
CRC
,
Cleveland, OH
,
1971
), p.
B
150
.
17.
R. C.
Weast
,
Handbook of Chemistry and Physics
, 51st ed. (
CRC
,
Cleveland, OH
,
1971
), p.
B
94
.
18.
E. E.
Hoppe
,
R. S.
Sorbello
, and
C. R.
Aita
,
J. Appl. Phys.
101
,
123534
(
2007
).
19.
M. A.
Omari
,
R. S.
Sorbello
, and
C. R.
Aita
,
J. Vac. Sci. Technol. A
24
,
317
(
2006
).
20.
Joint Commission on Powder Diffraction Standards Card No. 05-0565.
21.
L. V.
Azaroff
,
Elements of X-Ray Crystallography
(
McGraw-Hill
,
New York
,
1968
), p.
193
.
22.
Monoclinic HfO2, Joint Commission on Powder Diffraction Standards Card No. 78-0050.
23.
Rutile TiO2, Joint Commission on Powder Diffraction Standards Card No. 73-1765.
24.
Orthorhombic HfTiO4, Joint Commission on Powder Diffraction Standards Card No. 40-0794.
25.
Tetragonal HfO2, Joint Commission on Powder Diffraction Standards Card No. 08-0342.
26.
C. R.
Aita
,
J. Vac. Sci. Technol. A
24
,
2054
(
2006
).
27.
C. R.
Aita
,
Appl. Phys. Lett.
90
,
213112
(
2007
).
28.
C. R.
Aita
,
J. Vac. Sci. Technol. A
27
,
648
(
2009
).
29.
J. E.
Jaffe
,
R. A.
Bachorz
, and
M.
Gutowski
,
Phys. Rev. B
72
,
144107
(
2005
).
30.
O.
Ohtaka
,
T.
Yamanaka
, and
S.
Kume
,
J. Am. Ceram. Soc.
78
,
233
(
1995
).
31.
T.
Kidchob
,
P.
Falcaro
,
P.
Schiavuta
,
S.
Enzo
, and
P.
Innocenzi
,
J. Am. Ceram. Soc.
91
,
2112
(
2008
).
32.
Fused SiO2, Joint Commission on Powder Diffraction Standards Card No. 77-0217.
33.
C. -K.
Kwok
,
C. R.
Aita
, and
E.
Kolawa
,
J. Vac. Sci. Technol. A
8
,
1330
(
1990
).
34.
J. R.
Siettmann
and
C. R.
Aita
,
J. Vac. Sci. Technol. A
6
,
1712
(
1988
).
35.
M.
Copel
,
M. C.
Reuter
,
E.
Kaxiras
, and
R. M.
Tromp
,
Phys. Rev. Lett.
63
,
632
(
1989
).
36.
K. N.
Tu
,
J. W.
Mayer
, and
L. C.
Feldman
,
Electronic Thin Film Science for Electrical Engineers and Materials Scientist
(
MacMillan
,
New York
,
1992
), p.
150
.
37.
C. R.
Aita
,
J. D.
DeLoach
, and
V. V.
Yakovlev
,
Appl. Phys. Lett.
81
,
238
(
2002
).
38.
C. R.
Aita
,
J. D.
DeLoach
, and
R. S.
Sorbello
,
J. Appl. Phys.
94
,
654
(
2003
).
39.
M.
Arbab
and
J. J.
Finley
,
J. Vac. Sci. Technol. A
12
,
1528
(
1994
).
40.
C.
Reinke
and
W. C.
Johnson
,
J. Am. Ceram. Soc.
78
,
2593
(
1995
).
41.
T.
Marten
,
O.
Hellman
,
A. V.
Ruban
,
W.
Olovsson
,
C.
Kramer
,
J. P.
Godowski
,
L.
Bech
,
Z.
Li
,
J.
Onsgaard
, and
I. A.
Abrikosov
,
Phys. Rev. B
77
,
125406
(
2008
).
42.
J.
Dumont
,
R.
Sporken
,
M. J.
Verstraete
,
J.
Ghijsen
, and
X.
Gonze
,
J. Phys.: Condens. Matter
21
,
315002
(
2009
).
43.
H.
Ikawa
,
A.
Iwai
,
K.
Hiruta
,
H.
Shimojima
,
K.
Urabe
, and
S.
Udagawa
,
J. Am. Ceram. Soc.
71
,
120
(
1988
).
44.
A.
Lakhlifi
,
P.
Satre
,
A.
Sebaoun
,
Y.
Saikali
, and
M.
Roubin
,
Ann. Chim. Fr.
19
,
155
(
1994
).
45.
M. A.
Omari
,
R. S.
Sorbello
, and
C. R.
Aita
,
J. Vac. Sci. Technol. A
23
,
1568
(
2005
).
46.
M. A.
Krebs
and
R. A.
Condrate
, Sr.
,
J. Mater. Sci. Lett.
7
,
1327
(
1988
).
47.
A.
Jayaraman
,
S. Y.
Wang
,
S. K.
Sharma
, and
L. C.
Ming
,
Phys. Rev. B
48
,
9205
(
1993
).
48.
S. P. S.
Porto
,
P. A.
Fleury
, and
T. C.
Damen
,
Phys. Rev.
154
,
522
(
1967
).
49.
W. D.
Kingery
,
H. K.
Bowen
, and
D. R.
Uhlmann
,
Introduction to Ceramics
, 2nd ed. (
Wiley-Interscience
,
New York
,
1976
), p.
131
.
50.
N. A.
Dubrovinskaia
,
L. S.
Dubrovinsky
,
R.
Ahuja
,
V. B.
Prokopenko
,
V.
Dmitriev
,
H. -P.
Weber
,
J. M.
Osorio-Guillen
, and
B.
Johansson
,
Phys. Rev. Lett.
87
,
275501
(
2001
).
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