Inverse Design of Ultralow Lattice Thermal Conductivity Materials via Materials Database Screening of Lone Pair Cation Coordination Environment

Abstract

The presence of lone pair (LP) electrons is strongly associated with the disruption of lattice heat transport, which is a critical component of strategies to achieve efficient thermoelectric energy conversion. By exploiting an empirical relationship between lattice thermal conductivity, κ L , and the bond angles of pnictogen group LP cation coordination environments, we develop an inverse design strategy based on a materials database screening to identify chalcogenide materials with ultralow κ L for thermoelectrics. Screening the ∼635 000 real and hypothetical inorganic crystals of the Open Quantum Materials Database based on the constituent elements, nominal electron counting, LP cation coordination environment, and synthesizability, we identify 189 compounds expected to exhibit ultralow κ L . As a validation, we explicitly compute the lattice dynamical properties of two of the compounds (Cu 2 AgBiPbS 4 and MnTl 2 As 2 S 5 ) using first-principles calculations and successfully find both achieve ultralow κ L values at room temperature of ∼0.3−0.4 W/(m•K) corresponding to the amorphous limit. Our data-driven approach provides promising candidates for thermoelectric materials and opens new avenues for the design of phononic properties of materials.

Single‐Bonded Cubic AsN from High‐Pressure and High‐Temperature Chemical Reactivity of Arsenic and Nitrogen

“…The presence of electron lone pairs is indeed relevant to important physical properties [2] . In particular, together with other features observed in AsN, like the large size of the unit cell and the local static distortion, it has been related to the disruption of lattice heat transport, [64–66] by reducing the mean free path of phonons, [67] and has been identified among the main targets to achieve ultra‐low thermal conductivity and thermoelectric performance, [68–71] as recently predicted in 2D puckered α‐arsenene [42] . Within this perspective, the synthesis of AsN represents the first step towards the exploration of the high pressure chemistry of As and N, possibly leading to the discovery of other structures and stoichiometries.…”

Single‐Bonded Cubic AsN from High‐Pressure and High‐Temperature Chemical Reactivity of Arsenic and Nitrogen

“…The presence of electron lone pairs is indeed relevant to important physical properties. [2] In particular, together with other features observed in AsN, like the large size of the unit cell and the local static distortion, it has been related to the disruption of lattice heat transport,[ 64 , 65 , 66 ] by reducing the mean free path of phonons, [67] and has been identified among the main targets to achieve ultra‐low thermal conductivity and thermoelectric performance,[ 68 , 69 , 70 , 71 ] as recently predicted in 2D puckered α‐arsenene. [42] Within this perspective, the synthesis of AsN represents the first step towards the exploration of the high pressure chemistry of As and N, possibly leading to the discovery of other structures and stoichiometries.…”

Chemistry, Structure, and Function of Lone Pairs in Extended Solids

“…There are several aspects of lone pair behavior not considered in this account. A partial list includes their role in ion conducting materials, 29 in phase change materials, 30 their ability to reduce thermal transport in thermoelectrics, [31][32][33] band structure inversion in semiconductors such as GeTe, SnTe, and PbTe 34 more recently associated with topological properties in materials like SnTe, 35,36 and finally, their use as a symmetry-breaking element in non-linear optical materials. 37,38 3 Chemistry and Stereochemical Activity Figure 3: Room-temperature crystal structures of oxides and chalcogenides of the divalent tetrel (carbon group) elements.…”