Reentrant semiconducting behavior in polymerized fullerite structures with increasing sp³-carbon content

Area of Science:

• Materials Science
• Condensed Matter Physics
• Computational Chemistry

Background:

• Fullerites are allotropes of carbon with unique electronic properties.
• Polymerization of fullerites can significantly alter their electronic band structure.
• Understanding structure-property relationships is crucial for designing novel electronic materials.

Purpose of the Study:

• To investigate the electronic behavior of polymerized fullerite structures.
• To explore the impact of dimensionality (1D to 3D) and sp3-carbon content on electronic properties.
• To elucidate the mechanisms behind the observed electronic transitions.

Main Methods:

• Utilized density functional theory (DFT) calculations.
• Employed the hybrid Heyd-Scuseria-Ernzerhof (HSE) functional.
• Used the 6-31G(d,p) basis set for electronic structure calculations.

Main Results:

• Observed a decrease in bandgap with increasing sp3-carbon content, leading to metallic behavior.
• Discovered a reentrant semiconducting behavior upon further increases in sp3-carbon content.
• Attributed these electronic changes to new states from polymeric bonding and volume reduction effects on sp2-states.

Conclusions:

• Polymerized fullerites offer a versatile platform for tuning electronic properties.
• The observed electronic transitions are controllable via structural modifications.
• This class of materials holds potential for advanced electronic applications.