Reorganization Energy upon Controlled Intermolecular Charge-Transfer Reactions in Monolithically Integrated Nanodevices

Merces L.; Candiotto G.; Ferro L.M.M.; de Barros A.; Batista C.V.S.; Nawaz A.; Riul A.; Capaz R.B.; Bufon C.C.B.

Reorganization Energy upon Controlled Intermolecular Charge-Transfer Reactions in Monolithically Integrated Nanodevices

Tipo

Artigo

Data de publicação

2021

Periódico

Small

Citações (Scopus)

19

Autores

Merces L.
Candiotto G.
Ferro L.M.M.
de Barros A.
Batista C.V.S.
Nawaz A.
Riul A.
Capaz R.B.
Bufon C.C.B.

Resumo

© 2021 Wiley-VCH GmbHIntermolecular electron-transfer reactions are key processes in physics, chemistry, and biology. The electron-transfer rates depend primarily on the system reorganization energy, that is, the energetic cost to rearrange each reactant and its surrounding environment when a charge is transferred. Despite the evident impact of electron-transfer reactions on charge-carrier hopping, well-controlled electronic transport measurements using monolithically integrated electrochemical devices have not successfully measured the reorganization energies to this date. Here, it is shown that self-rolling nanomembrane devices with strain-engineered mechanical properties, on-a-chip monolithic integration, and multi-environment operation features can overcome this challenge. The ongoing advances in nanomembrane-origami technology allow to manufacture the nCap, a nanocapacitor platform, to perform molecular-level charge transport characterization. Thereby, employing nCap, the copper-phthalocyanine (CuPc) reorganization energy is probed, ≈0.93 eV, from temperature-dependent measurements of CuPc nanometer-thick films. Supporting the experimental findings, density functional theory calculations provide the atomistic picture of the measured CuPc charge-transfer reaction. The experimental strategy demonstrated here is a consistent route towards determining the reorganization energy of a system formed by molecules monolithically integrated into electrochemical nanodevices.

Assuntos Scopus

Density functionals , Electrochemicals , Electron transfer , Hopping , Marcu , Monolithically integrated , Nanogaps , Nanomembrane origami , Nanomembranes , Reorganization energies , Electrons