STRONGLY GEOMETRICALLY Frustrated Magnets

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Annu. Rev. Mater. Sci. 1994.24:453-80
Copyright © 1994 by Annual Reviews Inc. All rights reserved
STRONGLY GEOMETRICALLY
FRUSTRATED MAGNETS
Annu. Rev. Mater. Sci. 1994.24:453-480. Downloaded from www.annualreviews.org
A. P. Ramirez
Access provided by Iowa State University on 01/29/19. For personal use only.
AT&T Bell Laboratories, 600 Mountain Avenue, Murray Hill,

New Jersey 07974
KEY WORDS: frustration, antiferromagnetism, Heisenberg spins
INTRODUCTION
The study of cooperative phenomena in magnetism has provided fertile

ground for testing theories of interacting systems that possess different
spatial dimensions, ranges, and sign of interactions, and that exhibit local
anisotropy of the basic interacting unit, the magnetic spin. This study has
also motivated the development of new classes of materials, from the
oldest known type of magnets, namely ferromagnets, to modern substances
embodied in the unusual random field and spin glass compounds. In this
context, we use the term material class to mean a set of compounds that
share both microscopic, as well as macroscopic, or bulk, properties. Thus
for example, ferromagnets possess the microscopic uniform ferromagnetic
type exchange or dipolar interaction between spins, in addition to a bulk
low temperature magnetization approaching the theoretical saturated
moment value, and characteristic critical behavior at the Curie, or order
ing, temperature. Among the known classes of magnets, spin glasses are
among the most fascinating, displaying in their bulk properties simul
taneous sharp ordering features in their magnetic response while exhibiting
no such anomalies in their thermal response (1). These properties are
thought to arise from a ground state characterized not by a single potential
well representing the uniform arrangement of perfectly ordered spins, as
in a ferromagnet, but rather by an energy landscape with many nearly
degenerate ground state configurations separated by barriers of random
height ( 1 ).
The microscopic parameters empirically associated with spin glass
453
0084-6600/94/0801-0453$05.00
454 RAMIREZ
behavior are site disorder and frustration. These microscopic parameters,

however, are important for either defining or affecting each of the magnet
classes. With site disorder and frustration treated as independent, con
trolling parameters, the magnet classes have natural interrelationships, as
coarsely depicted in Figure 1. The top left box lists the well understood
magnet classes of ferromagnets, antiferromagnets (2), fcrrimagnets (3),
and metamagnets (4), which correspond to both weak frustration and low
disorder. By well understood, it is meant that the bulk phenomena in each
of the three temperature regions (high, low, and critical) can be completely
explained theoretically. For low frustration and high disorder, the

phenomena of random field magnetism and percolation effects are found.

Both high frustration and high disorder are exhibited by spin glasses. The
upper right box of Figure I represents materials that possess a high degree
of frustration, while having little or no disorder among the spins. In this
MAGNETIC GROUND STATES

FRUSTRATION
ferromagnetism
anti-ferromagnetism
ferrimagnetism geometrical
metamagnetism frustration
•
a: •
•
11
o
random fields spin

percolation glass
Figure J Ground states of insulating magnets from the perspective of site disorder and
frustration. The ground states associated with the class of geometrically frustrated magnets
have not been clearly defn
i ed.
GEOMETRICALLY FRUSTRATED MAGNETS 455
review, we demonstrate the existence of a distinct class of magnets having

these properties that we call geometrically frustrated magnets.
GEOMETRICAL FRUSTRATION DEFINED
It is important to distinguish the two classes where frustration effects are

observed, spin glasses and geometrically frustrated magnets. In the vast
majority of spin glasses, the microscopic conditions of site disorder and
frustration go hand-in-hand, namely the process of disordering the lattice
leads to frustrated interactions ( I ). A good example is found in the spin
glass CuMn, where the dilute Mn atoms sit at random sites in the Cu
host. Frustration occurs since the interaction between Mn atoms is of the

Ruderman-Kittel-Kasuya-Yosida (RKKY) type, which is oscillatory in
nature, and changes sign with a period given by the Fermi wavelength.
The typical Mn-Mn interaction is thus both random and has competing
interactions, which lead to frustration. This is illustrated in a simpler
fashion in Figure 2 (top) where a plaquette of a host lattice with a two
dimensional grid of spins with only antiferromagnetic (AF) bonds between
the spins is shown. Introduction of randomly spaced ferromagnetic (FM)
bonds, e.g. by modifying the exchange interaction by hole doping as in
La2Cu04 (5), leads to frustration that results from the nearly symmetric
and competing interactions; the local field at one spin on the plaquette is
much smaller than at its neighbors. A similar situation occurs when the
disorder involves site substitution of spins themselves, as in the case of
(Eu, Sr)S (6). The alternative to this type of frustration is shown in Figure
2 (bottom). Here the lattice itself, represented by the triangular plaquette,
possesses a fundamentally different symmetry than the square lattice (bi
partite) case. Because of this special symmetry, it is possible to have the
same qualitative local condition of frustration for one of the spins on the
plaquette, but without having to introduce disorder. In these examples,
the ground state is not uniquely defined. For the single plaquette, for
example, there are three lowest energy states, not including time reversal.
In the extended limit corresponding to a bulk solid, the ground state
entropy per spin of a triangular lattice of classical Ising spins is
So/kB � 0.32 which, if present in a real material, would violate the third
law of thermodynamics (7).
Frustrating Lattice Types

The example of geometrical frustration demonstrated in Figure 2 for the
case of a single plaquette can obviously be extended to infinite systems. In
addition to the geometry, however, the sign of the interaction and its range
are important. It is possible, in principle, to realize complete frustration
456 RAMIREZ
"SPIN GLASS" FRUSTRATION
I F I
o "".--... /\
-U--- H -
AF I( AF 'f)
-.!J, � iJ-
I AF I
GEOMETRICAL FRUSTRATION
Figure 2 ( Top) Plaquette of the square AF lattice with one bond replaced by a FM bond,
illustrating frustration induced by site disorder common to most spin glasses. (Bottom)
Plaquette of the triangular lattice, showing frustration occurring among spins in a site
ordered system.
either with a mixture of precisely tuned AF and FM nearest neighbor (nn)

interactions, or with next nearest neighbor (nnn) interactions. An example
of the former is the anisotropic triangular lattice where the interaction
strengths in the three directions defined by the triangle plaquette sides are
represented as (J b J 2, J 3) , where AF and FM interactions are < and > 0,
respectively. For interaction strengths to ( l , 1, - 1 ), in addition to the case
( - I , - I , - I ), as in the above example, Tc = 0, which indicates high
frustration (7). An example of the latter is the square lattice with nnn
interactions (along the plaquette diagonals) equal to precisely half of the
nn interaction (along the plaquette sides) (8). Since there is little control
over the precise magnitude of the different components of the interactions,
these situations are destined to remain merely mathematical constructs.
Much more likely are materials where all the interaction components are
isotropic. Therefore, compounds most likely to exhibit strong geometrical
frustration will possess triangle-based lattices and short-range AF
interactions.
There are, in fact many examples of realizable lattices that are based on
the triangle, in the same way that square and cubic lattices are based on a
square. The most obvious example of a geometrically frustrated system is
that of AF-nn-interacting spins arrayed on the triangular lattice, as shown
in Figure 3 along with an associated space group. A three-dimensional
analogue of the triangular lattice is the face-centered-cubic (FCC) lattice,
also shown in Figure 3. Here, as is clear from the lines drawn to depict
the nn interactions, it is most realistic to view the FCC lattice as a set
of edge-sharing tetrahedra, the tetrahedron being the three-dimensional
frustrating plaquette. The two-dimensional kagome lattice, also shown in
Figure 3, is distinguished from the triangular lattice by virtue of having

corner-sharing triangles. Its three-dimensional analogue is the pyrochlore,
Frustrating Lattices
2D
Triangle kagome
P63/mmc;2a P63/mmc;12k
3D
FCC Pyrochlore
Fm3 Fd3m;16c
Figure 3 Magnetic lattices that are frustrating when occupied by spins (black dots) with
nearest neighbor AF interactions. The left hand side corresponds to lattices with edge-sharing
triangles and the right side with corner-sharing triangles.
458 RAMIREZ
or B-site spinel lattice (Figure 3), which is built out of corner-sharing

tetrahedra. The distinction between corner and edge-sharing becomes
important when one goes beyond spins with Ising-type local symmetry to
planar, (x-y) and fully isotropic (Heisenberg) spins. For x-y spins on the
triangular lattice, there is, in fact a unique ground state, the so-called 120°
state, characterized by three sub-lattices, each FM with net moment at
1200 with respect to the other (9). For the kagome lattice, there is no
unique ground state, as is immediately recognized when the 120° state is
constructed for a single plaquette, and propagated to neighboring
triangles. There is a degeneracy in this procedure due to corner-sharing
in other words, the chirality, or sense with which the spins turn as the
triangle vertices are traversed in a given direction, cannot be transmitted

through a single bond. We are interested in the extent to which this extra
degeneracy is manifested in the low temperature behavior of real magnets.
There has been much theoretical work on Ising spins on frustrated
lattices (7). Typical calculated quantities are the ground-state degeneracy,
phase boundaries for varying interaction strengths, and thermodynamic
quantities. Although it is beyond the scope of this review to describe the
theoretical landscape, we simply emphasize that most real compounds
differ significantly from the idealized models. One example of departure
between models of frustration and real compounds has already been men
tioned, namely the inability to precisely control the interaction strength,
range, and anisotropy. Even for the optimal compounds, those with AF
nn interactions on triangle-based lattices, this inability can lead to a break
down of complete frustration-it is common, for example, to have nnn
interactions, and some amount of anisotropy, either within a two-dimen
sional plane, or by virtue of interactions between neighboring planes,
which will disrupt frustration for the triangular lattice. Another example
of a real-life constraint is that most spins are vectors and not scalar
Ising spins as frequently employed in models. The importance of this is
illustrated for the triangular system, which is completely frustrated (AF
nn interactions) for Ising spins, while topologically ordered in the 1200
state for x-y spins. Finally the role of impurities in frustrated systems
has not received much theoretical attention, whereas many of the most
interesting effects described below occur in systems with some amount of
quenched site disorder, usually dictated by chemical constraints. These
issues are more narrowly defined in the following sections.
Experimentally Identifying Frustration-Macroscopic
Properties
Since this is a review of materials, we must address how one goes about
identifying frustration in the laboratory. Wannier and Houtapple inde-
pendently demonstrated the basic feature of frustrated systems in theor

etical studies of Ising spins on a triangular lattice 00, 1 1). Wannier found
that for FM (nn) interactions, the internal energy takes the zero tem
perature value U(O) = 1.51, and a singularity occurred at T � 1 .8 1,
-
where 1 is the isotropic exchange constant that signals the phase transition
to the uniformly ordered state. On the other hand, for the AF interaction,
U(O) = 0.51, and no ordering singularity occurs. Since U(O) is not experi
-
mentally accessible, but the presence of a phase transition can be tested,

the overriding experimental principle for identifying frustration in an
anti ferromagnet is, therefore, that an ordering temperature, generically
called Te, is much less than the Te had the interactions been FM.
Experimentally, Te for an antiferromagnet is relatively easy to define,

using only bulk probes-one looks for singularities in either the specific
heat C(T), or the temperature-derivative of the susceptibility, ')G(T). In
order to determine the temperature at which the system would order for
FM interactions, we appeal to the mean-field (MF) solution to the simple
Hamiltonian in the absence of an applied magnetic field,
1.
where Jij is the nn exchange interaction, and S is the spin. Here the sign
convention is that J > 0 corresponds to the FM interaction. The MF
solution for Te is
2.
where z is the number of nearest neighbors, and kB the Boltzmann constant

( 1 2). The important point is that Te has the same value for FM as for
AF coupling (for the simple two sub-lattice case). The high-temperature
susceptibility in this model is given by
C
= -- - T» Te·
(J cw '
')G 3.
T -
2
Here the Curie constant C lt�p /3kB' where ItB is the Bohr magneton,
and p g[S(S + 1)] / , where g is the g-factor governing the splitting of the
=
1 2
=
spin multiplet by a magnetic field. In Equation 3, (Jew is equivalent to Te in

Equation 2, but with the sign of 1 not suppressed. Thus for FM exchange,
')G(T) will diverge at positive T, while for AF exchange, it will diverge with
a negative value of ()cw. This gives us an effective way, in principle, to
determine the temperature at which an antiferromagnet would order were
the interaction sign FM -- by fitting X(T) to Equation 3, extracting ()ew,
and rcvcrsing the sign. This procedure is depicted in Figure 4.
This procedure for determining ()ew seems straightforward, but for typi-
460 RAMIREZ
NON FRUSTRATED FRUSTRATED

TN Sew - TN« Sew
1 1
X X
/1
/ 1
/ 1
/ 1
/ 1
1 /
/ 1 /
/ 1 /
/ 1 /
/ 1 /
Sew TN T Sew TN T
Figure 4 How frustration is identified in an AF system. The left hand side shows a typical
case of the inverse susceptibility, Ih, vs temperature for a non frustrated magnet where
B,w � TN, the Neel, or ordering temperature. The right-hand side shows a frustrated magnet
where T « O,w'
cal nonfrustrated magnets it is usually extremely difficult to perform. This

is because Equation 3 dictates that the temperature range over which the
fit is made is much greater than Te. More exact solutions beyond MF
theory verify this necessity, as shown by the results of high temperature
series expansion (HTSE) calculations sketched in Figure 5 (13). Here, it is
seen that for the Heisenberg AF-nn square lattice, l /x. is linear only for
T > 2Tc• The deviation from linearity arises from a growing correlation
length (order parameter fluctuations), a feature not included in MF theory.
Fortunately, frustrated systems do not suffer the effect of growing cor
relation length at such high temperatures. This is demonstrated in Figure
5 by the HTSE calculation for the Heisenberg AF-nn triangular lattice,
where l /x. is clearly linear well below Bcw, the linear region limited only by
the region of applicability of the calculation. In real systems, a linear-in
T l /x can extend to even lower temperatures, as demonstrated by the
behavior of the s = 1/2 triangular lattice magnet NaTi02 (AP Ramirez, E
Bucher, unpublished information), also shown in Figure 5. Here l /x. devi
ates from linearity only at T � Bew/5. This behavior is a common feature
of geometrically frustrated magnets and is remarkable in the sense that it
portrays a completely free spin in a strongly interacting environment.
There is, at present, no analytical understanding of this exceedingly simple
bulk behavior and it probably deserves further study.
As was mentioned above, and is demonstrated below, (Jew is an experi-
series
expansion
experiment (Heisenberg)
Sew
triangular
1.
.
""
\ lattice
.....
"
"
.. �
"
-
..
en
.t::
c: \ " . . \. .... � ....
.... '"
-
.. "-
::J .... '
"' ,
\..
�
" , �-""--
.ci ,a,. --.�
=::r·7.:-: \square
····
....
-
� 1'-
I �
?-<! Sew lattice
- .
� NaTi02
Sew � 1060
J "" 350 K
TN <4 K
I
o 700 1400
T (K)
Figure 5 The inverse susceptibility, l/x, for the triangular delafossite system NaTiO"
compared to high-temperature series expansion results for the triangular and square lattices.
The two curves for each lattice show the result of summing up to the 9th and I Oth (8th and
9th) terms for the triangular (square) lattice. The square lattice shows deviation from linear
in-T behavior for T ;:::: 28,w as expected due to order-parameter fluctuations, whereas the
triangular lattice shows no deviation down to O.758,w, the limit of the calculation, and
perhaps to lower temperatures.
mentally well defined quantity for frustrated AF systems. This allows the
definition of an empirical measure of frustration by the quantity
4.
where Tc represents any cooperative-ordering transition temperature (14).
Clearly, J> 1 corresponds to frustration. This is the norm for anti
ferromagnets (2), although care must be taken in assessing published
values of /Jew-sometimes strict linearity is not obtained. In the examples
described below, the criteria we use are that linearity is observed over a
temperature range of order or greater than /Jew' and that the moment
462 RAMIREZ
obtained through the Curie constant corresponds to the expected value

for the magnetic ion in the particular ligand environment ( 1 5). Examples
of moderately large / values include the FCC materials FeO, MnS, and
MnSe, for which/� 3 ( 1 6). The MF solution to the simple two sub-lattice
antiferromagnet, however, yields/ 1 , as for the ferromagnet. Anderson
=
showed that by extending the number of sub-lattices to four, as is natural

for the FCC lattice, / = 3 could be obtained in a MF theory ( 1 7). By
including nnn interactions and employing eight sub-lattices, Anderson also
found/ 5 could be achieved, the value appropriate for MnO. Ter Haar
=
& Lines (TH-L) ( 16) generalized the MF method for third- and fourth
nearest neighbor interactions and up to thirty-two sub-lattices and found

that in this extreme limit of interaction range, / 1 5 could be achieved.
=
On the other hand, they noted that for large/values, e.g. the FCC lattice
with nn interactions, where / = 00, MF theory breaks down in the sense
that it predicts a finite Te. Thus TH-L ascribe experimental values off'? 10
not to a MF multisub-lattice picture, but to a more complicated state, not
accessible by MF theory. We use this value as a benchmark of strong
geometrical frustration. Materials with /> 1 0 are for our purposes
strongly geometrically frustrated (SGF) and are not describable by MF
theory. Below we list examples of such SGF compounds and demonstrate
that they constitute a distinct class of magnets.
Materials with Strong Geometrical Frustration-Microscopic

Properties
Table 1 lists several compounds having /> 1 0. We see a wide range of
Bcws from 2.3 to 1000 K, and materials whose ground state is either AF or
spin glass (SG), depending on the presence or absence of magnetic site
disorder. The most obvious similarity between the compounds is that all
have magnetic lattices built out of triangles. For the two-dimensional
compounds, the lattices are either triangular or kagome. For the three
dimensional lattices, they are mostly based on tetrahedra, although for the
garnet Gd3GasO 12, the lattice is more complicated, yet still incorporates
triangles. The other similarity among these materials is the single-ion
symmetry of the magnetic constituent. Nearly all compounds in this list
possess highly isotropic ions, either s-state ions like Mn 2+ or Gd 3+, or
transition metal ions with fully quenched orbital moments. This is con
sistent with expectations for ordering based on numerical and MF theory
modeling (7). The simultaneous occurrence of (a) the macroscopic property
of high frustration, as evidenced by the large / values shown in Table 1;
(b) the microscopic properties of triangular lattice symmetry; and (c)
isotropic local moment among this small group of materials is taken as
criterion for a new class of magnetic materials. The latter point could
able 1 Strongly geometrically frustrated magnets
Magnetic -/Jew T, Ordered Electronic

Compound lattice (K) (K) f state configuration R eference
'wo-dimensional magnets
VCI, triangular 437 36 12 AF 3d' 64
NaTiO, triangular 1000 <2 >500 3d' 34
LiCrO, triangular 490 IS 33 AF 3d' 35
Odo.8LaoiCuO, triangular 12.5 0.7 16 SO 4[1 38
SrCrSOa40'9 kagome 515 3.5 150 SO 3d' 23
KCrJ(OHMS04)1 kagome 70 1.8 39 AF 3d3 31

'hree-dimensional magnets
ZnCr,04 B-spine1 390 16 24 AF 3d' 54
K,IrC16 FCC 321 3.1 10 AF 5d' 62
FeF3 B-spinel 240 15 16 AF 3d' 65
CsNiFeF, B-spinel 210 4.4 48 SO 3d8,3d' 60
MnlnlTe4 zinc blende 100 4 25 SG 3d' 66
Od,Ga,O'2 garnet 2.3 <0.03 >100 4[7 52
Sr,NbFe06 perovskite 840 28 30 SO 3d' 67
Ba1NbV06 perovskite 450 15 30 SO 3d3 A Ramirez,
E Bucher,
unpublished
information
have been anticipated-we have already discussed the need for highly
anisotropic interactions to achieve a SGF state. It is known, however, that
both moment and interaction anisotropies have the same origin rooted in
the orbital degrees of freedom, and that they usually appear in consort in
a given material ( 1 8). Tn some sense, this class complements the class of
metamagnets (4). The interesting physical effects in these materials arise
from competition between applied field and strong local anisotropy. It is
apparent that the interesting effects in SGF magnets arise from the inter
play between temperature and strong conflicting interactions.
Difference Between Strong Geometrical Frustration and Low

Dimensionality
The phenomenon of a transition temperature much lower than predicted
by a given exchange constant magnitude and number of nearest neighbors
is not unique to SGF systems. In one dimension, for example, it can easily
be shown that entropy effects. prohibit long. range ordering, regar.dless of
the spin-dimensionality. In. two dimensions, lon g range configurational
order only occurs for Ising systems (19)'. Thus these are examples of
systems where Tc can, in principle, be suppressed 'and perhaps confused
464 RAMIREZ
with strong geometrical frustration. Experimentally there are many ex

amples of magnets whose structure allows magnetic interactions in a par
ticular low-dimensional subspace to dominate (20). There is, however, a
practical difference between low dimensionality and frustration-the for
mer will develop correlations well above the MF To. as would any non
frustrated system-order parameter fluctuations are not suppressed at
high temperatures, they just never develop fully below the MF Te. As a
result there still remains the difficulty in determining Bew via bulk sus
ceptibility, as detailed above. So the low-dimensional systems gain entropy
by a rarefication of spin density, whereas SGF systems gain entropy by a

particular dense spin arrangement. One expects the way the two types of
systems approach the zero-entropy ground state will also be qualitatively
different, and that for SGF magnets there will emerge new physics at low
temperatures of a type not anticipated by MF or spin wave theory (2).
In this review we are concerned primarily with the effect of strong
frustration on the ground state and its associated excitations. The effects
of frustration are also observed in the critical region of magnets that have
moderate frustration. In these systems, frustration is considered to be
an added parameter, along with dimensionality, local anisotropy, and
interaction range, which govern the detailed approach to the transition
temperature of the various thermodynamic quantities (21). A treatment of
the experimental aspects of this subject is beyond the scope of this article.
In the following sections, we describe in more detail, the materials
properties and physical effects of several SGF compounds. Some of these
materials have recently been identified and studied more closely from the
standpoint of modern ideas of frustration. Other compounds have been
in the literature for some time-many of these can be viewed in a different
light at this time and warrant further study.
MODEL COMPOUNDS
SrCr9pGal2_9pO 19
MAGNETIC RESPONSE The compound SrCr9pGal2_9pOl9 (SCGO(p)) (22)
forms in the magnetoplumbite structure in which the majority of Cr ions
occupy the 12k positions of the P63/mmc space group, which form a
kagome lattice (23), as shown in Figure 6. Since the density of spins in this
layer is three times the density in the other two types of (triangular) layers,
the cooperative behavior will be characteristic of coupled kagome lattices.
Obradors found that for p = 0.89, no ordering occurred in this material,
despite its having Bcw :::::: - 500 K (22). This concentration is an upper limit
for achieving single-phase material, and refinement of neutron diffraction
data showed that for this concentration, the density in the kagome layer
/ •
: ,
I
I�
:
•
\4f
1(\1
AA�9»
", '7/ \"irii::--...
•
""'/ / , .....
,
\
--S1
12k
'Z,.
''Ii?
v. \za
•
. · •
I 1\
Figure 6 The magnetic lattice for SrCr,Ga,OI" The planes labeled 12k are kagome nets,
and the other planes are triangular with one third the density of sites of the 12k layer. In the
nonstoichiometric but single phase compound SrCr,Ga40I9, the 12k sites are only 86%
occupied . The interatomic distances are shown in Angstroms.
is 86%, the shortfall being made up in an overall less densc triangular

layer between the kagome planes. As shown in Figure 7, l /x is remarkably
linear down to less than 100 K. Ramirez et al showed that for this con
centration, hysteretic behavior in the dc-susceptibility, similar to that of a
spin glass, occurred at 3.5 K (23). Spin glass order was verified by the
observations that the nonlinear susceptibility, X3' defined by
M = X1H+X3H3+ . . . . 5.
X3 diverged a s (T - Tc) -Y' Here y was found t o lie i n the range 2-3 for a
freezing temperature Tc 3.5 K, in accord with typical values found
=
for three-dimensional SGs. The authors proposed that SCGO(p) is a

manifestation of a quasi-two-dimensional SG, similar to quasi-two-dimen
sional site-ordered magnetic systems, where the correlated spin motion is
mainly in the two-dimensional planes except in the vicinity of the transition
to three-dimensional order, which occurs at a temperature much lower
than the effective temperature because of small interlayer coupling. Neu
tron scattering studies by Broholm et al confirmed both the two-dimen
sional nature of the interactions, and that SO freezing does occur at
roughly the same temperature for a p = 0.72 sample. The correlation
length remains small, ::= 7 A, even down to the 1.5 K, as expected for a SG
(24).
466 RAMIREZ
:::J
E
9 Fe Q)
Q) �400
'0 ...:
E Q)
.....
�200
::::s
E 7 ...
Q)
I
)(
It) 200 400
b T (K)
5
U
"0
><
3 �------+---�--�--�
�0.2
I
Q)
(5
E
.....
J 0.1
5 10 15 20
TEMPERATURE (K)
Figure 7 The susceptibility, X (top) and specific heat divided by temperature, CIT, for
SrCrSGa4019' The temperature at which a sharp anomaly occurs in the hysteresis between
zero field cooled (ZFC) and field cooled (FC) data signals a spin glass transition at 3.5 K,
also seen in other experiments as a diverging nonlinear X and a finite neutron scattering
correlation length. The inset shows l/x for three different samples (a) ceramic SrCr sGa40 19,
(b) microcrystalline SrCr693Ga'O,OI9, and (c) crystalline SrCr34,Ga8.5S019' The bottom
panel demonstrates the quadratic-in-T behavior of C, below the freezing temperature 3.5
3
K. The dashed line is a T term for the sake of comparison. The lattice contribution, not
subtracted from the data, is only about one fifth of the magnitude represented by the dashed
line.
SPECIFIC HEAT The specific heat, C(T), of the SCGO(p) was measured for
several different p values by Ramirez et al (23, 25). The low temperature
C(T) is a common probe of elementary excitations in magnetic solids
from its temperature and magnetic field dependence, it is usually possible
to infer the ground state from which the excitations arise. Normally, one
finds in SGs, a broad maximum in C(T) at a temperature about 50% above
the freezing temperature ( I ) . Below this temperature, C(T) ex T, which is
commonly understood to arise from a distribution of two-level systems
linear in energy (26) dictated by the homogeneous disorder inherent in SG.
Surprisingly for SCGO(0.89), it was found that, despite the magnetic
behavior usual for a SG, C(T) IX. T2 (Figure 7), the form expected for
spin waves in a quasi two-dimensional antiferromagnet. [For a magnet
possessing long range order, C(T) IX. Td/v, where d is the spatial dimen
sionality (2 in this case) and v the exponent in the excitation dispersion,
equal to I for an antiferromagnet.] Further, it was shown in the same
samples, which exhibited the 7 A neutron scattering correlation length,
that there was no evidence for a finite-size gap in C(T). This ruled out an
extrinsic explanation for such behavior, e.g. from chemical clustering of

an AF phase not representative of the average stoichiometry. Thus the

elementary excitations of SCGO(p) imply an ordered state in the kagome
sub-lattice, with the same dispersion relation as that of an antiferromagnet.
Further the large amount of entropy, :::::: 10% Rln(2S+ 1), developed below
5 K implies an extremely soft excitation. Normally, for a system that
orders at 500 K, one expects only of order 5/500 = 1 % of the total entropy
developed at this temperature. By relating the coefficient of the T 2-specific
heat term to a spin wave stiffness, Ramirez et al argue that the stiffness of
the frustrated modes is about 0.04 of that expected were the same mag
nitude of interactions not frustrated (25).
NEUTRON SCATTERI NG The short correlation length found by elastic neu
tron scattering has already been mentioned. In addition, by investigating
the combined elastic and inelastic response, Broholm et al were able to
estimate the fraction of moment frozen into a static configuration and
found the surprising result that this accounted for only 25% of the total
moment (24). In other words, ground state quantum fluctuations account
for 75% of the total moment-these fluctuations are presumably respon
sible for the unusual C(T).
Presently there is not a firm understanding of the origin of C(T) in this
system. Suggestions have been made that the ordered state implied by the
quadratic-in-T behavior of C(T) corresponds to the Edwards-Anderson
(27) order parameter proposed for SG almost two decades ago, and never
detected. In the present system, its detectability could be a result of the
extremely largc frustration relative to the amount of disorder. In this
respect, it is natural to ask whether a similar C(T) might be observed in a
SGF three-dimensional system. Another theory speculates that the ordered
state is akin to that of a nematic, where the order is represented by the
"sense" of a twisting vector, in this case the spin (28). Since this is a tensor
quantity, it will not be directly observable by neutron scattering, but will
nevertheless yield a quadratic C(T). Further measurements are needed to
resolve this issue.
468 RAMIREZ
DILUTION STUDIES The dependence of the thermodynamic quantities on

magnetic dilution has been studied for SCGO(p) in two different ways,
first using solvent-grown crystals (23), and secondly using ceramic poly
crystalline material (25, 29). The studies already mentioned, for p = 0.89,
were performed on ceramic material. Ramirez et al studied the dependence
of transition temperature on p in several nonceramic samples synthesized
by different solvent methods (23). The first was grown from SrO-B203
solvent and consisted of grains of < 1 .urn in size. Susceptibility measure
ments showed that p = 0.77 and Tc = 4.3 for these microcrystallites. The
second type of noriceramic sample was grown from Bi203-V 20S solvent
and the single crystal grain was of order 2 mm. For these samples, it was
found that p 0.38 and Tc 7 K.

= =
The dilution dependence of Tc in the crystals is to be contrasted with

that observed in ceramic specimens. The first such study was made by
Ramirez et al (23), who showed that in ceramic samples with p 0.72 and
=
0.39, Tc was 2.5 and <2.0 K respectively. Martinez et al performed a

similar study with a larger number of specimens and found a linear depen
dence of Tc on p between p = 5 (Tc 1.8 K) and 8.78 (Tc 4.05 K), in
= =
rough agreement with the previous work (26).

The doubling o[ Tc on going [rom p = 0.89 to p = 0.38 is a surprising
result-normally when the average number of nearest neighbors decreases,
the cooperative ordering temperature decreases linearly, as in Equation 2,
for example. This has been confirmed for ceramic material by Martinez et
aI, who show that the various Cr-sites are randomly occupied for the
diluted samples (29). Since the density in the kagome layer for the p = 0.89
ceramic samples is only 86%, presumably it is lower than the p value for
the solvent-grown crystals. Ramirez et al speculated that the unbalance of
density between the kagome layers and the other triangular layers is
enhanced in the crystalline samples, i.e. the dilution becomes more inhomo
geneous than in the ceramics, possibly driven by a steric constraint not
present in the high temperature ceramic processing (23). This unbalance
would lead to both a lower effective interaction between spins in the
kagome planes and larger coupling between the planes. Since the SG
transition is thought to be a three-dimensional transition, a higher Tc
would naturally result from this scenario. To test the hypothesis of pref
erential site occupation in the crystalline samples, Ramirez et al processed
p = 0.38 single crystals as starting material for a ceramic sample and found
that Tc was reduced to below 2 K (as shown in Figure 8), consistent with
results from other ceramic specimens (AP Ramirez, unpublished
information).
A secondary effect of inhomogeneous Cr distribution in the crystals is
a change of the f ratio upon dilution. In the dilution studies in ceramic
ceramic
processing
4
0.5 1.0
P (Cr)
Figure 8 The spin glass ordering temperature, TO' for SrCr9 Gal2_9pOl9 crystals grown
p
using solvent methods (upper set), and by high temperature ceramic techniques (lower set).
The arrow represents the experiment in which crystals were processed to form a ceramic
sample. The difference in T,s is ascribed to inhomogeneous site occupation in the crystalline
samples.
samples it was found that!:::::: 1 50 and remains virtually unchanged (25,

29) as Tc is varied, consistent with mean-field expectations. On the other
hand, in the solvent grown crystals,! is 90 and 27 for the microcrystallites
and single crystals, respectively (23), which further indicates a change in
the relative site occupation of the Cr sub-lattice.
Jarosite KCr3(OHJdS04J2
The kagome-lattice jarosite compound KCr3(OHMS04)2 has been less
well studied than SCGO(p), mainly due to difficulty of synthesis. It has a
simpler structure than SCGO(p), possessing only one Cr site, that of
the kagome plane, and thus might be more attractive theoretically. The
susceptibility has been measured yielding Bow -67.5 K (30). No ordering
=
was found to occur down to 2 K, thus!> 34. Subsequent C(T) measure-

470 RAMIREZ
ments showed an ordering anomaly at 1.75 K (31 ). In Figure 9 a more

complete set of C(T) data on a different sample, with Tc 1 . 55 K is shown
(AP Ramirez, unpublished information). At low temperature C(T) seems
=
to be approaching TZ behavior as expected for a two-dimensional anti

ferromagnet. Neutron scattering studies also show the expected onset of
Bragg scattering between 1 .8 and 2 K, in agreement with C(T) (3 1). The
observed wavevector dependence is consistent with the so-called q 0 =
structure, in which the magnetic structure has the same unit cell as the
lattice. An alternative possibility for the kagome lattice is the J3 x J3
structure, corresponding to tripling of the unit cell area. This is an
intriguing possibility since it allows for zero-energy modes, which imply a

finite entropy at T 0 (32).

=
Rare Earth Delafossites-RCuO 2

The delafossite structure with stoichiometry ABOz, shown in Figure 1 0,
is ideal for studying the effects of geometrical frustration (33). Among the
two-dimensional materials listed in Table I, NaTiOz (34), LiCrOz (35-37),
Te = 1.55 K
� I
(l)
(5
E
-
-,
-
t:
o
0.1 10
T (K)
Figure 9
The specific h�at divided by temperature, CjT, for the jarossite compound
KCrlOHMS04h
Figure 10 The lattice structure for the delafossite compound LaCuO,. The lanthanide site
is represented by the encapsulating oxygen octahedron. The copper atoms on a triangular
lattice are two-fold coordinated, monovalent and therefore nonmagnetic.
and Gdo.sLao.2Cu02 (38) possess this structure. The latter compound is

one of the family RCu02, where R is a rare earth ion. We note that Cu is
monovalent in this structure, to maintain charge balance, and is therefore
nonmagnetic. As shown in Figure 1 0, the Cu atoms are arrayed in tri
angular layers connected to neighboring layers only by apical oxygens.
RCu02 is the only triangular lattice system involving rare earth ions. It
forms single phase material for the early rare earths, up to Gd, so the
systematics of frustration can be investigated. Another motivation for
studying these compounds is that the exchange interactions in rare earth
compounds are typically on the order of a few degrees Kelvin, thus it is
possible to alter the cooperative behavior with easily attainable magnetic
fields. Ramirez et al investigated the compounds with R Pr, Nd, Sm, =
Eu, and GdosLao.2 (38). Compounds with higher Gd concentrations, as

well as the later rare earths, were found to be unstable. Not surprisingly,
the ground states of the Pr and Eu members are nonmagnetic singlets,
thus no cooperative low temperature behavior is observed. The Sm com-
472 RAMIREZ
pound has a susceptibility possibly arising from oxygen deficiency and

associated multiple valence states. For R Nd, ordering was observed at
=
0.7 K as a large A-type anomaly in C(T), and eew was -4.4 K, giving
J 6. 1. For R Gdo.sLao.z, no sharp ordering anomaly was found, but
= =
rather a broad C(T) peak with a maximum at T = 1.8 K. Measurements

of the ac-susceptibility, Xae, at various frequencies showed an anomaly at
about 0.6 K at 10 Hz, which increased slightly to 0.8 K at 10 kHz, an
effect that is a characteristic signature of SG ( 1). Combining this Te with
(Jew 1 2 . 5 K yields J 17. This is a demonstration of the effectiveness of
= =
the isotropic ion, here the s-state ion Gd J+, for producing a frustrated
state.
The low temperature C(T) for Gdo.sLao.zCuOz is shown in Figure 11,

on a reduced scale, for comparison with two other SG compounds and
SCGO(O.89). We see that the quadratic-in-T dependence is also present in
this compound, which suggests an explanation that is not specific to one
compound. In particular, the influence of quantum effects on the quali
tative nature of the ground state are probably irrelevant since Gd J+ has a
large moment and can be considered a classical quantity.
Transition Metal Dela/ossites-LiCrOz, NaTiOz, LaCu02+b

The delafossite structure can also be realized with transition metals as the
magnetic species. The highest interaction strengths are found in NaTiOz
(34). In neutron scattering and susceptibility studies no magnetic Bragg
peaks signaling an ordered state were found down to 1.4 K. Ramirez et al
studied the susceptibility of this compound and found a well-defined Curie
Weiss susceptibility in one sample with ()cw � 1 000 K and no ordering
down to 2 K, which yields J> 500 (Figure 5) (AP Ramirez, E Bucher,
unpublished information). This material is potentially the most interesting
of a ll SGP magnets because Ti 3+ has s = 1 /2, thus quantum effects might
be pronounced at low temperature where there is still no long range
order. Unfortunately, NaTi02 is very unstable-it cannot yet be made
reproducibly and the samples degrade on the time scale of hours.
LiCr02
This delafossite-type compound has been studied by a number of tech
niques. Susceptibility measurements yielded a linear l /X between 450 and
800 K, giving (Jew = 570 K (35). An ordering anomaly is observed at 12
-
K, thus f 48. The magnetic structure was determined with neutron

=
scattering and the strong two-dimensional character was confirmed (36).

The ordering temperature in the susceptibility measurements is in seeming
disagreement with that reported in an ESR study, 65 K (37). In the latter
....
I-
"
I-
�
U
"
• a
I- a
,.
" 0.3 6
a
•
U A
a
<> EuO•4SrO•6S
a
a o Cdo.aMnO.2 Te
6. Lao. aGdo. eCuOa

a
a o SrCraGa4019
0.1
0.1 0.3
Figure 11 The specific heat divided by temperature, CjT, normalized to the value at the
spin glass transition for two well-studied spin glass compounds, Cdo.8Mno.2Te (39), and
EuO.4SrO. 6S (40), and two highly frustrated, (J,w» Too compounds, La02Gdo.8CU02, and
SrCrgGa.O'9' The former two display the linear behavior associated with a two-level,
disorder-generated density of states, whereas the latter two show behavior consistent with a
(two-dimensional) spinwave mode.
study the temperature dependence of the ESR linewidth was interpreted

as evidence for the unbinding of Z2 defects, which are the analogue of
Kosterlitz-Thouless vortices in a nonfrustrated system. The Z2 defect is
stable topologically and differs from the Kosterlitz-Thouless vortex in that
it takes on only one of two topologically distinct forms instead of an
infinite variety characterized by a winding number (4 1 ) .
474 RAMIREZ
LaCU02+o' YCU02+o
These compounds are nonmagnetic for the pure delafossite phase, cor
responding to b = O . For this phase, the Cu I + ions are connected to the
rest of the lattice only by oxygens in the neighboring planes (Figure lO)
and are nonmagnetic. Cava et al showed the possibility of intercalating
oxygen atoms into the copper planes, and were able to make single-phase
polycrystalline material over most of the range 0 < b < 0.67 (42). They
showed that two phases resulted. For the yttrium compound, the sus
ceptibility and resistivity both show a gap in the excitation spectrum, with
the former having a broad peak at about 450 K. The La compounds suffer
some phase decomposition below b = 0.55, and above this value display
Curic-Weiss behavior. For b 0.57, Bew = - 57 K, and no ordering

=
anomaly is seen down to 0. 1 K (AP Ramirez, RJ Cava, unpublished

information). There are possibly two structure types corresponding to
different modifications of the oxygen superlattice. For the Y compound,
a dimerization of the oxygens would help to explain the data, whereas for
the La compounds a disordered superstructure is possible.
A Frustrated Garnet-Gd3Gas012
The compound Gd3Gas012 (GGG) forms in the garnet structure, which
incorporates sparse triangles of corner-sharing spins in a cubic lattice (43,
44). Like most of the rare earth garnets, GGG has been the subject of
extensive thermodynamic investigation for specific heat (45-50), thermal
conductivity (49), and magnetization (46-48, 50), above 0.3 K. Among the
rare earth-gallium garnets, RGG, most display AF ordering around I K.
Like the rare earth delafossites, though, the behavior of the R = Gd
member is anomalous. Figure 1 2 shows C(T) on a reduced scale for several
members of the series, and it is obvious that all but Gd have sharp ordering
anomalies, whereas R = Gd displays a broad peak with maximum at 0.7
K. Although this peak was originally ascribed to a crystal field splitting,
two results argue against this. The first is the ESR study of dilute Gd ions
in the nonmagnetic hosts YGG and LuGG, which show an overall splitting
of only lOO mK (5 1 ). This would produce a C(T) Schottky anomaly
with peak at roughly half this temperature, or 50 mK, much lower than
observed. The second result is the field dependence, which shows the peak
maximum decreases in temperature with increasing field (46-48), opposite
to that of a crystal field splitting, which should increase with field. However,
this is the behavior of a short range order peak for an incipient AF
transition. Measurements of Xae down to 25 mK showed no sharp ordering
anomaly in zero field (52), so with a (Jew = - 2.3 K, we see that GGG has
J> 90. These measurements, along with specific heat and thermal
R = Gd
1
><
tU
E
Q Dy
()
- - - - Sm
Nd
Er
0.8 0.9 1 .0 1 .1
(TITmax)
Figure 12 The specific heat, C, of rare earth�ga\lium garnets, normalized to (approximately)
the maximum value. This figure shows the qualitative difference in the behavior of the highly
frustrated R = Gd compound, compared with the other nonfrustrated compounds (data
were compiled from References 45, 68). Curves have been offset slightly for clarity.
expansion measurements (53), were also performed in applied fields (Figure

1 3). In C(T) where there was no ordering peak in zero field, in a finite field
an extremely sharp ordering peak appeared, as shown in Figure 1 2, and
associated with it, a highly unusual phase diagram appeared, as shown in
Figure 14 (53). There is still no good understanding of the nature of the
ground state or the ordered phase in this compound. It seems to be
an excellent candidate for further experimental work, despite the low
temperatures involved, since the interactions are well understood (44) and
since the interesting cooperative behavior occurs in site-ordered matcrial.
Zn Cr 20 4-A Model Spinel

The spinel compound ZnCr20 4 (54) has been well characterized by a
variety of diffcrent methods. It can be thought of as the parent compound
to SCGO(p)-(1 1 1 ) planes of the spinel lattice are k agome nets, and the
local Cr3+ environment is identical in the two compounds except for a
difference in Cr-O bond length. The interaction range and sign are critical
to understanding the origin of frustration in these compounds. Blazey
studied the fluorescence spectrum of Cr3+ pairs in ZnAl204 and found a
ferromagnetic nn exchange of 14.7 K (55), in contrast to the AF
476 RAMIREZ
10
�
I
"0
<.!)
Q)
o
E
.......
J
5
u
O L- __ -L____L-__�____�__�____�__�
o 0. 5 1 .0 1 .5
T (K)
Figure 13 The specific heat, C, of Gd3GasO 1 2 (GGG) for several different applied fields.
Bcw =- 392 K (54). Kino & Luthi (56) found a smaller Bcw ( - 330 K) in =
a single crystal used for susceptibility and elastic measurements. They infer
a nnn AF exchange constant of - 7.3 K which, because of the larger
number of nnns (30) compared to the nns (6), leads to a net AF interaction.
They observe a sharp first-order anomaly in the shear modes at 9.3 K for
their crystal, in addition to an AF signature in the susceptibility, the former
indicating that a structural transition accompanies the AF transition. The
frustration index f ranges from 25 to 35 for different samples. Neutron
diffraction and specific heat studies (57, 58) confirm a first-order transition
in the vicinity of 1 3 K, to noncollinear ordered structure. The dilution
series ZnCrxGa2 _ x0 4 has been studied by Fiorani et al by susceptibility,
neutron diffraction, Mossbauer, and EPR techniques (59). These measure
ments yield a phase diagram with an AF phase above x ;:::: 1 .70 , below
which a SG state develops that the authors attribute to the presence of
geometrical frustration.
2.0 r-----.---��---.
.. . ...... . .. ... . .
.
. .. .. ... . . .
. ..
o
"
.
..
. . ..
1 .5 [1 00('" . .
....... .... .. ..
[111 ] .
..
. .
·"·
0
o
.
..
..
...
. ..
..
..
.
..
<II :
� 1 .0 .
:
'
. .. .
.
.. .
.
..
.
.
.. .
.
..
. .
.
. . ..
. .. ..
..
.
. ..
. . . . . .. . . . . ...
. . . . . . . . . . . . . . . . . . . . . . . .. - .. .
. .
. .. .
• • • • ••••• ••• . . .. .
• • • •••• • • • • •• • • •• • •
• • • • • h • • • • • • • • • • • • • • • • • • • • ..
• •
0.5
o � �________�______�______�
1
______
o 0. 0.2 0.3 0.4

T( K )
Figure 14 The phase diagram of Gd 3Ga sO 1 2, showing positions of the ac-susceptibility
anomalies (dotted lines) for two different crystallographic directions, specific heat anomalies
(open circles) and thermal expansion anomalies (reproduced from Reference 53).
CsNiFeF 6
The compound CsNiFeF 6 is also a B-site spinel, but unlike ZnCr20 4, there
are two magnetic ions that share the same crystallographic site, leading to
inherent site disorder and spin glass behavior, even without magnetic
dilution (60). The Curie-Weiss constant is .(Jew - 2 1 0 K and the SG =
transition is at 5 K, yielding f 40. The related compound CsMnFeF 6 =
has f = 1 1 , and the susceptibility for both compounds has a complicated

temperature dependence.
K2Ir Cl 6
The last entry among the three-dimensional systems i s K 2IrCI6, a n FCC
antiferromagnet. This compound was found by EPR measurements to
478 RAMIREZ
possess nearly isotropic AF exchange interactions among the Ir 4 + ions

(effective spin s 1 /2) (6 1 ) . Susceptibility measurements yield 8cw 32 ± 4
= =
K and a TN 3 .08 ± 0.05 K, so f 1 0 (62). Specific heat measurements

= =
show a sharp anomaly at 3 K (63). Surprisingly, the ammonium version

of this salt, (NH 4) 2IrCI6 (f 9), shows a sharp first-order-like C(T)
=
anomaly at 2 K, which suggests a structural transition.
CONCLUSION
We have presented arguments that the materials reviewed here can be

viewed as a separate class of magnets, distinct from the usual classes of
ferromagnets, antiferromagnets, ferrimagnets, and metamagnets, to name
a few. The crucial elements that define this class are (a) the bulk property
of frustration, namely a low transition temperature compared to the Curie
Weiss constant, and (b) shared microscopic properties of a triangle-based
magnetic lattice and isotropic local symmetry and exchange interactions.
We have also attempted to show some of the fascinating cooperative
properties that arise from a highly geometrically frustrated ground state.
Many of the materials reviewed here were reported up to decades ago, but
now should be restudied in the light of a new perspective on the effects of
frustration. Finally, and most importantly, the empirical observation of
this class provides direction for theory. Most theoretical work on frus
trating lattices has been done for Ising spin systems. Conversely, we find
that only Heisenberg-type systems are likely to exhibit frustration effects.
Clearly, theoretical efforts should be made to directly confront experiment
by focusing on Heisenberg systems.
Any Annual Review chapter, as well as any article cited in an Annual Review chapter,
may be purchased from Annual Reviews Preprints and Reprints service.
1-800-347-8007; 415-259-5017; email: arpr@c1ass.org
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474-84
ANNUAL
REVIEWS Further
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Annual Review of Materials Science
Volume 24, 1994
CONTENTS
MATERIALS SCIENCE AND ENGINEERING, AN EDUCATIONAL

DISCIPLINE, Morris E. Fine and Harris L. Marcus
C> CARBON-CARBON COMPOSITES, J. E. Sheehan, K. W. Buesking,

and B. J. Sullivan 19
THE PROBLEM OF DOPING IN II-VI SEMICONDUCTORS, D. J. Chadi 45

C> POLYMER COMPOSITES, F. J. McGarry 63
C> WHISKER TOUGHENING OF CERAMICS: Toughening Mechanisms,
Fabrication and Composite Properties, Murat Bengisu and
Osman T. Inal 83
ION IMPLANTATION OF OPTICAL MATERIALS, Ch. Buchal,
S. P. Withrow, C. W. White, and D. B. Poker 125
ELECTRODEPOSITED MULTILAYER THIN FILMS, C. A. Ross 159
C> TECHNOLOGY OF SELF-REINFORCED SILICON NITRIDE, A. J. Pyzik
and D. F. Carroll 189
SURFACE AND INTERFACE STRESSES, Robert C. Cammarata and
Karl Sieradzki 215
CARBON NANOTUBES, Thomas W. Ebbesen 235
NEUTRON-DIFFRACTION DETERMINATION OF RESIDUAL STRESSES
IN ADVANCED COMPOSITES, D. S. Kupperman 265
C> FRACTURE MECHANICS FOR FAILURE OF CONCRETE, S. P. Shah
and C. Ouyang 293
C> PLASTIC FLOW IN SIC/ AL COMPOSITES-STRENGTHENING AND
DUCTILITY, N. Shi and R. J. Arsenault 321
C> PROGRESS IN TRANSFORMATION TOUGHENING OF CERAMICS,
M. V. Swain and R. H. J. Hannink 359
C> ORDERED INTERMETALLICS, E. P. George, M. Yamaguchi,
K. S. Kumar, and C. T. Liu 409
STRONGLY GEOMETRICALLY FRUSTRATED MAGNETS,
A. P. Ramirez 453
PLASTIC AND ELASTIC PROPERTIES OF COMPOSITIONALLY
MODULATED THIN FILMS, Scott A. Barnett and
Meenam Shinn 481
(continued) VB

STRONGLY GEOMETRICALLY Frustrated Magnets

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STRONGLY GEOMETRICALLY Frustrated Magnets

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ANNUAL

AT&T Bell Laboratories, 600 Mountain Avenue, Murray Hill,

KEY WORDS: frustration, antiferromagnetism, Heisenberg spins

The study of cooperative phenomena in magnetism has provided fertile

behavior are site disorder and frustration. These microscopic parameters,

explained theoretically. For low frustration and high disorder, the

phenomena of random field magnetism and percolation effects are found.

MAGNETIC GROUND STATES

random fields spin

review, we demonstrate the existence of a distinct class of magnets having

GEOMETRICAL FRUSTRATION DEFINED

It is important to distinguish the two classes where frustration effects are

host. Frustration occurs since the interaction between Mn atoms is of the

Frustrating Lattice Types

"SPIN GLASS" FRUSTRATION

either with a mixture of precisely tuned AF and FM nearest neighbor (nn)

Figure 3, is distinguished from the triangular lattice by virtue of having

corner-sharing triangles. Its three-dimensional analogue is the pyrochlore,

or B-site spinel lattice (Figure 3), which is built out of corner-sharing

triangle vertices are traversed in a given direction, cannot be transmitted

pendently demonstrated the basic feature of frustrated systems in theor­

mentally accessible, but the presence of a phase transition can be tested,

Experimentally, Te for an antiferromagnet is relatively easy to define,

where z is the number of nearest neighbors, and kB the Boltzmann constant

spin multiplet by a magnetic field. In Equation 3, (Jew is equivalent to Te in

NON FRUSTRATED FRUSTRATED

cal nonfrustrated magnets it is usually extremely difficult to perform. This

::J .... '

obtained through the Curie constant corresponds to the expected value

showed that by extending the number of sub-lattices to four, as is natural

nearest neighbor interactions and up to thirty-two sub-lattices and found

Materials with Strong Geometrical Frustration-Microscopic

Magnetic -/Jew T, Ordered Electronic

KCrJ(OHMS04)1 kagome 70 1.8 39 AF 3d3 31

Difference Between Strong Geometrical Frustration and Low

with strong geometrical frustration. Experimentally there are many ex­

by a rarefication of spin density, whereas SGF systems gain entropy by a

is 86%, the shortfall being made up in an overall less densc triangular

for three-dimensional SGs. The authors proposed that SCGO(p) is a

extrinsic explanation for such behavior, e.g. from chemical clustering of

an AF phase not representative of the average stoichiometry. Thus the

DILUTION STUDIES The dependence of the thermodynamic quantities on

found that p 0.38 and Tc 7 K.

The dilution dependence of Tc in the crystals is to be contrasted with

0.39, Tc was 2.5 and <2.0 K respectively. Martinez et al performed a

rough agreement with the previous work (26).

samples it was found that!:::::: 1 50 and remains virtually unchanged (25,

was found to occur down to 2 K, thus!> 34. Subsequent C(T) measure-

ments showed an ordering anomaly at 1.75 K (31 ). In Figure 9 a more

to be approaching TZ behavior as expected for a two-dimensional anti­

intriguing possibility since it allows for zero-energy modes, which imply a

finite entropy at T 0 (32).

Rare Earth Delafossites-RCuO 2

and Gdo.sLao.2Cu02 (38) possess this structure. The latter compound is

Eu, and GdosLao.2 (38). Compounds with higher Gd concentrations, as

pound has a susceptibility possibly arising from oxygen deficiency and

rather a broad C(T) peak with a maximum at T = 1.8 K. Measurements

The low temperature C(T) for Gdo.sLao.zCuOz is shown in Figure 11,

Transition Metal Dela/ossites-LiCrOz, NaTiOz, LaCu02+b

K, thus f 48. The magnetic structure was determined with neutron

scattering and the strong two-dimensional character was confirmed (36).

6. Lao. aGdo. eCuOa

study the temperature dependence of the ESR linewidth was interpreted

pendently demonstrated the basic feature of frustrated systems in theor

with strong geometrical frustration. Experimentally there are many ex

to be approaching TZ behavior as expected for a two-dimensional anti