Abstract
The lattice vibration and crystal structure of alkaline earth metal-substituted $RuSr_{1.9}A_{0.1}GdCu_{2}O_{8}$ (A = Ca, Sr, and Ba) have been investigated with micro-Raman spectroscopy. The present $RuSr_{1.9}A_{0.1}GdCu_{2}O_{8}$ materials show not only several weak Raman peaks corresponding to the vibrations of $O_{Cu}$ and $O_{Ru}$ but also strong characteristic phonon lines related to $O_{Sr}$ vibration mode. A comparison between the frequency of $O_{Sr}$ vibration and the bond distances of (Ru$O_{Sr}$) and (Cu‒$O_{Sr}$) in the present ruthenocuprates reveals that the vibration energy of $O_{Sr}$ is mainly dependent on the bond distance of (Ru‒$O_{Sr}$). The peak splitting of the $O_{Sr}$ phonon lines was observed for the unsubstituted $RuSr_{1.9}A_{0.1}GdCu_{2}O_{8}$, suggesting the existence of two different (Ru‒$O_{Sr}$) bond distances. Such a peak splitting caused by the appearance of low-energy shoulder reflects the presence of internal charge transfer pathway from the $RuO_2$ plane to the superconductive $CuO_2$ one. After the substitution of Sr with Ca or Ba, the low-energy shoulder peak of $O_{Sr}$ vibration becomes suppressed, underscoring the depression of internal charge transfer between the $RuO_2$ and $CuO_2$ planes. The weakened role of $RuO_2$ layer as charge reservoir in the $RuSr_{1.9}A_{0.1}GdCu_{2}O_{8}$8 (A = Ca, Ba) would be responsible for the depression of $T_c$ upon the Ca/Ba substitution.