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Many monumental breakthroughs in p-type PbTe thermoelectrics are driven by optimizing a Pb0.98Na0.02Te matrix. However, recent works found that x 0.02 in Pb1-xNa x Te further improves the thermoelectric figure of merit, zT, despite being above the expected Na solubility limit. We explain the origins of improved performance from excess Na doping through computation and experiments on Pb1-xNa x Te with 0.01 ≤ x ≤ 0.04. High temperature X-ray diffraction and Hall carrier concentration measurements show enhanced Na solubility at h