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Boron nitride nanomesh as a template for guided self-assembly of molecular arrays

English title Boron nitride nanomesh as a template for guided self-assembly of molecular arrays
Applicant Osterwalder Jürg
Number 122703
Funding scheme Sinergia
Research institution Physik-Institut Universität Zürich
Institution of higher education University of Zurich - ZH
Main discipline Condensed Matter Physics
Start/End 01.10.2008 - 30.09.2012
Approved amount 1'876'588.00
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All Disciplines (2)

Discipline
Condensed Matter Physics
Physical Chemistry

Keywords (11)

nanotemplate surfaces; molecular films; photoemission; scanning tunnelling microscopy; femtosecond lasers; solid-liquid interface; self-assembly; boron nitride; scanning tunneling microscopy; electrochemistry; functional surfaces

Lay Summary (English)

Lead
Lay summary
The Zürich surface physics group has, some years ago, discovered a surprising new nanostructured material based on a single layer of hexagonal boron nitride (h-BN) on a Rh(111) surface. A highly regular structure with the appearance of a nanomesh forms by high-temperature self-assembly in ultrahigh vacuum, with a three-nanometer periodicity and a two-nanometer pore size. It was later shown that this material is a perfect template for the self-assembly of ordered arrays of well separated molecules, and that this single-layer template is also stable in various liquids and can be imaged by scanning tunneling microscopy (STM) in an electrolyte solution. It is the mission of this project to establish the boron nitride nanomesh as a stable template for self-assembling molecular arrays by simple dip coating, drop casting or by electrochemical deposition, making it an attractive substrate for potential applications where massive and regular arrays of a wide range of organic molecules are required. The pore size and pore spacing in the few nanometer range leads to a separation of individual molecules, while the insulating character of the boron nitride decouples them from the underlying metal surface. Therefore, it is expected that the chemical, electronic, magnetic and spectroscopic properties of the individual free molecules are preserved to some degree. To explore the resulting properties of these two-dimensional (2D) molecular arrays as a whole is an important part of this project, as is the continuous search for their potential applications as functional surfaces, or as support for sensors and electronic devices.These issues will be addressed within a focussed consortium of four groups, funded within the Sinergia Programme of the SNF. The fundamental questions related to the molecule trapping and the physical properties of such arrays can be best studied under ultrahigh vacuum, which will be the main roles of the surface physics groups of the University of Zürich and EMPA Thun. While the EMPA group covers also direction of electrochemical STM in aqueous solvents, the physical chemistry group from the Katholieke Universiteit Leuven in Belgium (KULEUVEN) contributes the important knowhow in STM under organic solvents. The largely experimental approach will be supplemented, in specific and well defined cases, by theoretical efforts, including ab-initio density functional theory (DFT) methods and molecular dynamics simulations for the structure and dynamics at the solid-liquid interface, by the computational chemistry group of the University of Zürich (UZH-TH). For more information we refer the interested reader to the website www.nanomesh.ch.
Direct link to Lay Summary Last update: 21.02.2013

Responsible applicant and co-applicants

Employees

Publications

Publication
Comparative study of the nature of chemical bonding of corrugated graphene on Ru(0001) and Rh(111) by electronic structure calculations
Marcella Iannuzzi, Jürg Hutter (2011), Comparative study of the nature of chemical bonding of corrugated graphene on Ru(0001) and Rh(111) by electronic structure calculations, in Surface Science, 605(15-16), 1360-1368.
Investigation of Boron Nitride Nanomesh Interacting with Water
Ding Y, Iannuzzi M, Hutter J (2011), Investigation of Boron Nitride Nanomesh Interacting with Water, in JOURNAL OF PHYSICAL CHEMISTRY C, 115(28), 13685-13692.
Corrugated single layer templates for molecules: From h-BN nanomesh to graphene based quantum dot arrays
Ma HF, Thomann M, Schmidlin J, Roth S, Morscher M, Greber T (2010), Corrugated single layer templates for molecules: From h-BN nanomesh to graphene based quantum dot arrays, in FRONTIERS OF PHYSICS IN CHINA, 5(4), 387-392.
Nanotexture Switching of Single-Layer Hexagonal Boron Nitride on Rhodium by Intercalation of Hydrogen Atoms
Brugger T, Ma HF, Iannuzzi M, Berner S, Winkler A, Hutter J, Osterwalder J, Greber T (2010), Nanotexture Switching of Single-Layer Hexagonal Boron Nitride on Rhodium by Intercalation of Hydrogen Atoms, in ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 49(35), 6120-6124.
Supramolecular Assemblies Formed on an Epitaxial Graphene Superstructure
Pollard AJ, Perkins EW, Smith NA, Saywell A, Goretzki G, Phillips AG, Argent SP, Sachdev H, Muller F, Hufner S, Gsell S, Fischer M, Schreck M, Osterwalder J, Greber T, Berner S, Champness NR, Beton PH (2010), Supramolecular Assemblies Formed on an Epitaxial Graphene Superstructure, in ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 49(10), 1794-1799.
Nano-ice on Boron Nitride Nanomesh: Accessing Proton Disorder
Ma HF, Brugger T, Berner S, Ding Y, Iannuzzi M, Hutter J, Osterwalder J, Greber T (2010), Nano-ice on Boron Nitride Nanomesh: Accessing Proton Disorder, in CHEMPHYSCHEM, 11(2), 399-403.
Chiral Distortion of Confined Ice Oligomers (5,6)
Ma H., Ding Y., Iannuzzi M., Brugger T., Berner S., Hutter J., Osterwalder J., Greber T., Chiral Distortion of Confined Ice Oligomers (5,6), in Langmuir.
Investigation of h-BN/Rh(111) Nanomesh Interacting with Water and Atomic Hydrogen
Ding Y, Iannuzzi M, Hutter J, Investigation of h-BN/Rh(111) Nanomesh Interacting with Water and Atomic Hydrogen, in CHIMIA, 65(4), 256-259.
Nano-ice models for the water aggregates observed on the h-BN/Rh(111) nanomesh
Ding Yun, Iannuzzi M., Hutter J., Nano-ice models for the water aggregates observed on the h-BN/Rh(111) nanomesh, in J. Phys.: Condens. Matter, 24, 445002.

Scientific events

Active participation

Title Type of contribution Title of article or contribution Date Place Persons involved
Workshop on Statistical Physics and Low-Dimensional Systems (SPLDS 2011) 18.05.2011 Nancy, France


Associated projects

Number Title Start Funding scheme
111895 Density functional theory based calculations of large molecules and condensed systems 01.04.2006 Project funding (Div. I-III)
124691 Spin physics and electron dynamics at surfaces, interfaces and in ordered molecular layers 01.04.2009 Project funding (Div. I-III)
140441 Atomistic simulations of molecules at interfaces 01.07.2012 Project funding (Div. I-III)
165512 Probing 2D materials interaction with Graphene Quantum Dots (PIQuaDo) 01.02.2017 Project funding (Div. I-III)
150017 Periodic strain fields in graphene and hexagonal boron-nitride on transition metal substrates 01.02.2014 Project funding (Div. I-III)
116096 Static and dynamic phenomena on solid surfaces, interfaces and in nanostructures 01.04.2007 Project funding (Div. I-III)
132509 Periodic strain fields in graphene and hexagonal boron-nitride on transition metal substrates 01.02.2011 Project funding (Div. I-III)
149627 Molecular Surface Science on Ultra-Thin Insulator (MOSSUL) 01.01.2014 Project funding (Div. I-III)
135321 Spin physics and electron dynamics at surfaces, interfaces and in ordered molecular layers 01.04.2011 Project funding (Div. I-III)
128756 State-of-the-art Surface Analytics for Use Inspired Materials Research 01.03.2011 R'EQUIP
159690 Chiral Intermetallic Surfaces for Enantioselective Reactions 01.11.2015 Project funding (Div. I-III)

Abstract

The Zürich surface physics group (UZH-PH) has, some years ago, discovered a surprising new nanostructured material based on a single layer of hexagonal boron nitride (h-BN) on a Rh(111) surface. A highly regular structure forms by self-assembly, with the appearance of a nanomesh, and with a three-nanometer periodicity and a two-nanometer pore size. It was later shown that this material is a perfect template for the self-assembly of ordered arrays of well separated molecules, and that this single-layer template is also stable in various liquids and can be imaged by scanning tunneling microscopy in an electrolyte solution. This extreme stability of a structured single-layer dielectric makes it an attractive system for molecule adsorption studies at the solid-liquid interface.It is the mission of this project to establish the boron nitride nanomesh as a stable template for self-assembling molecular arrays by simple dip coating, drop casting or by electrochemical deposition, making it an attractive substrate for potential applications where massive and regular arrays of a wide range of organic molecules are required. The pore size and pore spacing in the few nanometer range leads to a separation of individual molecules, while the insulating character of the boron nitride decouples them from the underlying metal surface. Therefore, it is expected that the chemical, electronic, magnetic and spectroscopic properties of the individual free molecules are preserved to some degree. To explore the resulting properties of these two-dimensional (2D) molecular arrays as a whole is an important part of this project, as is the continuous search for their potential applications as functional surfaces, or as support for sensors and electronic devices.The principle issues and milestones are as follows:-Understand the character and properties of the trapping potential of the pores-Determine the range of solvents, solute concentrations and temperatureswhere the nanomesh remains stable-Understand the influence of the liquid environment on the molecular adsorption and self-assembly processes on the nanomesh -Direct comparison of molecular arrays prepared in a liquid and in UHV-Characterize physical and (electro-)chemical properties of such molecular arraysThese issues will be addressed within a focussed consortium of four groups, to be funded within the Sinergia Programme of the SNF. It includes two physicist, one physical chemist and one theoretical chemist groups. The fundamental questions related to the molecule trapping and the physical properties of such arrays can be best studied under ultrahigh vacuum (UHV), which will be the main roles of the surface physics groups of the University of Zürich (UZH-PH) and EMPA Thun. Given the scientific goals of the project, it has been absolutely crucial to include the expertise in scanning tunnelling microscopy (STM) at the solid-liquid interface. While the EMPA group covers the direction of electrochemical STM in aqueous solvents, we needed a strong partner for STM studies of molecular assemblies in organic solvents. We cannot find this expertise in Switzerland, but an excellent partner could be found at the Katholieke Universiteit Leuven in Belgium (KULEUVEN). The largely experimental approach will be supplemented, in specific and well defined cases, by theoretical efforts, including ab-initio density functional theory (DFT) methods and molecular dynamics simulations for the structure and dynamics at the solid-liquid interface, by the computational chemistry group of the University of Zürich (UZH-TH).
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