Achieving ZT > 1 in Cu and Ga Co-doped Ag₆Ge₁₀P₁₂ with Superior Mechanical Performance and Its Fundamental Physical...

Recently, phosphorus-based compounds have emerged as potential candidates for thermoelectric materials. One of the key challenges facing this field is to achieve ZT > 1, which is the benchmark for thermoelectric device applications. In this study, it is demonstrated that the thermoelectric performance of environmentally friendly Ag₆Ge₁₀P₁₂ is enhanced by co-doping Cu and Ga. The mechanical properties, coefficient of linear thermal expansion, work function, and compatibility factor are comprehensively clarified to provide guidelines for reliable device applications. The peak and average dimensionless figures of merit of Ag_5.85Cu_0.15Ge_9.875Ga_0.125P₁₂ reach 1.04 at 723 K and 0.63 at 300-723 K, respectively, which are the highest values for phosphorus-based thermoelectric materials. The Young's modulus, Vickers microhardness, fracture toughness, and compressive strength of Ag_5.85Cu_0.15Ge_9.875Ga_0.125P₁₂ are 132 GPa, 589, 1.23 MPa m^1/2, and 219 MPa, respectively, which are superior to those of typical state-of-the-art thermoelectric materials. The remarkable thermoelectric and mechanical performance of Ag_5.85Cu_0.15Ge_9.875Ga_0.125P₁₂ mean that it is a promising candidate for medium-temperature thermoelectric conversion. Ti, V, Rh, and Pt are suitable for electrodes without exfoliation under thermal expansion and with ohmic contacts to Ag_5.85Cu_0.15Ge_9.875Ga_0.125P₁₂ in terms of the coefficient of linear thermal expansion and work function. Considering that the compatibility factor of Ag_5.85Cu_0.15Ge_9.875Ga_0.125P₁₂ is approximately 2.8, half-Heusler, skutterudite, and magnesium silicide-stannide compounds are suitable n-type thermoelectric counterpart materials in thermoelectric devices. These insights will lead to the development of phosphorus-based thermoelectric materials toward practical thermoelectric device applications.