Mater. Res. Soc. Symp. Proc. Vol. 848 © 2005 Materials Research Society FF2.10.

New Magnetic Zintl Phases in Eu-In-P System

Jiong Jiang, Amy C. Payne, and Susan M. Kauzlarich

Departments of Chemistry, One Shields Avenue, University of California, Davis, CA 95616

ABSTRACT

Single crystals of two new compounds, Eu3InP3 and Eu3In2P4, were prepared by In flux
synthesis. Eu3InP3 crystallizes in the Pnma orthorhombic space group with a = 12.6517(15) Å, b
= 4.2683(5) Å, c = 13.5643(14) Å, and Z = 4 while Eu3In2P4 belongs to Pnnm space group, a =
6.6999(6) Å, b = 16.1019(13) Å, c = 4.2725(4) Å, and Z = 2. These two compounds are isotypic
to the main group compounds Sr3InP3 and Sr3In2P4 respectively. Both structures consist of
distorted In-P tetrahedra and isolated Eu2+ ions. In Eu3InP3 these tetrahedra share corners to
form one-dimensional chains. The Eu2+ ions occupy three different sites, and form a
complicated network containing some triangles. In Eu3In2P4 these tetrahedra form edge-shared
dimers, and these dimers form chains. Eu3InP3 shows unusual magnetic properties: there are
three magnetic ordering transitions at 14 K, 10.4 K, and around 5 K and the magnetization curve
shows steps in the low temperature region. Eu3In2P4 magnetically orders at 14.5 K. Its
magnetization curve saturates at around 1T. Eu3InP3 and Eu3In2P4 are both semiconductors.

INTRODUCTION

Zintl phases are compounds with a precise valence count. These compounds consist of
elements from group 1, 2 with those from group 13, 14, 15. In recent decades, scientists have
extended the Zintl boundary to include transitional metals and rare earth metals because of their
special electron configuration.1-4 By doing so, many compounds with new structure types and
novel physical properties have been discovered.5, 6
Zintl phases containing europium have been attracting much attention. There are several
ternary europium compounds that show unusual magnetic properties. EuNi5P3 has a
magnetization curve with several steps resulted from magnetic spin-flop and thermally activated
domain wall motion.7 Similar steps also occur in EuAs3. Studies on this compound suggest that
temperature and field dependence of the lattice size are important.8 Eu containing Zintl phases
are typically antiferromagetic with low magnetic ordering temperature,9, 10 however, many of
them show a positive Weiss constant, which suggests a ferromagnetic correlation in the
paramagnetic region.11, 12 Here we introduce two europium containing Zintl phases, Eu3InP3 and
Eu3In2P4.

EXPERIMENT DETAILS

Eu3InP3 and Eu3In2P4 were synthesized by heating a mixture of the elements. The
starting materials were Eu (99.999%, Ames Lab) 1/8” ribbon, cut into small pieces, red P (J.
Matthey, Puratronic), crushed into small pieces, and In shot (Aesar, 99.99%), used as received.
In the reactions, indium acts as both reactant and flux.13 The europium and phosphorus were
packed into an alumina crucible between layers of granular indium metal. A second crucible
containing quartz wool was inverted over the reaction crucible, and the entire reaction vessel was
sealed in a fused silica jacket that was back-filled with argon at 0.2 atm. The vessel was heated
to 1373 K using a programmable furnace, and then removed, inverted, and centrifuged at 1123
 FF2.10.2

K. During the centrifuging the excess flux was decanted into the quartz wool and thus separated
from the crystals.
Crystal structures of Eu3InP3 and Eu3In2P4 were determined by single crystal X-ray
diffraction. The crystals were mounted on the tip of a glass fiber and positioned under a 90(2) K
cold N2 stream provided by a CRYO Industries low temperature apparatus on the goniometer
head of a Bruker SMART 1000 diffractometer. Mo Kα radiation and a graphite monochromator
were used for collecting data. Absorption correction was done using the program SADABS.
SHELXTL 97 was used for structure solving and refinement.14
Resistance measurements of Eu3InP3 were applied using a two-probe method since its
resistance exceeds the measurement limit of our four-probe instrument in most temperature
ranges. We were able to measure the resistance of Eu3In2P4 using a 4-probe throughout most
temperatures, however, at temperatures below 130 K we have to return to the two-probe method
because of the high resistance. Platinum probes were attached on the crystal by Epoxy
Technology H20E-175 silver epoxy. In four-probe measurement, a constant current of 100 nA
was applied through two outer leads by a Keithley Model 224 current source, and a Keithley 181
voltmeter was used to measure voltage between the two inner leads. A Keithley Model 617
programmable electrometer (200 G& limit) was used in two-probe measurement.
A Quantum Design MPMS Superconducting Quantum Interference Device (SQUID)
magnetometer with a 7 T superconducting magnet was used for the dc magnetization
measurements. A single crystal sample was placed in a straw provided by Quantum Design.
Magnetism measurements were conducted on both orientations with the applied field parallel and
perpendicular to the needle crystals long axis. The data were analyzed with the software
MultiVue.

RESULT AND DISCUSSION

Indium is a good flux due to its low melting point, relative inertness to alumina crucibles,
and low vapor pressure. By using an indium flux, we were able to produce Eu3InP3 and Eu3In2P4
crystals as large as 2-4 mg, which is enough for our physical property measurements. Both
Eu3InP3 and Eu3In2P4 are black needle-shaped air-sensitive crystals.
Both Eu3InP3 and Eu3In2P4 can be rationalized using the Zintl concept. Eu3InP3 may be
formulated as containing three Eu2+, one In3+, and three P3-; Eu3In2P4 can be formulated as three

Figure 1. Crystal structure of Eu3InP3 (left) and Eu3In2P4 (right).

 FF2.10.3

Eu2+, two In3+, and four P3-.

Eu3InP3 and Eu3In2P4 are isotypic with Sr3InP315 and Sr3In2P4,16 respectively. Their
structures are shown in Figure 1.
Eu3InP3 crystallizes in the orthorhombic Pnma space group with a = 12.6517(15) Å, b =
4.2683(5) Å, c = 13.5643(14) Å, and Z = 4. The crystal grows fastest in the [010] direction and
forms a needle along this direction. In the structure, [InP2P2/2]6- tetrahedra form one-dimensional
chains along b axis by sharing corners. These chains are isolated by the divalent europium
cations. There are three crystallographically different europium sites in this compound. The
shortest Eu-Eu distance is 3.5954(7) Å.
Eu3In2P4 structure belongs to Pnnm space group. The cell dimensions are a = 6.6999(6)
Å, b = 16.1019(13) Å, c = 4.2725(4) Å, and Z = 2. The needle direction is [001] in this
compound. Eu3In2P4 also contains In-P tetrahedra. Every two tetrahedra form one [In2P2P4/2]6-
unit by sharing an edge. These [In2P2P4/2]6- units, sharing corners with each other, stack to form
one-dimensional chains along the c axis. Two distinct europium sites exist in this compound.
The shortest Eu-Eu distance is 3.7401(7) Å.
Electrical transport measurements show that both compounds are semiconductors with
small band gaps. Conductivity as a function of temperature for both samples is shown in Figure
2. The data were fitted with the following equation:
Eg
ln σ = F − .
2k B T
Gap energy of 0.454(3) eV and 0.452(4) eV were obtained for Eu3InP3 and Eu3In2P4,
respectively, which is consistent with the black color of both compounds.
Susceptibility as a function of temperature for the two compounds is shown in Figures 3
and 4. Both compounds show paramagnetism at room temperature and magnetically order at
low temperature. In paramagnetic region, χ vs T data were fit with Curie-Weiss law to obtain the
Curie constant (C) and Weiss temperature (θ). In Eu3InP3, we get C = 22.70(4) emu·K/mol and θ
= 19.9(3) K. The C value corresponds to a effective magnetic moment, µ eff, of 13.47(1) µ B,
which is close to the theoretical value 13.75 µ B. In the case of Eu3In2P4, the fitting gives slightly
different results for measurements parallel and perpendicular to c axis: C = 22.88(3) emu·K/mol
and θ = 19.9(2) K for parallel direction; C = 22.52(9) emu·K/mol and θ = 23.3(7) K for

Figure 2. Conductivity as a function of temperature for Eu3InP3 and Eu3In2P4.

 FF2.10.4

perpendicular direction. The C values are essentially the same in this compound, and are also
close to the theoretical value.
Eu3InP3 shows complicated magnetic behaviors below 15 K. In the measurement parallel
to b axis, there are three susceptibility maxima at 14 K, 10.4 K, and around 5 K; while in the
perpendicular measurement, the transitions corresponding to 14 K and 10.4 K are still obvious,
however, the 5 K peak almost disappears. The 5 K magnetization curve of Eu3InP3 in the b axis
direction has a step around 0.05 T, as shown in Figure 3. This suggests a metamagnetic
mechanism in the compound.
The magnetism of Eu3In2P4 is not as complex as Eu3InP3. The magnetic ordering
temperature occurs at 14.5 K. Below this temperature, in the direction parallel to the c axis, the
compound shows magnetization behavior similar to that of antiferromagnetism. While in the
direction perpendicular to the c axis, it has ferromagnetic characteristics. This might be the
result of a canted magnetic system.

Figure 3. Susceptibility as a function of temperature (left) and magnetization curve in b axis

direction at 5 K (Right) for Eu3InP3.

Figure 4. Susceptibility as a function of temperature for Eu3In2P4.

 FF2.10.5

CONCLUSIONS

Two new rare earth metal Zintl phases, Eu3InP3 and Eu3In2P4, were discovered. Both
compounds are magnetic semiconductors, which are quite rare. The magnetic properties of the
two compounds were studied from different aspects. Eu3InP3 is a complicated magnet with three
magnetic transitions at 14 K, 10.4 K, and 5 K. At low temperature, metamagnetic transition
occurs with the applied field rising. Eu3In2P4 shows magnetic ordering below 14.5 K.

ACKNOWLEDGMENTS

The authors thank Prof. Kai Liu, University of California Davis, for useful discussions.
The authors acknowledge NSF (DMR- 0120990) for financial support.

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