Single crystals of Ca1-xLaxFe2As2 for x ranging from 0 to 0.25 have been grown and characterized by structural, transport and magnetic measurements. Coexistence of two superconducting phases is observed, in which the low superconducting transition temperature (Tc) phase has Tc ~ 20 K, and the high Tc phase has Tc higher than 40 K. These data also delineate an x - T phase diagram in which the single magnetic/structural phase transition in undoped CaFe2As2 appears to split into two distinct phase transitions, both of which are suppressed with increasing La substitution. Superconductivity emerges when x is about 0.06 and coexists with the structural/magnetic transition until x is ~ 0.13. With increasing concentration of La, the structural/magnetic transition is totally suppressed, and Tc reaches its maximum value of about 45 K for 0.15 < x < 0.19. A domelike superconducting region is not observed in the phase diagram, however, because no obvious over-doping region can be found. Two superconducting phases coexist in the x - T phase diagram of Ca1-xLaxFe2As2. The formation of the two separate phases, as well as the origin of the high Tc in Ca1-xLaxFe2As2 is studied and discussed in detail.
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