Optimizing Photodetectors in Two-Dimensional Metal-Metalloporphyrinic Framework Thin Films

Two-dimensional (2D) metalloporphyrin-based MOF thin films possessing abundant π-π interactions are promising materials for photoelectronic devices, but no reports on fabrication of photodetectors are available so far. Herein, a series of 2D MOF Zn₂[TCPP(M)] (named ZnTCPP(M); TCPP = 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin; M = Zn, Mn, Fe, and H₂) films with [001] orientation are fabricated on SiO₂/Si substrates by the liquid-phase epitaxial (LPE) layer-by-layer (lbl) approach and further assembled to photodetectors. The obtained ZnTCPP(M)-based photodetectors exhibit an excellent photoresponse due to abundant π-π stacking between the MOF layers. Moreover, the metalloporphyrinic groups in ZnTCPP(M) have a significant influence on modulating the photoresponse of the photodetectors, among which the prepared ZnTCPP(Zn) film-based device exhibits the best photodetection performance with a high on/off ratio of 2.3 × 10⁴, responsivity (R_λ, up to 10.3 A W^-1), short rise/fall times (0.09/0.07 s), and a large detectivity (D*) of 8.1 × 10¹³ Jones. Density functional theory (DFT) calculations reveal that the perturbation of the ring π-electron system and the introduction of low-lying states as well as the large delocalization of the metalloporphyrinic group will adjust the photodetection performance of ZnTCPP(M) films. These results will provide a new understanding of the modulation of 2D metalloporphyrinic MOFs toward photodetection performance and perspective for the fabrication of photoelectronic devices.