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

• Autor(a) principal: Merces, Leandro
• Data de Publicação: 2021
• Outros Autores: Candiotto, Graziâni, Ferro, Letícia Mariê Minatogau, de Barros, Anerise, Batista, Carlos Vinícius Santos [UNESP], Nawaz, Ali, Riul, Antonio, Capaz, Rodrigo B., Bufon, Carlos César Bof [UNESP]
• Tipo de documento: Artigo
• Idioma: eng
• Título da fonte: Repositório Institucional da UNESP
• Texto Completo: http://dx.doi.org/10.1002/smll.202103897; http://hdl.handle.net/11449/222542
• topic: density functional; electrochemical; electron transfer; hopping; Marcus; nanogap; nanomembrane origami

Intermolecular 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.