Mat. Res. Bull., Vol. 26, p p . 1027-1034, 1991. Printed in the USA.

0025-5408/91 $3.00 + .00 C o p y r i g h t (c) 1991 Pergamon P r e s s plc.

SYNTHESIS AND TRANSPORT PROPERTIES OF Ca3Cu204C12

J.-G. Lee, K.V. Ramanujachary and M. Greenblatt*

Department of Chemistry
Rutgers, The State University of New Jersey,
P.O. Box 939, Piscataway, NJ, 08855-0939.

(Received July 2, 1991; Communicated b y J . B . Goodenough)

ABSTRACT

Synthesis, electrical, and magnetic properties of serniconducting Ca3Cu204C12 with a

perovskite-related structure are reported. Synthetic conditions required for the
formation of single phase polycrystalline Ca3Cu204C12 were determined. Powder
X-ray diffraction analysis confirmed the body-centered-tetragonal (I4/mmm) structure
as proposed earlier. Differential thermal studies in air indicate incongruent melting at
960°C. Temperature dependent electrical resistivity measurements carried out in 02
and He atmospheres respectively in the range 20 - 600°C show semiconducting
behavior regardless of the atmosphere, although the conductivity is higher by at least
two orders of magnitude in oxygen atmosphere. No evidence for magnetic order is
seen in the susceptibility measurements down to 2 K.

MATERIALS INDEX: calcium, c o p p e r , R u d d l e s d e n - P o p p e r p h a s e s ,

oxyehlorides

Since the discovery of high temperature superconductivity in perovskite related Ba-La-Cu-O

phases by Bednorz and Mtiller (1) in 1986, the physical and chemical properties of many oxo-
cuprates have been the subject of numerous investigations (2). Despite their structural resemblance
to oxo-cuprates, the halo-oxo-cuprates have received relatively less attention, probably due to
a) the absence of metallic behavior in this class of compounds, b)inability to carry out
substitutions required to induce mixed valency on the copper site, and c) difficulties encountered
in handling the samples in ambient, due to their hygroscopic nature. Copper oxychlorides of the
type A2CuO2X2 (A = Ca or Sr and X = C1 or Br) have been prepared and their structural and
physico-chemical characteristics have been well established (3). The structures of other halo-oxo-
cuprates of the typeA2Cu304X2 (A = Sr or Ba and X = C1 or Br) have also been examined by
X-ray diffraction (3). A common structural feature in this class of compounds is the presence of
CuO2 layers as in La2CuO4, with the apical positions of the CuO6 octahedra replaced by halide

* To whom correspondence should be addressed.

1027
1028 J . - G . LEE, et al. Vol. 26, No. 10

ions. The alkaline-earth and halide ions form rock-salt type layers that alternate with the CuO2
layers. The absence of out-of-plane oxide ions in these structures may be responsible for the
observed semiconducting behavior.

Recently, new halo-oxo-cuprates, of the type Ca3Cu204X2 (X = CI or Br) (4) and

MLnCuO3C1 (M = Ca or Sr; Ln = Sm, Nd, Eu, or Gd) (5) have been reported, in which the
copper exists essentially in five-fold coordination of four oxide ions in square-planar configuration
and a halide ion in the lone apical position. However, in the former compound the double layers of
square-pyramids are separated by calcium ions, while the latter adopts the T* structure.
Ca3Cu204CI2 can also be viewed as the second member of the modified Ruddlesden-Popper series
with the general formula AX'(ACuO2X)°(ACuO2)n-I (A = Alkaline earth ion and X = CI or Br).
The synthesis of single phase Ca3Cu204CI2 is rather complicated, due to the formation of
undesired impurities such as Ca2CuO2C12, CaCu203, Ca2CuO3 etc., competing with the main
phase. The presence of these impurity phases has been a major obstacle in the characterization of
the structure and physical properties, and hence it was necessary to optimize the synthetic
conditions leading to the formation of X-ray pure, single phase specimens of Ca3Cu204CI2. The
objectives of the present investigations were: i) optimization of the synthetic conditions for the
formation of single phase Ca3Cu2OaC12, ii) determination of the thermal stability of the phase,
iii) electrical conductivity studies as a function of temperatures and different ambients and
iv) magnetization studies in the temperature range 2 - 400 K. Results of these studies are reported
in this communication.

Ex.~rim.e,nlal
Stoichiometric amounts of CaCO3 (Aldrich, 99+%), CaC12 (Strem Chemicals, 99.99%) and
CuO (Aldrich, 99.99+%) were weighed and mixed thoroughly in a He-filled glove box. The
powdered mixtures were subsequently transferred into gold crucibles and subjected to various heat
treatments in the temperature range 800 - 900°C under different atmospheres (including 02, air,
N2, air/N2, and Ar) followed by quenching or slow cooling to room temperature. Products were
characterized by a SCINTAG PAD V diffractometer with monochromatized CuKa radiation and
with mica powder (SRM 675 from NBS) as an internal standard. Variable temperature X-ray
diffraction studies were conducted in a similar diffractometer fitted with a high-temperature
accessory. Thermogravimetric (TGA) and differential thermal analysis (DTA) studies were
performed in a Du Pont 9900 and 951, respectively. A heating rate of 5 - 20 °C/min was used in
both the TGA and DTA measurements. AC impedance characteristics were measured as a function
of temperature in the range 20 - 600°C in various atmospheres. The data were collected with a
SOLARTRON frequency response analyzer (Model 1250) coupled to an electrochemical interface
(Model 1186) with HEWLETT PACKARD 9816 computer control. Impedance spectra were
recorded at various frequencies in the range 10 Hz - 65 KHz. Contacts were made by deposition of
thin layers of gold (50 - 60 A thickness) on both sides of disc shaped pellets (6.5 mm diameter and
1.0 - 1.5 mm thickness) pressed from the powder specimens at 5000 - 7000 lb/in2; pellets were
sandwiched between spring-loaded platinum foils for better electrical contact. However, when the
contacts were made by painting platinum paste alone on opposite sides of the pellets, evidence of
significant electrode interference effects in the form of semicircles with high surface resistances
were found. Accordingly, the electrical resistivity measurements were performed on pellets coated
with gold. Samples were sintered in 02 atmosphere at 600°C for two hours and quenched or
slowly cooled to room temperature prior to the impedance measurements. Magnetic susceptibility
was measured on brick-shaped pellets in the temperature range 2 - 400 K at an applied magnetic
field of 1000 G in a SQUID magnetometer (Quantum Design). High pressure oxygenation studies
were conducted in a modified version of a LECO hydrothermal apparatus.
Vol. 26, No. 10 OXYCHLORIDES 1029

Results and Discussion

The synthetic conditions leading to the formation of black single phase Ca3Cu204CI2 have
been optimized by varying : a)the stoichiometry, b)the reaction atmosphere, and c)the
calcination temperature and heating period. Table 1 gives a summary of the products formed from
stoichiometric CaCO3, CaCI2 and CuO to yield Ca3Cu204CI2 under various experimental
conditions. The formation of Ca3Cu204C12 is favored in air, much more than in N2 or Ar
atmospheres, although with some impurities such as CaCu203, Ca2CuO3 and Ca2CuO2CI2. Pure
Ca3Cu204C12 was prepared by gradually heating the starting materials in flowing 02 atmosphere
from 600 to 900°C; six to seven intermediate grindings were carried out at 50 ° intervals.
Intermediate grindings not only enhance the homogeneity of the samples (minimize impurity phase
segregations), but also prevent the evaporation of CaC12 from the surface material. In fact, we see
the formation of a white coating, identified as CaCI2, on the powders calcined at 740°C. The
preparation of a single phase sample is optimized by heating at 900°C for 4 - 6 hours in 02
atmosphere. Although the formation of single phase specimens is not affected by quenching or
slow cooling the sample, the physical properties are considerably dependent on the sample history
as will be shown later.

Table 1
Results of various experimental conditions examined in the synthesis of Ca3Cu204C12

Temp(°C)/Period(hr) Atmosphere Phases observed

800/10 02 Ca2Cu02C12, Ca3Cu204Cl2(vs)*,
Ca2Cu03, CaCu203, CuO
800/12 Air Ca2Cu02Cl2, Ca3Cu204Cl2(s),
Ca2Cu03, CaCu203, CuO
800/12 N2 Ca2Cu02C12, Ca3Cu204C12(vs),
Ca2Cu03, CaCu203
800/12 Air/N2 Ca2CuO2C12, Ca3Cu204C12(vs),
Ca2CuO3, CaCu203, CuO
800/12 Ar Ca2CuO2C12, Ca3Cu204C12(vs),
Ca2CuO3, CaCu203, CuO
820/12 02 Ca2CuO2C12, Ca3Cu204Cl2(vs),
Ca2CuO3, CaCu203, CuO
860/12 02 Ca2CuO2CI2, Ca3Cu204Cl2(s),
Ca2CuO3, CaCu203, CuO
860/12 Air Ca3Cu204CI2(1), Ca2CuO2C12(s),
Ca2Cu03, CaCu203, CuO
900/4--6t 02 Pure Ca3Cu204C12
: vs = very small, s = small, 1 = large
t : with intermediate grindings

The powder X-ray Diffraction (XRD) pattern of the Ca3Cu204C12 prepared by the above
conditions is presented in Figure 1. All the observed diffraction peaks were indexed based on the
unit cell proposed by Sowa et al.(4). The cell parameters as determined from the least squares
refinement of the observed XRD data are a = 3.8609(4) and c = 21.345(2)/~. High temperature
1030 J.-G. LEE, et al. Vol. 26, No. 10

X-ray diffraction studies in air indicate that Ca3Cu204C12 remains stable from 25 to 700°C with no
apparent structural transformations. DTA measurements carried out in air confirm the high
temperature XRD results and show that the compound melts incongruently at 960°C.

100

80

eo
v

40

,----, 20
_......,

O , , , I , i , , I , , , , I , , , I I = , , i I , , i ,

5 15 25 35 45 55 65
20 (degrees)

Figure 1
X-ray powder diffraction pattern of Ca3Cu204CI2

Figure 2 presents the temperature variations of the electrical resistivity in He and oxygen
atmospheres. As can be seen, the compound is highly resistive and remains semiconducting in the
temperature range of measurements, regardless of ambient atmosphere. However, the electrical
resistivity measured in oxygen atmosphere on an initially quenched sample is one order of
magnitude higher than that obtained in helium atmosphere. Furthermore, samples that were
quenched from 900°C, displayed relaxation behavior in the Cole-Cole plots when measured below
230°C in flowing oxygen atmosphere. This implies mixed ionic and electronic transport.

In order to examine the effect of oxygen annealing on the resistivity of the samples, pellets
were subjected to various pre-treatments prior to the measurement (see figure 2). It is clear from
these plots that the electrical resistivity of Ca3Cu204C12 is a sensitive function of the sample
history. Samples that were quenched in 02 atmosphere from high temperatures (i.e., first
quenched from 900°C heated in 02, then annealed in 02 at 600°C and quenched) display higher
room-temperature resistivity (PRT ~- 150 Kflocm) and show an abrupt decrease in p at ~ 200°C,
when measured in flowing 02 atmosphere (curve a of figure 2). In contrast, samples that were
slowly cooled from 900 and 600°C showed relatively lower resistivity (PRT ~ I Kf~°cm) and
smaller decrease in p at ~ 200°C, in 02 atmosphere (curve c of figure 2). We attribute these
anomalous variations in the electrical resistivity to changes in oxygen content/ordering induced via
pretreatment. For example, samples that were quenched from high temperatures (curve a of figure
2) are expected to be oxygen-deficient and thus the decrease in resistivity at ~ 200°C could be
explained in terms of uptake of small amount of oxygen. On the other hand, samples that were
slowly cooled in oxygen atmosphere (curves c and d of figure 2) could be stoichiometde or nearly
Vol. 26, No. 10 OXYCHLORIDES 1031

oC
727 394 227 127 60
5.5 . . . . I . . . . I . . . . I . . . . t

5.0

4.5 a
E
¢J
4.0
"/
v
3.5
EL
/, /" f o J C
3.0 / o o o "~S---. • "
..9_o /'" o ° o o • • e
°

2.5 ~o/~ o o ° °t . . . . ~ " . • * •

2.0

1.5 I ~ h ' l l ~ J l i ' b ' ' l ' ' ~ ' l ' l l '

1.0 1.5 2.0 2.5 3.0 3.5

1000/T
Figure 2

Plot of log p vs. 1000/T of Ca3Cu204C12 in 02 and He atmospheres: a, b = heating (A) and
cooling (x) in 02 of a sample quenched from high temperatures in 02; c, d = heating (*) and
cooling (<>) in 02, of a sample slowly cooled from high temperatures in 02; e, f = heating (+) and
cooling (o) in He, of a sample slowly cooled from high temperatures in 02. The error in the
resistivity is _+10 %.

so, consistent with the lower resistivity observed under these conditions. It is noteworthy, that the
initial room temperature resistivity of the sample (curve a of figure 2) is the highest, and after
cooling the sample in 02 (curve b of figure 2), the original high resistivity is not restored (PRT
400 fbcm). This indicates that the as-prepared sample is oxygen deficient and is slightly
oxygenated during the resistivity measurement. Subsequent heating and cooling cycles of the
resistivity measurement in 02 did not show significant change in the resistivity behavior, which
suggests that the oxygen, once incorporated, is not lost at least up to 600°C. The thermal activation
energies (Ea), evaluated from the Arrhenius plots, are low (Table 2). This implies an extrinsic
mechanism of conductivity. We have repeated these measurements several times (>3) on samples
with different thickness and the results are reproducible.
We have also measured the electrical resistivity of the oxygenated sample of Ca3Cu204CI2 in
inert atmosphere by switching the flowing gas from 02 to He. Upon heating the sample in He
atmosphere, there is a small increase in the resistivity above 400°C (curve e of figure 2), which,
we believe, is due to loss of oxygen from the sample. Moreover, we find that upon cooling this
sample in He from 600°C to room temperature, the resistivity increased (curve f of figure 2, PR'r
2.9 Kf2ocm). Thus, the electrical resistivity of Ca3Cu204C12 appears to be strongly correlated with
1032 J . - G . LEE, et al. Vol. 26, No. 10

oxygen content and/or ordering as has been observed for several other high Tc copper oxide based
superconductors.

Table 2.

Activation energies (Ea) and resistivity values (p) of Ca3Cu204C12

E a (eV) Ea (eV) p (fbcm)

Curve
20 - 360°C 20- 196°C 333 - 495°C 25°C 575°C

a 0.10(3) 0.09(3) 1.5 X 105 75

b 0.054(4) 75 365

c O.lO(3) 0.09(3) 103 68

d 0.054(4) 68 400

e 0.054(4) 400 91

f 0.19(3) 91 2.9 X 102

The higher electrical resistivity of samples quenched from high temperatures and the
increased resistivity of oxygen annealed samples in inert atmospheres (curves e and f of figure 2)
have led us to examine the possibility of oxygen and/or C12 loss with thermogravimetric analysis.
TGA patterns of samples annealed or quenched in oxygen were recorded up to 800°C in flowing
He atmosphere. The outlet of the TGA chamber was connected to a bubbler filled with 0.025M
AgNO3 solution to monitor the release of C12 gas if any. The turbidity of the bubbler solution
served as an indicator of chlorine gas in the product stream. Although the total weight loss is small
(~ 0.35 %) in the range 380 - 590°C for both annealed and quenched samples, we see evidence of
slight turbidity starting from 500°C. However, the powder XRD patterns of the sample before and
after the electrical resistivity measurements did not indicate any evidence of structural
transformation or the presence of impurities. Optical microscopic examination of the samples that
were subjected to longer heating periods in He atmosphere revealed portions of the sample
developing a brownish-black color on the surface which indicates a partial decomposition of the
sample under these conditions. Moreover, TGA studies of Ca3Cu204C12 prepared at 900°C and
quenched in 02 did not indicate significant weight gain in oxygen atmosphere. Similarly, TGA
measurements of "oxygen-rich" samples (i.e., samples that were slowly cooled from high
temperature in 02) in He atmosphere did not indicate significant weight loss.

Figure 3 presents the variation of magnetic susceptibility as a function of temperature in the

range 2 - 400 K for a polycrystalline sample of Ca3Cu204C12. The susceptibility remains nearly
temperature independent above 50 K; the low temperature upturn seen in the susceptibility can be
fit to a Curie-Weiss expression (Z = C/T-0) with C ~ 8.08 (+ 0.06) x 10-3 emu/mole,K and
0 = - 3.2 K. The positive curvature seen in the susceptibility plot (Figure 3) below 50 K could be
related to the presence of isolated Cu 2+ (S=1/2) defects or impurity phase inclusions near the grain
boundaries of the polycrystalline sample as proposed for Sr2CuO2CI2 (6). The susceptibility
values were corrected for the atomic diamagnetism of the component ions. The effective magnetic
Vol. 26, No. I0 OXYCHLORIDES 1033

moment at room temperature is 0.36 ~tB/Cu atom. This moment is comparable to those reported for
La2CuO4 and Sr2CuO2CI2 (6). No detectable anomalies due to magnetic ordering were seen in the
high temperature regions of the 2( vs. T plots. The absence of magnetic ordering on the copper
sublattice of Ca3Cu204CI2 appears to be related to the absence of Dzyaloshinsky-Moriya
interactions (7) which are present only in materials with orthorhombic distortion. Nevertheless the
small moment of the sample is indicative of the presence of antiferromagnetic interactions on the
copper lattice.

0.004
d.)
0.003

"~ 0.003

--'--
o ~
0 .002

o.ool
o

0.000 o
o

0.000 , , , , I , , , i I , , , , I . . . . L . . . . i . . . . i . . . . i . . . .

O 50 100 150 200 250 300 350 400

Temperature (K)

Figure 3

Magnetic susceptibility of Ca3Cu204CI2 as a function of temperature in the range 2 - 400 K

Recently Cava et al. have reported superconductivity at - 60 K in La2.xSrxCaCu206,

prepared at high oxygen pressure (8). In view of the structural similarities between La2SrCu206
and Ca3Cu204C12, we have carded out high pressure oxygenation of our samples in order to test
superconductivity. Pressed pellets were wrapped in a gold foil and were inserted into the high
pressure vessel charged at 30 - 60 atm of oxygen at room temperature. The vessel was then heated
to temperatures between 400 - 600°C for 7 hours. Regardless of the condition of the oxygenation,
the samples remained semiconducting. At oxygen pressures exceeding 100 atm, we see the
presence of impurity peaks in the XRD pattern indicating partial decomposition of the sample.
However, at relatively low oxygen pressures (< 30 atm), no apparent change in the powder X-ray
diffraction was discernable. The failure to observe metallic and/or superconducting behavior in
these halo-oxo-cuprates may be related to the presence of halide ions in the apical position of the
Cu-O octahedra. This view is further supported by the fact that isostructural pairs of oxo-cuprates
and halo-oxo-cuprates (such as La2CuO4/Sr2CuO2CI2, L a 2 S r C u 2 0 6 / C a 3 C u 2 0 4 C I 2 ,
Nd2.x.yCexSryCuO4/CaSmCuO3Cl) differ very widely in their physical properties.
1034 J . - G . LEE, et al. Vol. 26, No. 10

Conclusion

Preparation of single phase Ca3Cu204CI2 has been achieved by calcination of stoichiometric

mixtures of the constituent oxides at 900°C for 4 hours in oxygen atmosphere; six to seven
intermediate grindings are necessary while increasing the temperature from 600°C to 900°C in
increments of 50°C. The sample is tetragonal in the range 20 - 700°C as evidenced by XRD. DTA
measurements show that Ca3Cu204CI2 melts incongruently at 960°C. The magnetic susceptibility
in the range 2 - 400 K shows nearly temperature independent behavior with an effective magnetic
moment of 0.36 I.tB/Cu. Electrical resistivity measurements in various atmospheres from 20 to
600°C reveal semiconducting behavior. The electrical transport properties are dramatically affected
by sample history and the ambient of the measurement. Samples quenched from high temperature
are orders of magnitude more resistive than samples slowly cooled or annealed in oxygen (PRT ~
400 f~'cm for an "oxygen-rich" sample). Further experiments designed to modify the electrical
properties of the sample by chemical substitutions at the calcium site are currently in progress.

Acknpwledgmen|8

We thank Dr. R. L. Fuller for helpful discussions. This work was supported in part by the
Office of Naval Research and by National Science Foundation-Solid State Chemistry Program
Grant DMR-87-14072 and DMR-90-19301.

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2. See for example: Mat. Res. Soc. Syrup. Proc., vol. 156, "High Temperature
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