Journal of Solid State Chemistry 165, 372}374 (2002)
Structure and Electrical Transport Property of a Silicopnictide ZrCuSiP
Hideki Abe*ꢁꢀ and Kenji Yoshii-
*National Institute for Materials Science, 1-2-1 Sengen, Tsukuba, Ibaraki 305-0047, Japan;and -Japan Atomic Energy Research Institute,
Mikazuki, Hyogo 679-5143, Japan
Received October 4, 2001; in revised form February 1, 2002; accepted February 22, 2002
EXPERIMENTAL
A silicopnictide ZrCuSiP was prepared through the reaction
between ZrCuSi alloy and red phosphor in evacuated quartz
ampoules.Rietveld analysis of the powder X-ray di 4raction
pattern revealed that ZrCuSiP has the ZrCuSiAs-type structure
Stoichiometric amounts of the pure elements Zr (99.9%),
Cu (99.9%), and Si (99.999%) were melted together using an
arc furnace under pure Ar atmosphere. The obtained matte
silver buttons were ground into "ne powder and sealed in an
(P4/nmm) with the lattice constants of a ؍
0.35671(1) nm and
c ؍
0.94460(4) nm. Electrical resistivity measurements at tem- evacuated quartz ampoule with a stoichiometric amount of
peratures from 5 to 300 K indicated that ZrCuSiP is a metallic
compound. ꢀ 2002 Elsevier Science (USA)
red phosphor chunk (99.99%). The bottom of the quartz
ampoule was cooled by dipping in a water bath in order to
prevent the evaporation of phosphor during the sealing
procedure. The quartz ampoule was placed in a mu%e oven
and heated in the following sequence: up to 6003C for 24 h,
kept at 6003C for 24 h, 24 h up to 8503C, kept at 8503C for
24 h and quenched in a water bath. After checking that there
remains no residual P, the resulting grayish slug was taken
out of the ampoule and ground to "ne powder. The powder
was pressed into small pellets using a stainless-steel piston
cylinder, sealed in an evacuated quartz ampoule and sin-
tered at 8503C for 12 h. The sintered specimens were so
stable against both the humidity and the oxygen, that no
apparent change was observed in XRD (X-ray di!rac-
tometry) patterns after keeping the specimens in the open
air for about half a year.
INTRODUCTION
Silicochalcogenides and silicopnictides with a composi-
tion of ¹MX (for chalcogenides: ¹"Zr or Hf; M"Si or
Ge; X"O, S, Se or Te, and for pnictides: ¹"Nb; M"Si
or Ge; X"As or Sb) have been investigated from the
viewpoint of structural chemistry (1}3). They have the
PbFCl-type structure (P4/nmm, No. 129), where the atomic
layers are stacked alternatively in a sequence of [M }¹}X}
ꢂ
X}¹}M ] along the c-axis (Fig. 1). The layered nature of
ꢂ
the PbFCl-type structure suggested the existence of a stack-
ing variant formed by the insertion of atomic layers into
the inter-layer gaps. This kind of structure has been
actually found in ZrCuSiAs (4). The structure of ZrCuSiAs
is derived from the PbFCl-type structure by the insertion of
Cu atomic layers into the intervals between the X}X layers
(Fig. 1). A number of quaternary compounds with
ZrCuSiAs have been reported up to now (5). This paper
reports the preparation and the structural determination of
a novel silicopnictide ZrCuSiP. A typical ¹MX-type
silicochalcogenide ZrSiS was prepared as a reference to
ZrCuSiP, and the electric transport properties of both the
compounds are presented.
ZrSiS was prepared by a similar procedure for ZrCuSiP.
Stoichiometric amounts of the pure elements Zr and Si were
melted by an arc furnace, and the ZrSi buttons were ground
to "ne powder. The ZrSi powder was sealed in an evacuated
quartz ampoule with a stoichiometric amount of S chunk,
and was heated in the same sequence as that for ZrCuSiP.
Sintering of the ZrSiS powder was carried out at 8503C for
12 h in an evacuated quartz ampoule. XRD measurements
were performed on the powdered specimens using a RINT
2100 di!ractometer (Rigaku Co. Ltd, CuKꢀ radiation).
Measurements of the electric resistivity of ZrCuSiP and
ZrSiS were performed using a conventional four-probe
method at temperatures from 5 to 300 K.
RESULTS AND DISCUSSIONS
Figure 2 shows the observed XRD pattern of ZrCuSiP
and the calculated one, together with the di!erence curve.
ꢀ To whom the correspondence should be addressed. Fax: #81-298-59-
2801. E-mail: ABE.hideki@nims.go.jp.
372
0022-4596/02 $35.00
ꢀ 2002 Elsevier Science (USA)
All rights reserved.
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