Computational Screening of Bonding-Controlled Electronic Structures in One-Dimensional Cu/Ag-Based Hybrid...

Area of Science:

• Materials Science
• Solid-State Physics
• Computational Chemistry

Background:

• One-dimensional hybrid organic-inorganic semiconductors (HOISs) offer unique electronic properties due to reduced dimensionality and interfacial effects.
• Band-edge engineering is crucial for tuning semiconductor performance, particularly in optoelectronic applications.
• Cu/Ag-based systems remain underexplored despite their potential in HOISs.

Purpose of the Study:

• To investigate the electronic physics and bonding-dependent behavior of Cu/Ag halide HOISs.
• To elucidate the relationship between bonding characteristics and electronic band structure in 1D HOISs.
• To identify novel Cu-based HOISs with tunable light-harvesting properties.

Main Methods:

• High-throughput first-principles calculations were employed.
• 90 Cu/Ag halide HOISs derived from experimental structures were analyzed.
• Electronic band structures and orbital hybridization were examined.

Main Results:

• A transition in electronic behavior was observed, from isolated inorganic chains in ionic hybrids to strongly hybridized band edges in covalent/mixed-bonding hybrids.
• Ligand p orbitals and Cu-derived states, along with halogen p orbitals, cooperatively couple in covalent frameworks.
• This hybridization results in p-orbital-dominated band edges, enhanced dispersion, and light-hole effective masses along 1D chains.

Conclusions:

• Bonding nature fundamentally dictates the electronic properties of Cu/Ag halide HOISs.
• Strong interfacial orbital hybridization in covalent frameworks is key to achieving desirable electronic characteristics.
• Four promising Cu-based compounds were identified for tuning light-harvesting properties in low-dimensional hybrid semiconductors.