Atomic and Molecular Manipulation

Table of Contents

Cover image

Introduction

STM Manipulation of Single Atoms and Molecules on Insulating Films

1. Introduction

2. Ultrathin insulating films

3. Interface state in NaCl/Cu(111)

4. Manipulation of metal atoms

5. Imaging molecular orbitals

6. Manipulation of molecules: Molecular/orbital engineering

7. Conclusion

Electron Transfer Phenomena at the Molecular Scale

1. Introduction

2. TCNQ on Au(111): The neutral adsorption of an electron acceptor molecule

3. TTF on Au(111): Formation of a Wigner molecular lattice

4. TTF–TCNQ on Au(111): Molecular magnetism induced by CT

5. Conclusions and remarks

Imprinting Atomic and Molecular Patterns

1. Single-molecule imprinting on semiconductors

2. Single-molecule imprinting on metals

3. Self-assembly followed by pattern imprinting

4. Modes of reaction

5. Conclusion

Acknowledgements

Tunnel-Current Induced STM Atomic Manipulation

1. Introduction

2. Experimental methods

3. Desorption

4. Intramolecular bond dissociation

5. Nonlocal manipulation

Introduction

Andrew J. Mayne and Gérald Dujardin

Institut des Sciences Moléculaires d'Orsay, CNRS, Université Paris Sud 11, Orsay, France

Abstract

This chapter is an introduction to the book Atom and molecular manipulation. A short history of scanning tunnelling microscopy techniques (STM) and the development of nanoscience are followed by a fully referenced description of the two principle manipulation techniques. Each chapter of the book is then summarized. The introduction continues with a description of the progress in atomic-scale imaging with the Atomic Force Microscope (AFM) as well as recent STM technical developments and new materials. The conclusion considers the potential of STM to inspire new research and the general public as large with the remarkable images of the building blocks of matter.

Keywords: STM manipulation; single atoms and molecules; nanotechnology; AFM

Working with individual atoms and molecules is a demonstration that miniaturised electronic, optical, magnetic and mechanical devices can operate ultimately even at the level of a single atom or molecule. As such, manipulation of individual atoms and molecules with the scanning tunnelling microscope (STM) has played a very emblematic role in the development of nanosciences and nanotechnologies. New methods, based on the use of the STM, have been developed to characterise and manipulate all the degrees of freedom of individual atoms and molecules, electronic, vibrational, spin spectroscopy, lateral and vertical manipulation, ¹ with an unprecedented precision. Based on this knowledge, manipulation of individual atoms and molecules has been used in recent years to test and propose new concepts for nanoelectronics, molecular nanomachines and the design of functionalised materials. From this, it appears that manipulation of individual atoms and molecules goes well beyond the demonstration of spectacular experiments and is now able to provide innovative concepts. This book illustrates the main aspects of this ongoing scientific adventure and anticipates the major challenges for the future in ‘atomic and molecular manipulation’ from fundamental knowledge to the fabrication of new devices and materials.

This book is divided into two sections which illustrate some of the different research directions in atomic and molecular manipulation on surfaces:

Nanoscience really entered the public consciousness in 1990 with the writing of the IBM logo in Xenon atoms by Eigler. ² This clearly showed that it was possible, using the STM, to do experiments and to fabricate things with only a few atoms and molecules and ultimately a single atom or molecule. Since 1990, there have been spectacular demonstrations of single atom or molecular manipulation. These range from the manipulation of a wide range of individual atoms and molecules to far more sophisticated experiments where complex nano-objects are fabricated by STM manipulation.¹., ³., and ⁴.

The basic design and operation of the STM have been explained in earlier books or reviews.⁵., and ⁶. Low temperature operation and sophisticated software have improved STM performances over the years. ⁷ Further recent developments are discussed at the end of this introduction. Manipulation methods in STM can be categorised into two principal types, manipulation by direct contact and manipulation by inelastic electron tunneling.³., and ⁴.

The direct contact method involves to bring the tip into close proximity with the adsorbate and to induce a modification by moving the tip. This can be either lateral, that is, parallel to the surface, or vertical, that is, normal to the surface. In these manipulations, the active ingredient is neither the tunnel electrons nor the electric field but rather the forces between the atoms on the tip and the surface. Historically, the direct contact method arose from the fact that the early manipulation experiments, by Eigler, for example, were carried out on metal surfaces where manipulation induced movement in the surface plane. Lateral manipulation is most widely used on metal surfaces because metals have a relatively uniform surface potential allowing adsorbed molecules to be pushed, pulled or slid across the surface. ⁸ Over the years, a number of spectacular results have been produced. Metal atoms can be positioned individually on a metal surface to create different geometric shapes, such as circles, ellipses, squares or resonators. These quantum corrals act as electron traps with the formation of standing waves of electronic surface states inside the corral.⁹., and ¹⁰. One of the most spectacular atomic-scale experiments is the quantum mirage where the placement of a magnetic Cobalt atom at a focus of an elliptical corral led to the appearance of a phantom atom at the other focus (Figure 1.1). ¹¹ Further experiments engineered different atomic structures using the coupling of the spin of magnetic atoms. ¹² Atom manipulation on metal surfaces has become a fine art, whereby judicious positioning of metal atoms can control the confinement of quantum interference patterns to the extent that the metal can be quantum holographically encoded (Figure 1.2). ¹³ The direct contact between the STM tip and the surface can also be used for vertical manipulation of single atoms or molecules. This has been demonstrated by the vertical manipulation of individual germanium atoms from a Ge(111)-c(2×8) surface at room temperature.¹⁴., and ¹⁵.

Inelastic electron tunnelling has been proved to be the most versatile method for STM manipulation.¹., ³., and ⁴. Of special interest is the resonant inelastic electron tunnelling when tunnel electrons are in resonance with occupied or unoccupied states of adsorbed atoms and molecules. Most of the time, resonant inelastic electron tunnelling results in local vibrational excitation, which can be used to desorb, ¹⁶ to move single atoms and molecules or to dissociate molecules, ¹⁷ and isomerise or change the configuration of a single molecule.¹⁸., ¹⁹., ²⁰., ²¹., ²²., and ²³. To increase the efficiency of resonant inelastic electron tunnelling, molecules should ideally be decoupled electronically from the substrate. So a number of avenues of research have investigated different approaches towards electronic decoupling of molecular orbitals from the underlying surface. ²⁴ Molecular deposition and manipulation have been tested on several different surfaces; thin insulating layers on a metal substrate,²⁵., ²⁶., and ²⁷. passivated semiconductor surfaces²⁸., ²⁹., ³⁰., and ³¹. and bulk insulator surfaces.³²., and ³³. As a general rule, in the case of these three categories of insulating surfaces, the molecules are only very weakly bound. To immobilise the molecules and so avoid surface diffusion on surfaces, passivated or otherwise, there are several options; use low temperature studies, self-assembled molecular arrays,³⁴., ³⁵., and ³⁶. or molecules with organic ligands to increase the binding energy.³⁷., and ³⁸. An alternative avenue of research is a wide band gap semiconductor such as silicon carbide. Until recently, most of the focus had been on the structural and electronic properties of silicon carbide,³⁹., ⁴⁰., and ⁴¹. but its reactivity towards molecules had received very little attention, with experiments only of oxidation⁴²., and ⁴³. or hydrogenation. ⁴⁴ Theoretical studies predicting reaction with organic molecules prompted recent STM studies of the adsorption of large organic molecules. ⁴⁵ These new STM and STS results show that the wide band gap of silicon carbide can indeed be used to electronically decouple the molecules from the surface.⁴⁶., and ⁴⁷.

The four chapters in this book are not limited to the description and the use of the various methods for STM manipulation. Each chapter illustrates how atomic and molecular manipulation has opened up completely new concepts for nanoelectronics (Chapters 2 and3) and the design of new functionalised materials (Chapters 4 and 5). Complementary calculations have now become de rigueur for almost every STM experiment, be that a simple observation to complex molecular dynamics during STM manipulation. ⁴⁸ A variety of calculation methods are used from ab initio and semi-empirical calculations through to simulated STM images of the atoms or molecules adsorbed on a surface.

In Chapter 2, Jascha Repp and Gerhard Meyer review their recent approach of using thin insulating layers on metal surfaces for manipulating single atoms and molecules. Clean metal surfaces, which have been initially used for STM manipulation, may have some advantages for lateral manipulation due to low diffusion barriers of adsorbed atoms and molecules. However, they are obviously not ideally suited to investigate electronic properties of single atoms and molecules whose orbitals strongly couple with the surface states of metals. The role of a thin insulating layer deposited on a metal substrate is to electronically decouple adsorbed atoms and molecules from the substrate by introducing a second tunnel barrier between the atoms and molecules and the metal substrate. By this method, Repp and Meyer are able to considerably extend the capabilities of single-atom and single-molecule electronics. For example, they demonstrate the control of charge states of single atoms (Au, Ag). Due to the large ionic polarisability of the thin insulating film of alkali halides (NaCl), several charge states of the Au or Ag atoms are stable. Then the STM tip is used to charge and discharge at will a single atom with a unity quantum yield, that is, a single tunnel electron is sufficient. Such a giant efficiency of resonant inelastic electron tunnelling (usually the quantum yield is between 10−⁶ and 10−¹⁰) indicates that the resonance is very long lived, thus confirming the insulating role of the thin NaCl film. This ability to manipulate a single electron at the level of a single atom opens the perspectives of future single-electron and single-atom electronics. Repp and Meyer introduce another very promising concept, that of molecular orbital engineering. They show that single-molecular orbitals can be directly imaged with the STM when the molecule is decoupled from the metal substrate by the insulating thin film. This ability to monitor a single-molecular orbital and its detailed modifications upon STM manipulation is exploited to perform experiments that would be impossible on metal substrates. By various sequences of STM manipulations, Repp and Meyer are able to activate an organometallic synthesis (bond formation between a single metal atom (Au) and a molecule (pentacene)) or a coordination complex synthesis (bond formation between a single Fe atom and two molecules). Single molecular orbital imaging enables an unambiguous control of the synthesis results. This is also used to control a molecular switching based on a tautomerisation reaction induced by inelastic electron tunnelling with the STM. These results illustrate the huge potential of molecular orbital engineering to monitor in detail all kinds of molecular reactions.

In Chapter 3, Isabel Torrente, Katharina Frenke and Jose Pascual report their discovery of new types of materials, that is, metal-free molecular magnets. This is very emblematic of the new knowledge afforded by STM topography and spectroscopy at the molecular scale. Here, the authors' objectives are to understand charge-transfer processes in organic charge-transfer materials. In crystal form, these compounds form semiconducting organic solids which are attractive for applications in organic electronics and photovoltaics. The particular molecules chosen here are the well-known tetrathiafulvalene (TTF) and tetracyanoquinodimethane (TCNQ) which have the ability to either donate (TTF) or accept electrons (TCNQ). ⁴⁹ For their STM studies, Torrente, Frenke and Pascual produce a self-assembled layer of TTF and TCNQ molecules on a metal surface (Au(111)). By carefully studying low temperature local STM spectroscopy and microscopy, the authors resolve the electron redistribution processes taking place at the organic-metal interface. The outstanding result is that the TCNQ molecule is charged with one electron. This negatively charged molecular radical thus sits in a spin ½ state and becomes magnetic. This is evidenced by a Kondo resonance⁵⁰ analysed by STM spectroscopy which shows vibrational fingerprints. From these results, the authors conclude that organic donor–acceptor interactions are promising avenue towards the spontaneous self-assembled organisation of metal-free molecular magnets.

Chapter 4 by Iain McNab and John Polanyi discusses the concept of molecular scale imprinting (MSI). It entails the self-assembling of atomic and molecular patterns on semiconductor or metal surfaces followed by localised atomic reactions that can be activated either locally by the tunnelling current from an STM tip or by heating or by photon irradiation. These two concepts of MSI and localised atomic reactions introduced by the Canadian group are issued from very detailed studies of molecular reactions on surfaces at the atomic scale with the STM.⁵¹., and ⁵². Many types of molecular reactions are discussed in this chapter: single and double dissociative attachment reactions, cooperative reactions, chain reactions, recoil reactions. Also, self-assembling of molecules into various patterns, circles and lines are shown. These examples illustrate the unique advantage of STM to explore the complexity of molecular reactions on surfaces. From this knowledge, McNab and Polanyi are able to extract new methods for imprinting atomic and molecular patterns.

In Chapter 5, Peter Sloan reviews some of the fundamental processes of STM molecular manipulation, desorption and intramolecular bond dissociation, produced by inelastic electron tunnelling. These processes are key processes in catalysis or surface photochemistry. They also provide new insights in electron-induced reactions in semiconductors or condensed gases. This chapter brings us up to date by describing the subtle interplay between competing dissociation and desorption reaction pathways of molecules that can be tuned by suitable adjustment of the electron tunnel conditions.⁵³., and ⁵⁴. So far, most of the studies have considered the surface as a passive substrate. Peter Sloan shows, from recent examples, that non-local reactions involving the transfer of energy or charges across surface states can also produce reactions at a distance.

This book is focused on STM manipulation of atoms and molecules and yet several chapters allude to wider