Proton conductive spots on the membrane surface of sulfonated poly(arylene ketone) multiblock copolymer were investigated by current-sensing atomic force microscopy (CS-AFM) under the hydrogen atmosphere with changing relative humidity, temperature, and bias voltage. The bright spots, where the hydrophilic clusters should be effectively connected inside the membrane, were distributed rather inhomogeneously on the surface at low temperature and humidity but became more homogeneous at higher temperature and humidity. The average diameter of the spots was approximately 10nm at 40% RH, which increased to 13nm at 70% RH. The total area of the proton conducting spots, as well as current at each spot, on the membrane surface increased at high humidity and temperature. In addition, the diameter of the proton-conductive spots and the ratio of proton-conductive area on the membrane surface continuously increased with increasing the bias voltage. This increase of the conducting area and the current should be related to the change of the bulk ionic conductivity.
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