Mixed cation phases in sputter deposited Hf O 2 Ti O 2 nanolaminates

M. C. Cisneros-Morales and C. R. Aita

Citation: Applied Physics Letters 93, 021915 (2008); doi: 10.1063/1.2957670
View online: http://dx.doi.org/10.1063/1.2957670
View Table of Contents: http://scitation.aip.org/content/aip/journal/apl/93/2?ver=pdfcov
Published by the AIP Publishing
Articles you may be interested in
Addendum to Phase selection and transition in Hf-rich hafnia-titania nanolaminates (on SiO2) [J. Appl.
Phys.109, 123523 (2011)]: Hafnon formation
J. Appl. Phys. 111, 109904 (2012); 10.1063/1.4719968
Phase selection and transition in Hf-rich hafnia-titania nanolaminates
J. Appl. Phys. 109, 123523 (2011); 10.1063/1.3597321
Intrinsic metastability of orthorhombic HfTiO 4 in thin film hafnia-titania
Appl. Phys. Lett. 98, 051909 (2011); 10.1063/1.3551543
Crystallization, metastable phases, and demixing in a hafnia-titania nanolaminate annealed at high temperature
J. Vac. Sci. Technol. A 28, 1161 (2010); 10.1116/1.3474973
Suppression of near-edge optical absorption band in sputter deposited Hf O 2 Al 2 O 3 nanolaminates
containing nonmonoclinic Hf O 2
Appl. Phys. Lett. 92, 141912 (2008); 10.1063/1.2907331

Reuse of AIP Publishing content is subject to the terms at: https://publishing.aip.org/authors/rights-and-permissions. Download to IP: 128.125.125.150 On: Wed, 06 Apr
2016 23:51:55

APPLIED PHYSICS LETTERS 93, 021915 2008

Mixed cation phases in sputter deposited HfO2 TiO2 nanolaminates

M. C. Cisneros-Moralesa and C. R. Aitaa,b
Advanced Coatings Experimental Laboratory, College of Engineering and Applied Science,
University of Wisconsin-Milwaukee, P.O. Box 784, Milwaukee, Wisconsin 53201, USA

Received 22 April 2008; accepted 23 June 2008; published online 17 July 2008
Nanolaminate HfO2 TiO2 films are grown by reactive sputter deposition on unheated fused SiO2,
sequentially annealed at 573 to 973 K, and studied by x-ray diffraction. A nanocrystalline structure
of orthorhombic o HfTiO4 adjacent to an interface followed by monoclinic m Hf1xTixO2 is
identified. m-Hf1xTixO2, a metastable phase, is isomorphous with m-HfO2 and a high pressure
phase, m-HfTiO4. A Vegards law analysis shows that the Ti atomic fraction in m-Hf1xTixO2 is
much greater than Ti equilibrium solubility in m-HfO2. A space group-subgroup argument proposes
that m-Hf1xTixO2 arises from an o / m-HfTiO4 second order phase transition to accommodate the
larger Hf atom. 2008 American Institute of Physics. DOI: 10.1063/1.2957670
The addition of TiO2 to HfO2 has shown promise for
producing a Hf1xTixO2 ternary with an even higher dielectric constant than pure HfO2 while maintaining thermal stability with Si.14 The bulk pseudobinary HfO2 TiO2
temperature-composition phase diagram5,6 shows low miscibility between the end-point oxides, monoclinic baddelytetype HfO2 and tetragonal rutile TiO2. A single mixed cation
phase, orthorhombic -PbO2-type HfTiO4, exists at STP.
Two fundamental questions are: 1 What interfacial mixed
cation phases form in as-grown sputter deposited
HfO2 TiO2 nanolaminates, and 2 how do these phases
evolve upon annealing under conditions of kinetic constraint
to diffusion, e.g., at the temperatures that devices might experience in routine processing?
Multilayer stacks of HfO2 and TiO2 bilayers whose architectures are given in Table I were grown on unheated
Suprasil II fused SiO2 substrates in a rf-excited multiple
cathode reactor.7 The substrates were sequentially positioned
under Hf and Ti targets and sputtered in 20 mtorr 80% Ar
20% O2 discharges to build up the films. Four sequential
annealing stages were carried out in laboratory air at the
following temperatures: I 573 K, II 673 K, III 773 K,
and IV 973 K for 1 h each.
Double angle XRD using unresolved Cu K radiation
0.1542 nm wavelength was used to obtain crystallographic
data over the 2 = 5 75 range. High resolution scans of
individual diffraction peaks were used to determine precise
peak position to an accuracy of 0.02.
The high resolution XRD scans for all film states in the
26 2 34 range are shown in Figs. 13. This 2 range
contains the major diffraction peaks from all films. Six possible peak assignments in this range are given in Table II.812
Three relevant phases that are not bulk equilibrium structures
at standard-temperature-and pressure STP are included:
orthorhombic o-HfO2, a high pressure polymorph,10,13 tetragonal t-HfO2,9 a high temperature polymorph, and
monoclinic m-HfTiO4, a high pressure polymorph that is
isomorphous with both STP m-HfO2 and monoclinic
a

Also at Materials Department and the Laboratory for Surface Studies, University of Wisconsin-Milwaukee, P.O. Box 784, Milwaukee, Wisconsin
53201, USA.
b
Author to whom correspondence should be addressed. Electronic mail:
aita@uwm.edu.

m-TiO2, another elevated pressure phase found in rocks.14

Figure 1 shows the XRD intensity versus 2 for the
as-grown AG films. The scan of AG film A with the thinnest HfO2 layers is distinctly different from those for films B
and C. The assignment for the single broad peak of AG film
A is ambiguous. This pattern is similar to that from thin
HfO2 layers in AG HfO2 Al2O3 nanolaminates.15 In that
case, high resolution transmission electron microscopy
showed that HfO2 layers were mainly composed of t-HfO2
and o-HfO2. Despite this ambiguity of assignment, Fig. 1
shows that diffraction from pure m-HfO2 does not significantly contribute to the broad peak from AG film A.
The centroid of the lower angle peak in AG films B and
C lies between the 2 position expected for diffraction from
the 11 1 planes of two isomorphous phases, m-HfO2 and
m-HfTiO4. The centroid of the higher angle peak lies between the expected position for diffraction from 211
o-HfO2 planes and 111 m-HfO2 planes. The o-HfO2 and
m-HfO2 structures are closely related by polysynthetic
twinning13 experimentally observed in thin HfO2 layers in
HfO2 Al2O3 nanolaminates.15 The 111 planes of the
monoclinic daughter twin form directly from a rotation of the
orthorhombic parents 211 planes.15
The AG TiO2 layers are assumed to consist of a mosaic
structure based on an intergrowth of rutile and -PbO2-type
TiO2 domains.7,16 In thicker samples, the XRD pattern of this
structure yields a single weak peak at 2 27.5 corresponding to rutile 110 planes. Here, this peak cannot be
discerned from peaks attributed to Hf-bearing structures.
Figure 2 shows the high resolution XRD scans over the
26 2 34 range for all annealing stages of film A. The
single peak shown in Fig. 1 for the AG film narrows, intenTABLE I. Nominal architecture of HfO2 TiO nanolaminate films.
No. of
HfO2 / TiO2
layer
HfO2 / TiO2 HfO2 volume Hf atomic
Thickness
layers
thickness nm
fraction
fractiona
Film
nm
A
B
C

293
236
220

5/4
8/4
12/ 4

33/ 32
20/ 19
10/ 9

0.54
0.67
0.74

0.51
0.64
0.72

HfO2 mole fraction is equal to the Hf atom fraction. Calculated using the
densities of rutile TiO2 4.26 g / cm3 and monoclinic HfO2 9.68 g / cm3.

Reuse of AIP Publishing content is subject to the terms at: https://publishing.aip.org/authors/rights-and-permissions. Download to IP: 128.125.125.150 On: Wed, 06 Apr
0003-6951/2008/932/021915/3/$23.00
93, 021915-1
2008 American Institute of Physics
2016 23:51:55

021915-2

Appl. Phys. Lett. 93, 021915 2008

M. C. Cisneros-Morales and C. R. Aita

FIG. 1. High resolution XRD scans of the AG films in the all states in the
26 2 34 range. Vertical lines indicate the positions of relevant standard peaks in this range given in Table II.

sifies, and shifts toward the value for 111 o-HfTiO4 planes
as the annealing temperature increases. o-HfTiO4 is the STP
phase consistent with the films overall stoichiometry Table
I. However, a small peak not attributable to o-HfTiO4 is
observed in the scan of the stage IV anneal. This peak lies
between the 2 values of 11 1 m-HfTiO4 over the pressure range of this compounds existence in bulk material,
1 9 GPa.
Figure 3 shows the high resolution XRD scans over the
26 2 34 range for all annealing stages of films B and
C. The centroid of the higher angle peak shifts away from the
2 position for o-HfO2 211 planes and toward the m-HfO2
111 planes. This shift is consistent with the transformation
of o-HfO2 to m-HfO2 via polysynthetic monoclinic twinning.
The centroid of the lower angle peak shifts away from
the 2 position for 11 1 m-HfO2 planes and toward the
2 position for 111 m-HfTiO4 planes. The average interplanar spacing associated with the lower angle peak in films
B and C is graphed as a function of annealing temperature in
Fig. 4. The change in the 11 1 interplanar spacing with
annealing is consistent with the incorporation of Ti into the

FIG. 3. High resolution XRD scans of films B and C 26 2 34 range.

Vertical lines indicate the positions of relevant peak assignments in this
range given in Table II.

m-HfO2 lattice to produce a monoclinic mixed cation phase

m-Hf1xTixO2.
The atomic Ti fraction, x, in m-Hf1xTixO2 is likely to
vary with distance from the interfaces in films B and C.
However, we use the data in Fig. 4 for a Vegards rule
analysis17 to estimate the average value of x in
m-Hf1xTixO2 in films B and C. We used the lattice constants for the only three known compositions of the bulk
m-Hf1xTixO2 isomorphs to establish the feasibility of extensive solid solution formation. These isomorphs are
m-HfO2, m-HfTiO4 i.e., m-Hf0.5Ti0.5O2, and m-TiO2. We
TABLE II. Phase, lattice space group, plane, and interplanar spacing of
relevant standards for comparison with observed XRD peaks.
Space group
No.

Assignment

Lattice type

HfO2
HfTiO4

Monoclinic
Monoclinic

P21 / c 14
P21 / c 14

HfO2
HfTiO4
HfO2
HfO2

Tetragonal
Orthorhombic
Orthorhombic
Monoclinic

P42 / nmc 137

Pnab 60
Pbca 61
P21 / c 14

hkl
11 1
11 1
11 1
111
111
211
111

2
deg

dhkl
nm

28.35
0.3148
29.15a 0.3063
29.49b 0.3029
30.06
0.2973
30.43
0.2937
30.94 0.2890
31.65
0.2827

FIG. 2. High resolution XRD scans of annealed film A in the 26 2

a
At 1 GPa Ref. 12
34
range. The
vertical
lines indicate
the positions
of relevant peak asReuse of AIP
Publishing
content
is subject
to the terms
at: https://publishing.aip.org/authors/rights-and-permissions.
Download to IP: 128.125.125.150 On: Wed, 06 Apr
b
At 9 GPa Ref. 12
signments in this range given in Table II.
2016 23:51:55

021915-3

Appl. Phys. Lett. 93, 021915 2008

M. C. Cisneros-Morales and C. R. Aita

FIG. 4. Interplanar spacing of m 11 1 peak in films B and C vs annealing

temperature.

found that all individual lattice constants and the unit cell
volume decrease in a linear manner with x, establishing the
validity of using Vegards rule.
d111 for the three known bulk isomorphs is graphed as
a function of Hf atomic fraction in Fig. 5, and a regression
analysis linear fit with 98% confidence is made to the data.
The value of x for an unknown composition can now be
graphically determined from Fig. 5 if d111 is known. Doing
so for films B and C after the stage IV anneal yields an
average Ti atomic fraction of x = 0.22 for film B and x
= 0.18 for film C. These data, included in Fig. 5, indicate that
the average atomic fraction of TiO2 in m-Hf1xTixO2 in both
films after a 973 K anneal is greater than 0.05, the Ti atomic
fraction that is incorporated into bulk m-HfO2 at STP. Furthermore, the Ti atomic fraction in m-Hf1xTixO2 increases
with annealing temperature from values close to bulk HfO2
film B or within experimental error of bulk HfO2 film C.
Consideration of the behavior of all films shows that
annealing produces a complex interfacial structure consisting
of two crystalline mixed cation phases, o-HfTiO4 and
m-Hf1xTixO2. We propose that the seeds for this structure
are present in the AG films, similar to the case of ZrO2 TiO2
nanolaminates.18 In this model, o-HfTiO4 is formed directly
from the TiO2 mosaic domain structure in the AG films as
HfO2 is deposited on the underlying TiO2 layer. The incorporation of Hf into the TiO2 mosaic structure to form

o-HfTiO4 is aided by the structure of -PbO2-type TiO2, one

of the mosaics components. The o-HfTiO4 and -PbO2-type
TiO2 lattices represent two nonstandard settings of the same
space group, Pbcn.19 The cation-O coordination number
CN is 6 in this space group.
The growth of m-Hf1xTixO2 with a CN= 7 comes about
as the Hf-bearing flux that continues to arrive at the growth
interface cannot be accommodated by a structure in which
the CN= 6. The o-HfTiO4 and m-Hf1xTixO2 lattices are
closely related. The P21 / c monoclinic space group to which
m-Hf1xTixO2 belongs is a maximal subgroup of the orthorhombic Pbcn space group.20 A transformation between the
two structures at their common composition, o / m-HfTiO4, is
diffusionless12 and continuous as defined by the Landau
theory for second order phase transitions21 and
ferroelastic20. Annealing has the effect of moving the reaction interface in an AG HfO2 TiO2 nanolaminate further
into a TiO2 layer, i.e., ripening an interfacial structure that
has already formed in the AG films.
This research was supported by AceLab discretionary
funds and the Wisconsin Distinguished Professorship of
CRA. MCC-M was supported by a scholarship from CONACYT, Mexico.
1

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.
2
M. Li, Z. Zhang, S. A. Campbell, H.-J. Li, and J. J. Peterson, J. Appl.
Phys. 101, 044509 2007.
3
K. Honda, A. Sakai, M. Sakashita, H. Ikeda, S. Zaima, and Y. Yasuda, Jpn.
J. Appl. Phys., Part 1 43, 1571 2004.
4
F. Chen, X. Bin, C. Hella, X. Shi, W. L. Gladfelter, and S. A. Campbell,
Microelectron. Eng. 72, 263 2004.
5
R. Ruh, G. W. Hollenberg, E. G. Charles, and V. A. Patel, J. Am. Ceram.
Soc. 59, 495 1976.
6
J. P. Coutures and J. Coutures, J. Am. Ceram. Soc. 70, 383 1987.
7
M. A. Omari, R. S. Sorbello, and C. R. Aita, J. Appl. Phys. 99, 123508
2006.
8
m-HfO2: Joint Committee on Powder Diffraction Standards Card No. 780050.
9
t-HfO2: Joint Committee on Powder Diffraction Standards Card No.
8-0342.
10
o-HfO2: Calculated from a = 0.983 nm, b = 0.517 nm, c = 0.496 nm. J. E.
Jaffe, R. A. Bachorz, and M. Gutowski, Phys. Rev. B 72, 144107 2005.
11
o-HfTiO4: Joint Committee on Powder Diffraction Standards Card No.
40-0794.
12
m-HfTiO4: R. W. Lynch and B. Morosin, J. Am. Ceram. Soc. 55, 409
1972.
13
O. Ohtaka, T. Yamanaka, S. Kume, N. Hara, H. Asano, and F. Izumi, J.
Am. Ceram. Soc. 78, 233 1995.
14
A. El Goresy, M. Chen, L. Dubrovinsky, P. Gillet, and G. Graup, Science
293, 1467 2001; 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.
15
E. E. Hoppe, C. R. Aita, and M. Gajdardziska-Josifovska, Appl. Phys.
Lett. 91, 203105 2007; 92, 109903 2008.
16
C. R. Aita, Appl. Phys. Lett. 90, 21311 2007; J. Vac. Sci. Technol. A 24,
213112 2006.
17
W. D. Kingery, H. K. Bowen, and D. R. Uhlmann, Introduction to Ceramics, 2nd ed. Wiley-Interscience, New York, 1976, p. 131.
18
C. R. Aita, J. D. DeLoach, and N. N. Yakovlev, Appl. Phys. Lett. 81, 238
2002.
19
http://www/ccdc.cam.ac.uk/support/documentation/quest/volume3/
z307.html, Cambridge Structural Database System Appendix 7,
Cambridge Crystallographic Data Center, Cambridge, UK.
20
J.-C. Toldano and P. Toldano, Phys. Rev. B 21, 1139 1980.
FIG. 5. Vegards law analysis: interplanar spacing of m 11 1 peak for
21
L. D. Landau and E. M. Lifshitz, Statistical Physics Pergamon, London,
bulk Hf1xTixO2 and films B and C after 973 K anneal vs atomic fraction Ti
1958, pp. 430456.
in bilayer. Solid line is regression analysis fit to bulk Hf1xTixO2 data.
Reuse of AIP Publishing content is subject to the terms at: https://publishing.aip.org/authors/rights-and-permissions. Download to IP: 128.125.125.150 On: Wed, 06 Apr

2016 23:51:55