Large‐Area Endohedral Metallofullerene Single‐Crystal Arrays for High‐Performance Field‐Effect Transistors and Photodetectors

Abstract

A structure with high crystallinity and orderly molecular packing is a requirement for high‐performance optoelectronic devices. However, growing large‐area, long‐range order, highly crystalline micro or nanostructures remains a challenge. Endohedral metallofullerenes (EMFs) are spherical π‐conjugated molecules with unique electronic structures, hence they can be easily assembled into highly ordered crystals through intermolecular π–π interactions. In this work, large‐area single‐crystal microwire arrays of M3N@Ih‐C80 (M = Sc, Lu) are prepared with the assistance of a pillar‐structured template, and the microwire diameter can be tuned via the fullerene concentration. A field‐effect transistor is fabricated using Sc3N@Ih‐C80 microwire arrays, exhibiting a record‐high charge carrier mobility (6.16 cm2 V−1 s−1) among EMF‐based devices. Further, microwire‐based photodetectors are developed, with a response time as low as 0.1 s. The precise arrangement of the M3N@Ih‐C80 molecules helps improve the electron transportation channels, thereby enhancing the device performance.

Recent advances in supramolecular fullerene chemistry

“…417,418 For instance, Li and coworkers prepared long-range M 3 NCC 80 (M = Sc, Lu) single-crystal microwires by utilizing a pillar-structured template, which exhibited highly sensitive photoconductivity with a response time as low as 0.1 s, and also were employed in field-effect transistors. 469 Molecular gels have been used as spatially confined templates for the growth of C 60 crystals to obtain super-long crystalline C 60 fibers and large-area 2D crystals, which were utilized as photodetectors with high performance by Liu, Fang, and coworkers. 470,471 The dice-shaped Sc 3 NCC 80 3D crystals have been utilized as a support for the Pt-catalyzed methanol oxidation by Yang and coworkers.…”

Exploring Endohedral Metallofullerenes for Advanced Thin-Film Device Applications toward Next-Generation Electronics

“…In 2021, Su et al demonstrated a high-performance FET utilizing EMFs containing metal nitride clusters. 56 Unlike the single metal atom cases, metal-nitride cluster EMFs exhibit icosahedral symmetry, similar to that of C 60 . Through strong π−π interactions between molecules, M 3 N@C 80 can assemble into microcrystals of various shapes in a solution.…”

“…In 2021, Su et al demonstrated a high-performance FET utilizing EMFs containing metal nitride clusters . Unlike the single metal atom cases, metal-nitride cluster EMFs exhibit icosahedral symmetry, similar to that of C 60 .…”

Crystalline architectures of C84 with tunable morphology and linearly polarized red emission

“…6,7 To date, there have been plenty of examples of morphological and structural control of FMNAs by finely tuning their preparation conditions. It was also reported that these well-defined FMNAs may exhibit unprecedented properties such as high electron carrier mobility and magnetic properties, 8,9 which are otherwise unavailable for individual molecules and amorphous aggregations. Nevertheless, there are fewer attempts to understand the deterministic relationship between the morphologies/structures of FMNAs and their physical properties.…”