Synthesis and Transport Properties of ZnSnP2-yAsy Chalcopyrite Solid Solutions

TL;DR

This paper studies the synthesis and transport properties of ZnSnP2-yAsy materials, showing improved electrical and thermal performance with arsenic substitution.

Contribution

The paper introduces a novel solid solution synthesis method for ZnSnP2-yAsy with enhanced electrical conductivity and reduced thermal conductivity.

Findings

Electrical conductivity increases from 0.03 S cm−1 to 10.3 S cm−1 with As substitution.

Thermal conductivity decreases due to alloy phonon scattering in solid solutions.

Figure of merit zT reaches up to 2.8 × 10−3 at 700 K for undoped ZnSnAs2.

Abstract

This work focuses on the synthesis and properties of quaternary ZnSnP2-yAsy chalcopyrite solid solutions. Full miscibility of the solid solution is achieved using ball milling followed by hot press sintering. The measured electrical conductivity increases substantially with As substitution from 0.03 S cm−1 for ZnSnP2 to 10.3 S cm−1 for ZnSnAs2 at 715 K. Band gaps calculated from the activation energies show a steady decrease with increasing As concentration from 1.4 eV for ZnSnP2 to 0.7 eV for ZnSnAs2. The Seebeck coefficient decreases significantly with As substitution from nearly 1000 μV K−1 for ZnSnP2 to −100 μV K−1 for ZnSnAs2 at 650 K. Thermal conductivity is decreased for the solid solutions due to alloy phonon scattering, compared to the end members with y = 0 and y = 2, with the y = 0.5 and y = 1.0 samples exhibiting the lowest values of 1.4 W m−1 K−1 at 825 K. Figure of merit values are increased for the undoped solid solutions at lower temperatures when compared to the end members due to the decreased thermal conductivity, with the y = 0.5 sample reaching zT = 1.6 × 10−3 and y = 1 reaching 2.1 × 10−3 at 700 K. The largest values of the figure of merit zT for the undoped series was found for y = 2 with zT = 2.8 × 10−3 at 700 K due to the increasing n-type Seebeck coefficient. Boltztrap calculations reveal that p-doping could yield zT values above unity at 800 K in case of ZnSnAs2, comparable with ZnSnP2.

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