Design of Organic–Inorganic Hybrid Heterostructured Semiconductors via High-Throughput Materials Screening for Optoelectronic Applications

Abstract

Organic–inorganic hybrid semiconductors, of which organometal halide perovskites are representative examples, have drawn significant research interest as promising candidates for next-generation optoelectronic applications. This interest is mainly ascribed to the emergent optoelectronic properties of the hybrid semiconductors that are distinct from those of their purely inorganic and organic counterparts as well as different material fabrication strategies and the other material (e.g., mechanical) properties that combine the advantages of both. Herein, we present a high-throughput first-principles material screening study of the hybrid heterostructured semiconductors (HHSs) that differ entirely from organometal halide perovskite hybrid ion-substituting semiconductors. HHSs crystallize as superlattice structures composed of inorganic tetrahedrally coordinated semiconductor sublayers and organic sublayers made of bidentate chain-like molecules. By changing the composition (e.g., IV, III–V, II–VI, I–III–VI2 semiconductor) and polymorph (e.g., wurtzite and zinc-blende) of the inorganic components, the type of organic molecules (e.g., ethylenediamine, ethylene glycol, and ethanedithiol), and the thickness of the composing layers across 234 candidate HHSs, we investigated their thermodynamic, electronic structure, and optoelectronic properties. Thermodynamic stability analysis indicates the existence of 96 stable HHSs beyond the ZnTe/ZnSe-based ones synthesized experimentally. The electronic structure and optoelectronic properties of HHSs can be modulated over a wide range by manipulating their structural variants. A machine learning approach was further applied to the high-throughput calculated data to identify the critical descriptors determining thermodynamic stability and electronic band gap. Our results indicate promising prospects and provide valuable guidance for the rational design of organic–inorganic hybrid heterostructured semiconductors for potential optoelectronic applications.

Emerging Two-Dimensional Organic Semiconductor-Incorporated Perovskites─A Fascinating Family of Hybrid Electronic Materials

“…In contrast, several ML models have been successfully trained to accelerate the finding of new 3D halide perovskites. Deep learning models, classical ML models, as well as a high-throughput screening frameworks have been developed to predict various electronic properties and aid ligand design with well-discovered features. − Lin et al recently published a molecular dynamics (MD) simulation study of over 10k prospective OSiPs to establish design rules for stable ligand incorporation (Figure d) . Due to the ability of the ligands to relax across unit cells, they found that ligands larger than the unit cell along one dimension can still be accommodated in many cases and that linker selection plays a critical role for several specific body chemistries.…”

Design Rules for Two‐Dimensional Organic Semiconductor‐Incorporated Perovskites (OSiP) Gleaned from Thousands of Simulated Structures**

“…Published ligand data is scarce, lacks structural diversity, and also exhibits a strong bias toward positive examples (i.e., ligands that fail to form perovskites are rarely reported). While there has been other simulation and machine learning work to predict perovskite electronic properties or predict dimensionality, [22][23][24][25][26][27] there has been comparatively little dedicated to understanding the atomistic ligand factors that influence stability. There are thus clear opportunities to generate more diverse ligand data and establish ligand design constraints.…”

Solvothermal Synthesis of Bismuth-Based Halide Perovskite Nanostructures for Photocatalytic Degradation of Organic Pollutants under LED Light Irradiation

“…Therefore, narrowing the band gap of a Bi-based hybrid OIHP is necessary to make it an effective material for photocatalytic processes under visible-light irradiation. Prior efforts to narrow the band gap relied heavily on doping techniques to change the electrical band structure. − As an alternative to the doping method, surface and crystal facet techniques for synthesizing semiconductors with reduced band gaps have recently been presented and have demonstrated their ease of use and high efficacy. , Due to the presence of disorders or defects that cause longer local states to occur in the band gap, the material forms with a reduced bandgap. , …”