Electric Field Control of Molecular Charge State in a Single-Component 2D Organic Nanoarray

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Main Authors: Kumar, Dhaneesh, Krull, Cornelius, Yin, Yuefeng, Medhekar, Nikhil V., Schiffrin, Agustin
Format: Preprint
Published: 2024
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author Kumar, Dhaneesh
Krull, Cornelius
Yin, Yuefeng
Medhekar, Nikhil V.
Schiffrin, Agustin
author_facet Kumar, Dhaneesh
Krull, Cornelius
Yin, Yuefeng
Medhekar, Nikhil V.
Schiffrin, Agustin
contents Quantum dots (QD) with electric-field-controlled charge state are promising for electronics applications, e.g., digital information storage, single-electron transistors and quantum computing. Inorganic QDs consisting of semiconductor nanostructures or heterostructures often offer limited control on size and composition distribution, as well as low potential for scalability and/or nanoscale miniaturization. Owing to their tunability and self-assembly capability, using organic molecules as building nano-units can allow for bottom-up synthesis of two-dimensional (2D) nanoarrays of QDs. However, 2D molecular self-assembly protocols are often applicable on metals surfaces, where electronic hybridization and Fermi level pinning can hinder electric-field control of the QD charge state. Here, we demonstrate the synthesis of a single-component self-assembled 2D array of molecules [9, 10-dicyanoanthracene (DCA)] that exhibit electric-field-controlled spatially periodic charging on a noble metal surface, Ag(111). The charge state of DCA can be altered (between neutral and negative), depending on its adsorption site, by the local electric field induced by a scanning tunneling microscope tip. Limited metal-molecule interactions result in an effective tunneling barrier between DCA and Ag(111) that enables electric-field-induced electron population of the lowest unoccupied molecular orbital (LUMO) and hence charging of the molecule. Subtle site-dependent variation of the molecular adsorption height translates into a significant spatial modulation of the molecular polarizability, dielectric constant and LUMO energy level alignment, giving rise to a spatially dependent effective molecule-surface tunneling barrier and likelihood of charging. This work offers potential for high-density 2D self-assembled nanoarrays of identical QDs whose charge states can be addressed individually with an electric field.
format Preprint
id arxiv_https___arxiv_org_abs_2405_18855
institution arXiv
publishDate 2024
record_format arxiv
spellingShingle Electric Field Control of Molecular Charge State in a Single-Component 2D Organic Nanoarray
Kumar, Dhaneesh
Krull, Cornelius
Yin, Yuefeng
Medhekar, Nikhil V.
Schiffrin, Agustin
Materials Science
Mesoscale and Nanoscale Physics
Quantum dots (QD) with electric-field-controlled charge state are promising for electronics applications, e.g., digital information storage, single-electron transistors and quantum computing. Inorganic QDs consisting of semiconductor nanostructures or heterostructures often offer limited control on size and composition distribution, as well as low potential for scalability and/or nanoscale miniaturization. Owing to their tunability and self-assembly capability, using organic molecules as building nano-units can allow for bottom-up synthesis of two-dimensional (2D) nanoarrays of QDs. However, 2D molecular self-assembly protocols are often applicable on metals surfaces, where electronic hybridization and Fermi level pinning can hinder electric-field control of the QD charge state. Here, we demonstrate the synthesis of a single-component self-assembled 2D array of molecules [9, 10-dicyanoanthracene (DCA)] that exhibit electric-field-controlled spatially periodic charging on a noble metal surface, Ag(111). The charge state of DCA can be altered (between neutral and negative), depending on its adsorption site, by the local electric field induced by a scanning tunneling microscope tip. Limited metal-molecule interactions result in an effective tunneling barrier between DCA and Ag(111) that enables electric-field-induced electron population of the lowest unoccupied molecular orbital (LUMO) and hence charging of the molecule. Subtle site-dependent variation of the molecular adsorption height translates into a significant spatial modulation of the molecular polarizability, dielectric constant and LUMO energy level alignment, giving rise to a spatially dependent effective molecule-surface tunneling barrier and likelihood of charging. This work offers potential for high-density 2D self-assembled nanoarrays of identical QDs whose charge states can be addressed individually with an electric field.
title Electric Field Control of Molecular Charge State in a Single-Component 2D Organic Nanoarray
topic Materials Science
Mesoscale and Nanoscale Physics
url https://arxiv.org/abs/2405.18855