Reorganization Energy upon Controlled Intermolecular Charge‐Transfer Reactions in Monolithically Integrated Nanodevices
Year: 2021
Type: article
Abstract: 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.
Source: Small
Institutions: Brazilian Center for Research in Energy and Materials, Laboratório Nacional de Nanotecnologia, Universidade Federal do Rio de Janeiro, Universidade Estadual de Campinas (UNICAMP), Universidade Estadual Paulista (Unesp), Fondazione Bruno Kessler, FBK Center for Sensors & Devices, Universidade Presbiteriana Mackenzie
Language: English
Subfield: Electrical and Electronic Engineering
Field: Engineering
Domain: Physical Sciences
Open Access status: green
Funders: Fundação de Amparo à Pesquisa do Estado de São Paulo, Coordenação de Aperfeiçoamento de Pessoal de Nível Superior, Conselho Nacional de Desenvolvimento Científico e Tecnológico, Fundação Carlos Chagas Filho de Amparo à Pesquisa do Estado do Rio de Janeiro, Universidade Federal do Rio de Janeiro, Centro Nacional de Pesquisa em Energia e Materiais, Laboratório Nacional de Nanotecnologia
Awards: G1677423749, G1840770272, G2163278955, G2286822848, G2330941210, G2584274330, G3253354750, G3376402435, G3605092344, G3984251665, G4117782621, G4191467744, Fabrication and characterization of devices and systems based on hybrid nanomembranes, G4671817474, INCT 2014: in Functional Complex Materials, G5509007580, G6173158562, G7617736165, EMU: multiuser infrastructure dedicated to nanofabrication and characterization of nanodevices at LNNano/CNPEM, G8733947178, Interfaces in materials: electronic, magnetic, structural and transport properties
OpenAlex ID: W3204613618