Understanding molecular conduction

Supriyo Datta
School of Electrical and Computer Engineering
Purdue University, West Lafayette, IN 47907

Figure:
What is the
resistance of a
molecule?

It is common to differentiate between two ways of building a nanodevice: a topdown approach where we start from something big and chisel out what we want and a
bottom-up approach where we start from something small like atoms or molecules and
assemble what we want. When it comes to describing electrical resistance, the standard
approach could be called a top-down one where we start from big complicated resistors
and work our way down to molecules primarily because our understanding has evolved in
this top-down fashion. But I believe it is instructive to take a bottom-up view of the
subject starting from the conductance of something really small, like a molecule, and then
discussing the issues that arise as we move to bigger conductors. That is what I will try to
do in this tutorial lecture [1].
Remarkably enough, no serious quantum mechanics is needed to understand
electrical conduction through something really small, except for unusual things like the
Kondo effect that are seen only for a special range of parameters. I will (1) start with
energy level diagrams, (2) show that the broadening that accompanies coupling limits the
conductance to a maximum of (q^2/h) per level, (3) describe how a change in the shape
of the self-consistent potential profile can turn a symmetric current-voltage characteristic
into a rectifying one, (4) show that many interesting effects in molecular electronics can
be understood in terms of a simple model, and (5) introduce the non-equilibrium Greens
function (NEGF) formalism as a sophisticated version of this simple model with ordinary
numbers replaced by appropriate matrices. Finally I will describe the distinction between
the self-consistent field regime and the Coulomb blockade regime and the issues involved
in modeling each of these regimes.
1. S. Datta, Electrical Resistance: An Atomistic View, Nanotechnology, 15, S433
(2004).

Quantum chemistry
George C. Schatz and Mark A. Ratner
Department of Chemistry
Northwestern University, Evanston IL 60208-3113
This tutorial will provide an overview of electronic structure calculations from a
chemists perspective. This will include a review of the basic electronic structure
theories: Hartree-Fock and beyond, density functional theories and semiempirical
theories; the atomic orbital basis sets used to represent the wavefunction; and properties
that can be obtained from solutions to the Schrodinger equation. Much of the discussion
will center on quantum chemistry methods that use Gaussian orbital basis functions to
determine molecular orbitals, equilibrium geometries and the thermochemical properties
of small molecules. We will also consider extensions relevant to molecular electronics.

Probing molecular conduction with scanning probe microscopy

Mark C. Hersam
Department of Materials Science and Engineering
Northwestern University, Evanston IL 60208-3108
This tutorial will provide an overview of scanning probe microscopy (SPM) and
its application towards problems in molecular conduction. In an effort to communicate
the power and limitations of these instruments, the tutorial will describe design
considerations and reveal the detailed construction of a cryogenic variable temperature
ultra-high vacuum scanning tunneling microscope. With the microscope complete, the
tutorial will then discuss its use for a variety of techniques that have been used to study
the properties and performance of molecular-scale electronic devices. Specific examples
include Kelvin probe microscopy, conductive atomic force microscope potentiometry,
scanning tunneling spectroscopy, and inelastic electron tunneling spectroscopy.

Controlled molecular adsorption on Si: Laying a foundation for molecular devices

Bob Wolkow
Department of Physics, University of Alberta
and
National Institute for Nanotechnology, Edmonton Alberta
Our understanding of and control over molecular adsorption on silicon has
advanced very significantly in the last several years. It is now possible to provide a
microscopic picture of structure and bonding in covalently attached molecule-silicon
surface systems. This detailed understanding of adsorbate-surface structures was entirely
lacking when the first wave of enthusiasm for molecular devices crested roughly 20 years
ago. While many ideas for molecule-scale devices have been put forward in the past, the
tools - both synthetic and analytical - to pursue those ideas did not exist. Now, the
control necessary to begin exploring ways to incorporate organic function into existing
technologies or, eventually, to make new molecule-scale devices is within reach [1].
Experimental and modeling methods have emerged that effectively extend the resolution
of STM to see the details of adsorbed molecule structure and bonding. In the next several
years it is now realistic to expect structures and concepts dreamed about for decades to
begin to be realized. This talk will focus on a self-directed growth process for creating
molecular nanostructures on silicon [2] and extensions of that process [3-7].
1.
2.
3.
4.
5.
6.
7.

Controlled Molecular Adsorption on Si: Laying a Foundation for Molecular

Devices, R.A. Wolkow, Annual Review of Physical Chemistry, 50, 413-41,
1999.
Self-Directed Growth of Molecular Nano-Structures on Silicon, G.P Lopinski,
D.D.M. Wayner and R.A. Wolkow, Nature 406, 48 (2000).
Electronic structure and STM images of self-assembled styrene lines on a
Si(100) surface, W.A. Hofer, A.J. Fisher, G.P. Lopinski and R.A. Wolkow,
Chem Phys Lett, 365, 129134 (2002)
Patterning of vinyl ferrocene on H-Si(100) via self directed growth of
molecular lines and STM induced decomposition, Peter Kruse and
R.A.Wolkow, Nano Lett.; 2, 807-810 (2002).
Organic modification of hydrogen terminated silicon surfaces, Danial D. M.
Wayner and Robert A. Wolkow, J. Chem. Soc., Perkin Trans. 2, 23-34 (2002).
Reversible Passivation of Silicon Dangling Bonds with the Stable Radical
TEMPO, Pitters, J. L.; Piva, P. G.; Tong, X.; Wolkow, R. A. Nano Lett.;3,
1431-1435 (2003).
Gentle lithography'' with benzene on Si(100), Peter Kruse and Robert A.
Wolkow, Appl. Phys. Lett. 81, 4422-24 (2002).

Molecular electronics: Theoretical hits and misses

A. W. Ghosh, G-C. Liang, T. Rakshit, K. Bevan, S. Pati, M. Paulsson,
F. Zahid, D. Kienle, E. Polizzi, B. Muralidharan and S. Datta
Department of Electrical and Computer Engineering
Purdue University
Over the last few years, there have been a lot of experimental and theoretical
activity in the emerging field of molecular electronics. As in any new area of research,
progress has been stymied at times by experimental glitches including artifacts,
characterization problems and lack of reproducibility by different groups. In the
theoretical world as well, there has been similar confusion, with lack of proper
benchmarking and consistency between theory and experiments, and indeed among
different theories. In this talk, I will concentrate on our general theoretical understanding
of available experiments, concentrating on what is understood and what is not.
The non-equilibrium Green's function approach (NEGF) gives us a formally
rigorous platform for studying quantum kinetics, including effects of scattering and
many-body correlations. Our past endeavors in this direction have included making
NEGF part of the silicon device theorists' toolkit, as well as investigating various
molecular I-Vs [1]. Our approach consists of self-consistently combining the electronic
structures of the conducting species and the contacts with the NEGF transport formalism,
allowing us to explore various interesting physics as well as device prospects.
Encouraging quantitative agreements have been achieved with experiments showing
ohmic conduction on quantum point contacts [2], resonant conduction in phenyl [2] and
xylyl dithiol [3], and rectifying behavior arising from charging in other organic molecules
[4]. Furthermore, we have a clearer understanding of factors responsible for various
aspects of conduction, such as (a) the role of the potential profile [5], (b) the importance
of the conformational flexibility [6], (c) a proper understanding of level broadening by
the contacts [7], and (d) the position of the Fermi energy relative to the molecular levels
[8]. Our recent endeavors in this direction include incorporating electron-electron
interactions to develop a proper Coulomb Blockade theory of molecular conduction
within a model Hamiltonian for benzene, and a treatment of electron-phonon interactions
to study various observed inelastic tunneling (IETS) spectra.
From a scientific and technical point of view, one of the interesting directions to
pursue is molecules on silicon substrates. This is a system of inherent applied interest
with memory elements and sensors in mind. Furthermore, it promises new physics due to
the silicon bandstructure, making the contact an active player in the conduction process
rather than a passive electron injector. In particular, the silicon band-edge acts as a filter
which leads to peaks in the I-V (negative differential resistance, NDR) thereby
accentuating features intrinsic to the molecule. Based on a simple band-diagram, we
predicted a doping-dependent one-sided NDR [9] which was shortly thereafter
demonstrated through a powerful set of experiments from Mark Hersam's group at
Northwestern University [10]. Doing quantitative justice to this problem, however, has
been elusive for some time. One of the challenges was to formally integrate a semiempirical description of silicon surface physics (including band-bending, reconstruction
and surface state effects) with a first-principles description of the molecule, ie, bringing

the physicists' and chemists' worlds together within one formalism. I will outline some of
our endeavors in this manner, which have allowed us to obtain an atomistic theory of
molecular I-Vs on silicon with encouraging quantitative agreements with experiments
(such as with STM data on the bare silicon surface and with various measurements on
buckyballs on silicon). However, one of the outstanding puzzles remains the quantitative
explanation of the experiments from Northwestern University, where the NDRs seem to
appear prematurely compared to our theoretical estimates.
[1] P. S. Damle, A. W. Ghosh and S. Datta, in "Molecular Nanoelectronics," Ed. Mark
Reed and Takhee Lee.
[2] P. S. Damle, A. W. Ghosh and S. Datta, Phys. Rev. B 64, R201403 (2001).
[3] A. W. Ghosh, P. Damle, S. Datta and A. Nitzan, MRS Bulletin 29, 391 (2004).
[4] F. Zahid, A. W. Ghosh, M. Paulsson, E. Polizzi and S. Datta, cond-mat/0403401.
[5] G-C. Liang, A. W. Ghosh, M. Paulsson and S. Datta, Phys. Rev. B 69, 115302 (2004).
[6] A. W. Ghosh, T. Rakshit and S. Datta, Nano Letters 4, 565 (2004).
[7] P. S. Damle, A. W. Ghosh and S. Datta, Chem. Phys. 281, 171 (2002).
[8] A. W. Ghosh and S. Datta, Journal of Computational Electronics 1, 515 (2002).
[9] T. Rakshit, G-C. Liang, A. W. Ghosh and S. Datta, cond-mat/0305695.
[10] N. P. Guisinger, M. E. Greene, R. Basu, A. S. Baluch, and M. C. Hersam, Nano
Letters 4, 55 (2004).

Ballistic emission electron microscopy studies

of metal-molecule-semiconductor diodes
J. W. P. Hsu,1 W.-J. Li,2 K. L. Kavanagh,2 C. M. Matzke,1 A. A. Talin3
1
Sandia National Laboratories, Albuquerque, NM 87123
2
Department of Physics, Simon Fraser University, BC, V5A 1S6, Canada
3
Sandia National Laboratories, Livermore, CA 94551
Using ballistic electron emission microscopy (BEEM), an application of scanning
tunneling microscopy (STM), we measured the transport through alkanedithiol molecules
that are chemically bonded to GaAs and Au. In these devices, the molecules are
sandwiched between the two electrodes and are not easily accessible. BEEM is one of the
very few experimental techniques that is capable of measuring the local transport through
such buried interfaces. Carriers that are transmitted ballistically across the thin Au layer,
through the molecular layer, and into the GaAs are detected. The BEEM current is
measured as a function of the tip bias and thus, the local interfacial barrier height is
determined without applying a bias across the metal-semiconductor interface. Since
BEEM is a local measurement, it should be able to distinguish artifacts such as metallic
filaments from purely molecular transport. Our preliminary results on
Au/alkanedithiol/GaAs diodes with electron-beam evaporated Au contacts onto the
molecular layer show a large increase in the I-V barrier height (1.1 eV) in the presence of
the molecular layer, with a repeatable BEEM threshold voltage 1.4 eV occurring at
scattered locations. This is compared with 0.8 eV barrier heights for the Au/GaAs control
diodes.

Metal/molecule/semiconductor device structures

David B. Janes
School of Electrical and Computer Engineering
And Birck Nanotechnology Center
Purdue University, W. Lafayette, IN 47906 USA
This talk will describe the development and electrical characterization of
molecular electronic components involving metal/molecule/semiconductor (MMS)
device structures. The devices are lithographically defined and fabricated using an
indirect evaporation technique for the metal (top) contact and p+ GaAs for the bottom
contact. In these structures, the electronic conduction between the metal and
semiconductor can be modulated by choice of molecular species. Several alkyl thiol and
aromatic thiol molecules have been employed in order to determine the effects of
molecular length, conjugation and intrinsic dipole moment. The MMS devices exhibit
larger current densities than metal-GaAs control samples.
The current-voltage
characteristics and conductance of the devices have been studied versus temperature.
Generally, the MMS devices exhibit lower observed activation energies than that of a
metal/semiconductor Schottky barrier. These results reflect previous studies in which
nanoscale metal/molecule/semiconductor structures exhibited low resistance contacts,
implying that effective coupling and control of the surface electrical properties can be
achieved using a molecular layer1. An electrostatic model for the MMS structure has been
developed, in order to determine the band diagram of the structure. Two important
observations arise from this model. First, due to the relatively low dielectric constant of
the molecular layers, the majority of both the built-in and applied potentials is dropped
across the molecular layer. Second, there is generally a depletion region in the
semiconductor layer, with a width which is significantly smaller than that of the metalsemiconductor control sample. Therefore, the overall conduction appears to be
determined by a compound barrier consisting of both the molecular states and a modest
depletion region in the semiconductor. These results indicate that the interface Fermi
level is not pinned, consistent with our prior studies on surface Fermi level unpinning in
GaAs structures2. The model 1) T. Lee, et al., APL 76, 212 (2000). 2) S. Lodha, et al.,
Appl. Phys. Lett. 80, 4452 (2002).

Current-induced effects in molecular junctions

Max Di Ventra
Department of Physics
University of California at San Diego
I will discuss current-induced effects in molecular junctions such as
electromigration, local heating, inelastic current and current fluctuations. The main focus
will be on their description at the atomic level. Particular attention will be given to open
questions regarding these effects, and their impact on the stability of molecular structures
under current flow and as possible diagnostic tools.

Reading chemical information of a single molecule electronically

N. J. Tao
Department of Electrical Engineering
Arizona State University, Tempe, Arizona 85287
The ability to measure and control electron transport through a single molecule
electrically wired to two electrodes is a basic requirement towards the goal of building an
electronic device using single molecules. It also allows one to read the chemical and
biological information of the molecule electronically, which opens the door to chemical
sensor applications based on electrical measurement of individually wired molecules. To
reliably measure the conductance, one must provide a reproducible electronic coupling
between the molecule and the probing electrodes. One must also find a signature to
identify that the measured conductance is due to not only the sample molecules but also a
single sample molecule. Finally, for biologically relevant molecules, it is highly desired
to carry out the measurement in aqueous solutions in order to preserve the native
conformation of the molecule. We have developed a method to attach a single molecule
to two electrodes via covalent bonds, which allows us to reliably measure single molecule
conductance of many systems, including peptides and DNA in aqueous solutions. By
simultaneously measuring the conductance and the force required to break a molecule
from contacting the electrodes, we can identify how many molecules are involved in the
measurements and if the molecules are indeed covalently bonded to two electrodes. We
have studied the dependence of the conductance on the sequence, length as well as
specific bindings of the molecules with other species.

Inelastic effects in molecular conduction

Abe Nitzan
Department of Chemistry
Tel Aviv University
This work will give an overview of work done at Tel Aviv University and at
Northwestern University on effects of electron-phonon coupling on molecular
conduction, including dephasing, dissipation, heating and heat conduction, then describe
some recent observations, interpretations and predictions on inelastic electron tunneling
spectroscopy.
(with M. Galperin and M. Ratner, NWU, and D. Segal Weizmann Institute)

Non-linear conductance in molecular electronics

R. Shashidhar, David Long, and Jason Lazorcik
Geo-Centers Inc, Washington D.C. 20003
B. R. Ratna, J. Kushmerick, and A. Blum
Naval Research Laboratory, Washington D.C. 20375
Non-linear conductance is a very important factor in the development of
molecular electronic devices. We have carried out a variety of studies aimed at
understanding the fundamental aspects associated with conductance switching and other
non-linear molecular electronic behavior in two-terminal devices. The following results
covering both these aspects will be presented:
Results on conductance switching and non-linear electronic behavior:
1. Using molecules with asymmetric attachment groups on the two ends and stepwise self-assembly; it is shown that molecular rectification is derived solely from
the internal molecular asymmetry and not from the nature of metal-molecule
contacts.
2. By a combination of experimental techniques on the same molecular system, it is
demonstrated that voltage controlled molecular switching is distinct from
stochastic switching. Scanning tunneling spectroscopy and crossed-wire tunnel
junction measurements on the same molecule demonstrate that the switching is
indeed an inherently molecular event.
3. Inelastic tunneling spectroscopy studies on insulating alkyl and -conjugated
molecular wires are presented. The results provide experimental insight into the
coupling between tunnel charge carriers and molecular vibrations in molecular
electronic systems.
4. Systematic studies on conductance switching have been carried out (by using a
new test bed) on molecules with different chemical structures. These studies allow
us to correlate the extent of non-linear switching behavior with the specifics of the
molecular structure.

Perspectives on molecules and nanostructures for molecular conductance

James Yardley
Department of Chemical Engineering
Columbia University
Molecules offer attractive alternatives to silicon devices for use in for information
processing. The Columbia University Center for Electron Transport in Molecular
Nanostructures was created by the National Science Foundation of the United States as
one of six Nanoscale Science and Engineering Centers. The purpose of the Center is to
understand fundamental aspects of the conduction of electrons through molecules and
molecular nanostructures. The Nanocenter is bringing some new perspectives in
molecular constructs and some new perspectives in the fabrication of nanoscale
structures. I will describe the overall program and I will provide an overview of some of
these perspectives.

Charge transport in molecular wires

Hong Guo
Center for the Physics of Materials and Department of Physics
McGill University, Montreal, PQ, Canada H3A 2T8
Carrying out density functional theory (DFT) analysis within the Keldysh
nonequilibrium Green's function (NEGF) formalism, we have calculated nonlinear and
nonequilibrium charge transport properties of various molecular scale conductors without
involving phenomenological parameters. In this talk, I will report our recent
investigations using the NEGF-DFT formalism, on resistance of several molecular wires,
and compare our results with the corresponding experimental data. Time permitting, I
will also report our preliminary results on calculating switching speed of molecular
tunnel junctions when a pulsed bias is applied to an electrode.

Molecular materials and devices

Cherie R. Kagan
IBM T. J. Watson Research Center
Yorktown Heights, NY 10598
Efforts to fabricate devices based on active molecular components have been
driven by both the fundamental interest in using chemistry to build function at the
molecular level and the looming technological expectation of the end of Moores law. In
this talk, we describe the directed assembly of organic and metal-metal bonded
supramolecular systems that are interesting materials for potential electronic and memory
device applications. Molecules are chosen with head groups that bind to metal or oxide
surfaces and tail groups that bind to metal electrodes or that template the growth of the
particular molecular system. Optical spectroscopy, scanning probe microscopy, and
electrochemistry are used to characterize the chemistry and physics of molecular
assemblies. We incorporate these molecular systems in nanometer scale device test
structures aimed at understanding the electronic characteristics of two- and three-terminal
molecular devices.

Gated transport in single crystal organic semiconductors

probed with elastomeric stamps
John Rogers
Department of Materials Science and Engineering
University of Illinois at Urbana-Champaign
Physical lamination of organic crystals against elastomeric elements that support
gate electrodes, gate dielectrics and source/drain electrodes produces high performance
transistors in a manner that avoids exposing the fragile crystals to any form of
conventional processing. Van der Waals forces drive this completely reversible soft
contact lamination process. We describe a range of results, including temperature
dependent measurements of field effect mobilities that reach 32 cm2/V-s in p type
rubrene and 1.6 cm2/Vs in n type TCNQ. We also present data that reveal large
anisotropies in the transport in the a-b plane of rubrene crystals.

Spectroscopic probes of molecular junctions

Xiaoyang Zhu
Department of Chemistry
University of Minnesota, Minneapolis, MN 55455
Charge transport at or across molecule-electrode interfaces is central to the
operation of a wide variety of molecule-based devices. The critical charge transporting
interfaces in most systems are buried interfaces which are not readily accessible to
conventional structural or spectroscopic probes. For any given device, two critical
questions are: (1) What is the structural and chemical nature of the molecules at the
buried interface? (2) How is the electrical conductance across an interface related to
physical properties such as electronic energy level alignment and charge redistribution?
My lab is addressing both questions in spectroscopic experiments. The first experiment
relies on attenuated total internal reflection spectroscopy to establish the structure and
conformation of molecules at buried interfaces. The second experiment probes electronic
structure and electron transfer rates at molecule-metal interfaces using femtosecond timeresolved two-photon photoemission spectroscopy. These experiments are starting to
provide molecular insights into molecular electronics.

Modeling conduction through photoswitching molecules

Otto F. Sankey1, Jun Li1, Gil Speyer2
Department of Physics and Astronomy
2
Department of Electrical Engineering
Arizona State University, Tempe, AZ 85287-1504
1

We study theoretically a model photochromic molecule (dithienylethene

derivatives) which can switch from an off state to an on enhanced conductivity state
by the application of light. The light-induced intra-molecular conformation conversion
drives a swapping of the HOMO-LUMO molecular orbitals between the two distinct
conjugated structures. The shuffling of single and double bonds after conversion
produces a significant change in the single molecule conductance when the molecule is
sandwiched between metal electrodes. We model the switching event using quantum
molecular dynamics and the conductance changes using Green's function electronic
transport theory. We find large on-off conductance ratios (between 10 and over 100)
depending on the side-group outside the switching core.

Valence electronic structure of phenylene-ethynylene oligomers

Roger van Zee
Process Measurements Division
NIST, Gaithersburg, Maryland
The electronic structure of phenylene ethynylene oligomers chemisorbed on gold
have been studied using photoelectron spectroscopy and optical absorption spectroscopy.
In one series of experiments, the number of phenyl rings was varied from a single ring to
three rings in unsubstituted phenylene ethynylene-thiol oligomers. This provides a
qualitative picture of the extent of perturbation of the electronic structure caused by thiol
coupling and the changes to the molecular levels important for electron transport with
length. In another study, the effect of substitution on the middle ring was investigated.
Shifts that scale with the electronegativity of substitutent were observed. Finally, the
effect of the molecular linker was investigated by substituting isocyanide for thiol. This
change led to a shift of the occupied state of the molecule without significantly changing
its overall electronic structure. Together, these data begin to give a picture of the effects
of linker-group, substitution, and metal-molecule coupling chemistry on electron
transport through these model systems.

TBA
Jie Han
NASA Ames

Electrical transport properties of nanoscale molecular junctions

Theresa Mayer, Lintao Cai, Marco Cabassi, Thomas Mallouk,
Yoram Selzer, and David Allara
Department of Electrical Engineering
Pennsylvania State University
This talk will present temperature-dependent current-voltage characteristics and
inelastic electron tunneling (IET) spectra measured using sub 40-nm diameter in-wire
metal-molecule-metal junctions containing oligo-(phenylene ethynylene) (OPE)
molecular wires and their NO2 derivatives (NOPE). The in-wire junctions are
synthesized by replicating the pores of polycarbonate mesoporous membranes using
sequential electrodeposition and molecule self assembly steps. Following synthesis, the 5
m long nanowires are released from the membrane and electrofluidically aligned
between pairs of lithographically defined large area electrodes. Room temperature
electrical measurements on junctions containing these and other molecular wires such as
oligo-(phenylene vinylene) (OPV) show differences in conductance that are expected
based on their differing molecular structure. In particular, the current of OPV is
approximately one order of magnitude larger than that of the OPE and NOPE junctions.
IET spectra were obtained by cooling these junctions to 10 K and collecting the second
harmonic of the current as a function of bias using a digital lock-in amplifier. Several
predominant peaks were observed at positive and negative biases for the OPE and NOPE
junctions, which further confirm that our in-wire junctions are free of process induced
artifacts and can be confidently used to study transport mechanisms in metal-molecule
junctions.
The authors would like to acknowledge the Tour group (Rice University) for
providing the molecules used in this study.

Intrinsic electron conduction mechanisms in molecules

Wenyong Wang, Takhee Lee, and Mark A. Reed
Departments of Electrical Engineering and Applied Physics
Yale University
Electron devices containing molecules as the active region have been an active
area of research over the last few years. This talk presents measurements in a variety of
molecular systems to elucidate the transport mechanisms, specifically in self-assembled
monolayers (SAMs) using nanometer scale devices. Detailed kinetic studies are
necessary to distinguish between different conduction mechanisms; for example, in
alkanes temperature-independent electron transport is observed, proving tunneling as the
dominant conduction mechanism when defects are eliminated from the device structure.
This is distinct from Langmuir-Blodgett films, where only defect or filamentary
conduction has been observed. From the bias-dependence of b, a barrier height FB of 1.39
0.01 eV and a zero field decay coefficient b0 of 0.79 0.01 -1 are determined for
alkanethiols. Inelastic electron tunneling spectroscopy of the molecules in the junction
exhibits well-defined modes of the molecules in the junction, and yield a measurement of
the intrinsic linewidths of these modes. Deviation from this classic behavior for more
complex molecule structures, and a comparison of the differences and pitfalls of various
fabrication and characterization approaches, will be discussed.

What can we learn about electronic interfaces from single molecule measurements?
Stuart Lindsay
Department of Physics
Arizona State University
Single molecule measurements, with molecules attached to electrodes in a
reasonably well-defined way, leave no wiggle room for comparison with theory because
the number of molecules, their geometry and (hopefully) the attachments are defined. In
a number of cases investigated to date, the behavior of small molecules in which ballistic
transport dominates appears to be well described by theory. More challenging are cases
where intrinsic molecular properties might play a role, for example redox-active
molecules and photo-excitable molecules. I will outline some initial results with
electroactive and photochromic molecules.

Alkane monolayers: Temperature dependent tunneling

and template-stripped surfaces
Duncan Stewart
Quantum Structures Research Initiative Department
Hewlett-Packard Laboratories
I will discuss two related topics. First, I will show temperature dependent
transport through alkane monolayers sandwiched between upper and lower platinum
electrodes. The transport shows a large low-bias conductance anomaly and an anomalous
exponential temperature dependence. The exponential dependence can be partially fit
with two models: a standard thermionic field emission model with anomalous parameters,
or a less-conventional but general vibrating tunnel barrier model that can be associated
with thermal molecular vibrations. Second, I will describe AFM and STM physical
characterization of atomically-flat template-stripped platinum surfaces, and IR
spectroscopy of alkane monolayers self-assembled thereon.

Theoretical principles of single-molecule electronics:

A chemical and mesoscopic view
Yongqiang (Alex) Xue
Department of Chemistry
Northwestern University
The recent surge of activity in molecular electronics represents the convergence
of the trend of top-down device miniaturization and the progress in bottom-up singlemolecule manipulation and supramolecular self-assembly techniques. Detailed
understanding of the electronic and transport properties of single-molecules contacted by
electrodes is crucial for the development of this emerging technology.
In this talk, we summarize our understanding of the physical principles involved
in the operation of single-molecule devices. Our analysis is based on the extrapolation of
the concepts and techniques of mesoscopic physics into the molecular regime. We
emphasize insights obtained using a real-space microscopic theory which combines
rigorous transport theory with atomic-scale description of electronic processes within the
molecular junction. Key concepts are introduced and illustrated with detailed microscopic
studies regarding the nature of electron transport at the ultimate limit of device scaling
and the prospect of device design through bottom-up atom engineering. We conclude the
talk discussing some open issues and pointing out new directions in molecular
electronics.

Apparent conductance of molecular nanojunctions:

Roles of surface topography and metal contacts
Nikolai Zhitenev
Bell Laboratories
Lucent Technologies
Systematic conductivity measurements of nanoscale junctions containing selfassembled monolayer of conjugated molecules are carried out for a variety of metal
electrodes. The monolayers are assembled on 25-100 nm electrodes. Another 10-100 nm
electrode is defined on top of the monolayers by metal evaporation through apertures.
Unexpectedly, the characteristic energy scales of the dominant conductance channels are
small in comparison with the molecular level spacing. In all cases, the dominant room
temperature conductance is hopping with characteristic energy of the order of 10-100
meV determined by the nature of metal contacts. Relative contribution of tunneling
conductance strongly depends on the surface topography of the metal electrodes. For
smallest junctions assembled on a single grain of metal electrode, the direct tunneling
through the molecules is negligibly small. In the case of multi-grain junctions, tunnel
conductance is observed with low-energy Coulomb-blockade features.