Ca0.5Na0.5Cu2.5Mn4.5O12, CaCu3-xMn4+xO12 (0.5 less than or equal to x less
than or equal to 2) were prepared at 700 degrees C and 2600 PSI by combined
sol-gel and high oxygen pressure methods. CaCu0.5Mn6.5O12 and CaMn7O12 (x
= 2.5 and 3) were prepared by solid state reactions in evacuated quartz tub
es at 900 degrees C, These compounds crystallize in a body-centered cubic v
ariant of the perovskite structure except for CaMn7O12, which has rhombohed
ral symmetry, The oxidation states of Cu and Mn were investigated by X-ray
absorption spectroscopy and chemical analysis. The oxidation state of Mn is
near 4+ in Ca0.5Na0.5Cu2.5Mn4.5O12 and decreases with increasing x, Ca0.5N
a0.5Cu2.5Mn4.5O12, CaCu2.5Mn4.5O12 (x = 0.5), and CaCu1.5Mn5.5O12 (x = 1.5)
undergo a semiconductor-to-metal transition (T-SM), CaCu2Mn5O12 (x = 1.0)
is metallic, while the 2.0 less than or equal to x less than or equal to 3.
0 phases are semiconducting in the range 10-400 K, All of the materials (ex
cept the x = 2.5 and 3.0) undergo a paramagnetic-to-ferromagnetic-like tran
sition below their ordering temperatures (T-C). The CaCu0.5Mn6.5O12 and CaM
n7O12 (x = 2.5 and 3.0) materials order antiferromagnetically at (T-N) 40 a
nd 20 K, respectively. The magnetic and resistivity results are summarized
in a T-x phase diagram. The ordering temperatures decrease with increasing
Mn3+ content, hence the double exchange mechanism does not appear to govern
the ferromagnetic ordering. The highest magnetoresistance reaches a maximu
m of - 32% for Ca0.5Na0.5Cu2.5Mn4.5O12 and is - 28% for CaCu2.5Mn4.5O12 at
4.2 K and 5 T. In general, the magnetoresistance does not occur at the semi
conductor-to-metal transition and it decreases smoothly with increasing tem
perature or x, These materials show high sensitivity of the magnetoresistan
ce at low applied magnetic fields and good temperature stability of the mag
netoresistance, (C) 1999 Academic Press.