Symmetry Breaking Induced Anisotropic Carrier Transport and Remarkable Thermoelectric Performance in Mixed Halide Perovskites CsPb(I1–xBrx)3

We present a combination of first-principles calculations and the Boltzmann transport theory to understand the carrier transport and thermoelectric performance of mixed halide perovskite alloys CsPb(I_1-xBr_x)₃ with different Br compositions. Our computational results correlate the conduction band splitting in CsPb(I_1-xBr_x)₃ to the significant anisotropy in their carrier transport properties, such as effective masses and deformation potential constants. Such band splitting originates from the symmetry-broken crystal structures of CsPb(I_1-xBr_x)₃ polymorphs: with residue stresses/strains in asymmetric CsPb(I_1-xBr_x)₃, nondegenerate orbitals reconstruct the conduction band and reduce the Pb-halide antibonding character along certain directions. While the Seebeck coefficient (S) and the relaxation time-normalized electrical conductivity (σ/τ) show weak directional anisotropy, the carrier relaxation time (τ) is highly direction-dependent. The reconstruction of the conduction band finally leads to significantly anisotropic and enhanced thermoelectric power factors (PF = S²σ) in CsPb(I_1-xBr_x)₃ compared to those in pure CsPbI₃ and CsPbBr₃, showing anomalous nonlinear alloy behavior. A delicate balance between S²σ and combined measurement of the carrier effective mass and deformation potential constant, m*E_DP, is confirmed. The lattice thermal conductivities of CsPb(I_1-xBr_x)₃ are significantly suppressed compared to those of their pure counterparts due to strong mass disordering and strain fields upon halogen substitution. As a result, symmetry breaking in CsPb(I_1-xBr_x)₃ leads to anisotropy in carrier transport, high PF, and scattered phonon transport (ultralow thermal conductivity), concurrently contributing to their promising thermoelectric figures of merit (ZT) up to 1.7 at room temperature. The principles behind the asymmetry-induced factors would serve as new design concepts to tailor the thermoelectric properties of alloys, mixtures, superlattices, and low-dimensional materials.