The crystal structure and thermoelectric properties of type-I clathrate compounds in the Ba-Ga-Ge system have been investigated as a function of Ga content. The solid solubility of Ga in the type-I clathrate compounds is determined to be X = 16 when expressed with the formula of Ba 8 Ga X Ge 46−X . As the Ga content increases, the crystal structure changes from a superlattice structure to the normal type-I clathrate structure with the transition occurring at X = 3.5-5. The density of Ge

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... s in the type-I clathrate phase decreases as the Ga content increases. The absolute values of electrical resistivity and Seebeck coefficient increase, while that of lattice thermal conductivity decreases with the increase in the Ga content. The changes in electrical resistivity and Seebeck coefficient are explained in terms of the number of excess electrons, while the change in lattice thermal conductivity is explained in terms of the extent of the rattling motion of Ba atoms encapsulated in the cage structure.