NEWS & VIEWS
material witness
Old gold
In 1896 the Louvre museum
declared that it had bought
an ancient Greek gold tiara
for 200,000 French francs
roughly 1.3 million today,
but considered a bargain
in view of the objects
antiquity. It had allegedly
been given to the Scythian
king Satapharnes around
the end of the third century bc as part
of a bribe to leave the Greek colony of
Olbiaunmolested.
But almost immediately doubts
surfaced, as experts questioned both the
tiaras design and its apparent lack of
ageing. The Louvre defended the items
authenticity, but then one day a Russian
goldsmith named Israel Rouchomovsky
came knocking at the door with an
incredible claim. I made the tiara, he
said. He explained that two dealers had
commissioned him to make a gift in the
antique style for an archaeologist friend.
Now news had reached Rouchomovsky
of their true intent. When the goldsmith
demonstrated that he could reproduce
part of the tiara, the Louvre officials had
Condensed-matter physics
Complex oxides on fire
Oxide materials have long been known as hosts for exotic and useful physical properties.
Recent advances in their design and fabrication establish the means to tailor their response
forapplications.
Yoshinori Tokura1
and Harold Y. Hwang2
are in the 1Department of Applied Physics,
University of Tokyo, and ERATO Multiferroics
Project, JST, Tokyo 113-8656, Japan; 2Department
of Advanced Materials Science and the
Department of Applied Physics, University of
Tokyo, Kashiwa, Chiba 277-8561, Japan.
e-mail: tokura@ap.t.u-tokyo.ac.jp;
hyhwang@k.u-tokyo.ac.jp
D
espite the vast field and multiple
disciplines encompassed by the
term complex oxides, there has
been a growing convergence of trends for
694
no choice but to believe him. They quietly
consigned the gold object to theirvaults.
Were it not beyond the capabilities
of fin de sicle science, a new technique
for spotting forgeries of ancient gold
objects would have saved the Louvre its
embarrassment. Otto Eugster and his
co-workers at the University of Bern
in Switzerland say that radioisotope
dating can be used to estimate the
last time that gold was melted down
(O. Eugsteret al. Archaeometry
doi:10.1111/j.1475-4754.2008.00426.x; 2008).
Forgeries of gold artefacts are
probably the most difficult to detect of all
fakes. Aside from stylistic grounds, the
more objective criterion of patination is
unreliable because golds noble character
leaves signs of surface decay tenuous and
easily removed by cleaning. And gold has
no intrinsic isotopic signatures of age,
because it has only one stable isotope.
Eugster and his co-workers have
for over a decade been studying the
signatures of radioactive trace elements
such as uranium and thorium that get
incorporated into gold in the Earths crust.
Alpha decay of these elements leads to the
manipulating the functionality of oxides
on micro-, meso- and macroscopic scales.
The starting point for this endeavour is
the very rich variety of physical properties
of complex oxides, which has long been
noted and commercially used. These
include their use as dielectric, magnetic
and superconducting materials. Much of
the recent scientific interest in developing
oxides has been devoted to engineering
them for novel functionality. For this,
fundamental physics within their crystalline
unit, in their defect structure, or at thin-film
heteroepitaxial interfaces is being explored.
Exciting developments in these efforts were
nature materials | VOL 7 | SEPTEMBER 2008 | www.nature.com/naturematerials
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accumulation of helium-4 in the metal. So
measurements of U, Th and 4He in gold
can reveal when it was last solidified, as
radiogenic helium is expelled on melting.
The researchers proposed in 1996
that this approach could be used to date
ancient gold artefacts, but only now do
they have the instrumentation needed
to put the idea into practice. It demands
an ability to detect extremely small
amounts of 4He, both because it will
have accumulated for only a relatively
short time compared with geological
samples, and because such analyses, being
destructive, must be based on very small
amounts ofmaterial.
The Bern group has now used their
dating method on a variety of historical
gold items, ranging from gold bowls of
the first or second centuries bc from
Central Asia to a French gold coin minted
in 1857. Although at present the method
doesnt constrain the dates very tightly,
the researchers found that all the ancient
objects were made more than 350 years
ago, whereas the French coin is of more
recent provenance.
 Philip Ball
the focus of discussion amidst the falling ash
of the California wildfires at the Workshop
on Frontiers of Complex Oxides, held in
July2008 at the International Center for
Materials Research of the University of
California, Santa Barbara.
Tremendous progress has been made
at the level of engineering oxides on the
atomic scale, in both the understanding and
design of microscopic coupling between
magnetism and electric polarization. Large
magnetoelectric coupling is anticipated to be
hosted by multiferroics in which electric and
magnetic order can coexist1. Magnetically
induced ferroelectricity has recently been

recognized to exist in non-trivial magnetic
structures, such as the transverse spiral
(or cycloidal) spin order (see Fig.1a). This
model has succeeded very well in explaining
the recently developed (or rediscovered)
multiferroics such as TbMnO3, yet the
understanding has remained at a qualitative
level. In particular, the problem to be solved
is to what extent the observed electric
polarization is genuinely driven by electronic
contributions rather than lattice dilation. At
the workshop, David Vanderbilt (Rutgers
University, New Jersey, USA) presented
first-principles calculations of the electric
polarization of TbMnO3 in conjunction
with Berry-phase theory2. Underlining the
important contribution of the concomitant
lattice distortion, these calculations
successfully reproduced the magnitude and
direction of the experimentally observed
polarization3. This observed lattice effect in
cycloidal spin multiferroics still seems to be
materials-dependent, but the success of first-
principles calculations is an important step
towards the quantitative understanding and
design of these materials.
P oxide analogues to Si and GaAs. Similarly
C = S1 S2
T for eliminating these often harmful defects,
S2
T=
1
i ri Si
2 could be reversibly switched in a non-volatile
S1
S3
S2
S1
S3 = S1 (S2 S3)
Figure 1 Possible spin arrangements leading to
a coupling between magnetism and static and/or
dynamic electric polarization in multiferroics. a, Vector
spin chirality C, as observed in the cycloidal spin
structure leads to an electric polarization P. b, The spin
arrangement that, through spin-orbit interaction, leads
to a toroidal moment T. c, The scalar spin chirality
generates a fictitious magnetic flux (=2) and
produces a spontaneous orbital current. The red arrows
in each pane represent the electron spins.
nature materials | VOL 7 | SEPTEMBER 2008 | www.nature.com/naturematerials
New order parameters such as toroidal
moment (Fig.1b) and spin chirality have
recently been recognized as important
alternatives for creating large magnetoelectric
coupling. Some materials with specific spin
arrangements on geometrically frustrated
lattices, such as triangular or kagome lattices,
may show toroidal order or a ferrotoroidic
state, and hence large magnetoelectric
activity, as comprehensively reviewed by
Maxim Mostovoy (University of Groningen,
The Netherlands). Note that toroidal
moments with large optical magnetoelectric
effects can be readily formed at the interface
between epitaxial magnetic oxide layers.
In addition, the consequences of another
non-coplanar spin arrangement called scalar
spin chirality (Fig.1c) on magnetoelectric
coupling was pointed out by Daniel Khomskii
(University of Cologne, Germany). These
novel routes to multiferroic coupling
accentuate the fact that a full consideration of
novel spin textures is needed to explore new
spintronic functions in complex oxides.
Another general theme of the workshop
was the vision that the development of oxides
may follow the example set by conventional
semiconductors. Two wide-bandgap oxides,
ZnO and SrTiO3, emerged in discussions as
to the historical development of those
materials, understanding and control of the
defect structure in oxides is of paramount
importance. In the midst of much discussion
Regina Dittmann (Forschungszentrum
Jlich, Germany) showed how useful defects
can be. Using the extended defect structure of
oxygen vacancies decorating dislocation cores
in SrTiO3, she showed that the conductivity
fashion. The demonstration of switching
dislocation core arrays in single crystals and
multilayer thin films using a conducting
scanning probe tip demonstrates a potential
avenue toward extremely high-density
memory devices.
Herbert Kroemer (University of
California, Santa Barbara, California,
USA) described the understanding and
historical improvement of the interface
electronic structure and band alignment of
semiconductor heterointerfaces4. This gave
a very pertinent basis for considering recent
developments in oxide heterostructures. For
example, amongst other applications, ZnO
is currently a centre of attention as a UV
emitter for use in solid-state white lighting. A
sensitive indicator of the electrical cleanliness
that can be achieved in ZnO/(Mg,Zn)O
heterostructures is the high mobility of
the two-dimensional electron gas at the
interface between the layers (Fig.2). Electron
mobilities of a few thousand cm2V1s1) 7. Ohtomo, A. & Hwang, H.Y. Nature 427, 423426 (2004).
were already sufficient to demonstrate the
2008 Macmillan Publishers Limited. All rights reserved.
NEWS & VIEWS
Energy
P1 P2
(Mg,Zn)O ZnO
LaAIO3 SrTiO3
Figure 2 Schematic band diagram of the heterointerface
between two oxides. The discontinuity between the two
different polarizations P1 and P2 of the materials induces
an interfacial electron gas. At the (Mg,Zn)O/ZnO interface,
P1 and P2 arise from spontaneous and piezoelectric
polarization of the constituents. At the LaAlO3/SrTiO3
interface, an effective P1 is created by controlling the
atomic termination of the LaAlO3 surface and interface.
The diagram is not drawn to scale.
integer quantum Hall effect5. Continuing
this work, Masashi Kawasaki (Tohoku
University, Sendai, Japan) showed that recent
improvements have now raised that mobility
value to ~20,000cm2V1s1. Thus, ZnO
heterostructures seem well on their way along
a similar path of steady and yet remarkable
improvements that has been crucial for
the impact of GaAs/(Al,Ga)As devices6 on
scientific and technologicaldevelopments.
The frontiers of research in oxide
interfaces were represented by a number
of groups presenting work on oxide
heterostructures using perovskites and
perovskite-derived materials. Perhaps
the simplest example, the electron gas at
the LaAlO3/SrTiO3 interface7 (see Fig.2)
demonstrates both the promise and
challenge of these complex structures.
Jochen Mannhart (University of Augsburg,
Germany) showed that in addition to the
superconducting ground state reported in
20078, the interface could be gated to map
out the superconducting phase diagram, and
induce a two-dimensional superconductor
insulator transition. It remains to be seen to
what degree interfaces between ternary and
quaternary oxides can be engineered and
improved as has been the case for GaAs, and
now under way for ZnO. Nevertheless, the
conclusion of the workshop is that the future
looks bright indeed.
References
1. Cheong, S-W. & Mostovoy, M. Nature Mater. 6, 1320 (2007).
2. Kingsmith, R.D. & Vanderbilt, D. Phys. Rev. B
47, 16511654 (1993).
3. Yamasaki, Y. et al. Phys. Rev. Lett. 98, 147204 (2007).
4. Kroemer, H. Rev. Mod. Phys. 73, 783793 (2001).
5. Tsukazaki, A. et al. Science 315, 13881391 (2007).
6. Pfeiffer, L., West, K. W., Stormer, H.L. & Baldwin, K.W.
Appl. Phys. Lett. 55, 18881890 (1989).
8. Reyren, N. et al. Science 317, 11961199 (2007).
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