In the crystal structure of members of the (Cu,Mo)Sr2(Ce,R)
s
Cu2O5+2
s
+
δ or (Cu,Mo)-12s2 homologous
series of superconductive copper oxides, adjacent CuO2 planes are separated by a fluorite-structured
(Ce,R)-[O2-(Ce,R)]
s
-1 blocking block. Here we utilize the fluorite block as a “chemical-pressure medium”
for the s = 2 and 3 members of the series. The (Ce,R) sites readily accommodate rare earth elements (R)
ranging in size from La down to Yb. With decreasing size of the R constituent, T
c first monotonically
increases and then decreases, having a maximum around R = Y for both s = 2 and s = 3. At the same
time the average valence of copper, derived for the s = 2 samples from Cu L3-edge XANES spectra, is
found to remain constant at 2.20 ± 0.01. An explanation for the unique chemical-pressure effect is revealed
from O K-edge XANES spectra, the resolution of which allows us to distinguish the CuO2 plane holes
from those residing in the (Cu,Mo)O1+
δ charge reservoir. The result shows that the T
c value and the
density of CuO2 plane holes follow parallel trends with respect to the size of R.