Microsecond dynamics of molecular negative ions formed by low-energy electron attachment to fluorinated tetracyanoquinodimethane

Abstract

Low-energy (0–15 eV) electron interactions with gas-phase 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ) molecules are studied under single collision conditions using dissociative electron attachment spectroscopy. The experimental findings are supported by density functional theory calculations of the virtual orbital energies and energetics of the dissociative decays. Long-lived molecular negative ions F4-TCNQ− are detected in a wide electron energy range (0–3 eV) with electron detachment times in the range of milliseconds. Although plenty of decay channels are observed, their intensities are found to be very small (two to four orders of magnitude relative to the F4-TCNQ− signal). These findings prove that the structure of this strong electron-accepting molecule bearing an excess electron is robust in its electronic ground state, even when highly (up to 6 eV) vibrationally excited. As many as nine metastable fragment anions formed slowly (in the 16–23 µs range) are found in the negative ion mass spectrum of F4-TCNQ, as never observed before in compounds possessing high electron-accepting ability. The present results shed some light on microsecond dynamics of isolated F4-TCNQ molecules under conditions of excess negative charge, which are important for understanding the functionality of nanoscale devices containing this molecule as a structural element.

Large‐Area Deposition of Highly Crystalline F4‐Tetracyanoquinodimethane Thin Films by Molecular Step Templates

“…[16][17][18] Given the practical demands for complementary circuits, the quest for novel n-type crystalline OSC thin films remains of paramount significance.The fluorinated tetracyanoquinodimethane (Fx-TCNQ) family stands as a venerable and classic organic semiconducting materials that propel advancements in (opto)electronics and photonics. [19][20][21][22] Their allure stems from a high electron affinity, designating them as p-type molecular dopants for modulating the electrical properties of OSCs, [23,24] inorganic compound semiconductors, [25,26] 2D semiconductors, [19,27] and beyond. Additionally, Fx-TCNQ, enriched with fluorine atoms, can lower the lowest unoccupied molecular orbital (LUMO) energy level and enhance ambient stability, rendering it a promising candidate for high-performance n-channel OTFTs.…”