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

Author(s)

Merces, Leandro ^[1] ; Candiotto, Graziani ^{[2, 3]} ; Minatogau Ferro, Leticia Marie ^{[4, 1]} ; de Barros, Anerise ^[4] ; Santos Batista, Carlos Vinicius ^{[1, 5]} ; Nawaz, Ali ^[6] ; Riul Jr, Antonio ; Capaz, Rodrigo B. ^{[3, 1]} ; Bof Bufon, Carlos Cesar ^{[4, 7, 1, 5]}

Affiliation

^[1] Brazilian Ctr Res Energy & Mat CNPEM, Brazilian Nanotechnol Natl Lab LNNano, BR-13083100 Campinas, SP - Brazil

^[2] Univ Fed Rio de Janeiro, Inst Quim, BR-21941909 Rio De Janeiro, RJ - Brazil

^[3] Univ Fed Rio de Janeiro, Inst Fis, BR-21941972 Rio De Janeiro, RJ - Brazil

^[4] Univ Estadual Campinas, Inst Chem, BR-13083970 Campinas, SP - Brazil

^[5] Sao Paulo State Univ, Postgrad Program Mat Sci & Technol, BR-17033360 Bauru, SP - Brazil

^[6] Bruno Kessler Fdn FBK, Ctr Sensors & Devices, I-38123 Trento - Italy

^[7] Univ Prebiteriana Mackenzie, BR-01302907 Sao Paulo - Brazil

• Document type: Journal article
• Source: SMALL; v. 17, n. 45 OCT 2021.
• Web of Science Citations: 2

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, approximate to 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. (AU)

• FAPESP's process: 14/25979-2 - Fabrication and characterization of devices and systems based on hybrid nanomembranes
• Grantee: Carlos César Bof Bufon
• Support Opportunities: Research Grants - Young Investigators Grants
• FAPESP's process: 18/18136-0 - Hybrid nanodevices: magnetoelectronic transport and development of sensors based on molecules/nanomembranes
• Grantee: Leandro das Mercês Silva
• Support Opportunities: Scholarships in Brazil - Post-Doctoral
• FAPESP's process: 14/50906-9 - INCT 2014: in Functional Complex Materials
• Grantee: Fernando Galembeck
• Support Opportunities: Research Projects - Thematic Grants
• FAPESP's process: 19/10188-3 - Space-charge distributions at interfaces of metal/insulator and metal/organics applied to hybrid capacitors based on nanomembranes
• Grantee: Carlos Vinicius Santos Batista
• Support Opportunities: Scholarships in Brazil - Master
• FAPESP's process: 17/02317-2 - Interfaces in materials: electronic, magnetic, structural and transport properties
• Grantee: Adalberto Fazzio
• Support Opportunities: Research Projects - Thematic Grants
• FAPESP's process: 17/21117-4 - Development and characterization of nanomembrane-based electrochemical cells for biosensor application
• Grantee: Letícia Mariê Minatogau Ferro
• Support Opportunities: Scholarships in Brazil - Doctorate
• FAPESP's process: 19/14949-9 - EMU: multiuser infrastructure dedicated to nanofabrication and characterization of nanodevices at LNNano/CNPEM
• Grantee: Edson Roberto Leite
• Support Opportunities: Multi-user Equipment Program