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The effect of doping additional Bi on the magnetoresistance (MR) of La2/3Ca1/3BxMn1-x O3 was investigated. It is found that traditional colossal magnetoresistance (CMR) peak can only be observed in the x<0.05 samples and the peak value decreases with the increase of x, but the x≥0.05 samples show a magnetoresistance plateau above 200 K because of the presence of additional (La,Ca,Bi)-O layers. Moreover, this MR plateau is enhanced for the segregation of the La,Ca, and Bi elements.

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