J. Phys. Chem.

C 2007, 111, 4431-4444 4431

Analyzing Molecular Current-Voltage Characteristics with the Simmons Tunneling Model:

Scaling and Linearization

Ayelet Vilan†
Ilse Katz Center for Nanotechnology, Ben Gurion UniVersity, Israel
ReceiVed: October 18, 2006; In Final Form: December 31, 2006

Use of the Simmons model for analyzing tunneling transport across molecular junctions is reviewed, and its
inherent limitations are examined, specifically for cases where there are no molecular length-dependent data
(to extract a decay parameter), be it for experimental reasons or because of changes of the molecular energetics
or packing with molecular length. The potential barrier across a molecular junction is shown to be strongly
bias-dependent, much more so than is assumed in the commonly used version of the Simmons model. The
means to distinguish true tunneling from conduction via pinholes (or hot spots) are also considered. Power
expansion to the Simmons model shows that I/V vs V2 plots should be linear over that range, thus providing
a simple and standardized parameter extraction. From such plots, we can extract values for the equilibrium
conductance and for the “shape factor”, a complementary parameter that describes the shape of the I-V
relations. The applicability of these two parameters for describing actual transport is illustrated by analyzing
data for three different types of molecular junctions. The linearity of the I/V vs V2 plots can be used to
evaluate if, and if so, at which bias (and if at all) direct tunneling occurs and under which conditions this is
not the case. The extracted equilibrium conductance and the “shape factor” provide an empirical method for
quantifying electronic transport across practical molecular junctions where the exact packing of the molecules
is rather uncertain. As such, the analysis can be used to weigh and classify the effect of chemical modifications
to molecular junctions or compare contacting methods, so as to allow a deeper understanding of transport via
molecular junctions.

1. Introduction nominal molecular structures, ignoring possible structural

Molecular electronics is a fascinating scientific frontier, which
already has demonstrated proof of concept for such phenomena
as rectification,1 negative differential resistance,2 and others.3
Yet, basic understanding of electronic charge transport across
molecular systems is still rudimentary. One basic question is
that of structure-function relations,4 viz., which of the junction’s
parameters (e.g., conjugation, position, density and symmetry
of energy levels, bonding to the electrodes) affect the current
and to what extent?
An extreme example for a seemingly minor structural change
corresponding to a huge functional effect was given by Tomfohr
and Sankey5 for alkyl thiols on gold. On the basis of complex
band structure calculations, they showed that varying the
adsorption position from a hollow lattice site to an on-top Au
atom site shifts the HOMO level of the adsorbed molecule by
∼1 eV, which is expected to exponentially affect the molecular
conductance.5
Although this is only one example of what is nowadays a
very significant endeavor,6-9 transport modeling and simulations
generally rely on extremely well-defined atomic spatial posi-
tions, far beyond our experimental accuracy. This is important
because, although it is accepted that charge transport across
molecular junctions is dictated by both the spatial structure
(thickness, uniformity) and the energetics (energy levels and
effective mass or coupling), analyses of molecular current-
voltage (I-V) curves most commonly rely on schematic,
† Present address: Department of Chemical Research Support, Weizmann
Institute of Science, Rehovot, 76100 Israel.
10.1021/jp066846s CCC: $37.00 © 2007 American Chemical Society
Published on Web 02/28/2007
uncertainties (predominantly pinholes).
Indeed, although the example, given above, suggests that
chemical control over the exact binding site can have far-
reaching implications for molecular electronics, it is still an
elusive goal. We would like to devise and perform sets of
experiments to measure current-voltage (I-V) characteristics
that respond in a controllable and reproducible manner to a
controlled change in conditions. However, even if this is
achieved, the experimentalist still faces the problem of how to
quantify the observations and assign them to specific functional
properties such as energy level positions (which dictate the
barrier height), carrier delocalization (or coupling between
energy levels), or, for molecular monolayers, defect density,
something that may well affect not only the energy levels but
also the contact area for transport.
The limited knowledge on the exact molecular arrangement
in actual molecular junctions impedes the use of accurate
theories for quantification of experimental measurements.
Furthermore, reducing detailed theoretical models into few
averaged characteristic parameters (e.g., barrier height or
effective mass) enables decomposing experimentally measured
current-voltage (I-V) curves into a few basic parameters.
Therefore, approximate, effective models are at present a
necessary step for quantifying the increasing amount of mo-
lecular transport data.
Within the largely accepted simplifications of nonresonant
tunneling and that of the WKB (semiclassical) approximation
to nonresonant tunneling, one of the most ubiquitous of such
parameters is the decay parameter (β)10-12 (in Å-1, see equations
4432 J. Phys. Chem. C, Vol. 111, No. 11, 2007
a1 and a2 of the Appendix).13 This parameter describes the
exponential decay of the current, I, with the length of the
molecule (l): I ∼ exp(-βl). A major disadvantage of the decay
concept is that it requires a set of data with systematically
varying tunnel barrier width (molecular length), while keeping
all other molecular parameters the same. Practically, such a
strategy is limited mostly to simple alkyl chains and related
molecules, because, if functional groups are introduced (e.g.,
conjugated moieties, polar groups, redox centers), some variation
of energy levels or change in packing with molecular length is
nearly inevitable.
Alternatively, measuring current as a function of temperature
can be very informative. It can tell if transport is thermally
activated (pure tunneling is temperature-independent) and, if
so, what is the activation energy.14,15 This is a factor that needs
to be considered in the choice of experimental measurement
setup, as several types (e.g., Hg drop and electrochemical
junctions) allow only very limited temperature variation.
Furthermore, monolayers can undergo a liquid-solid phase
transition16 which can naturally influence their charge transport
characteristics. Other molecules, such as proteins, are mostly
incompatible with vacuum or dry conditions required for
cooling, again limiting the range of temperature variation
experimentally.
The question that we will address here is the following: Can
we extract from experimental current-voltage characteristics
functional parameters that allow meaningful comparisons
between experiments, in a way that is independent of tunnel
barrier thickness, i.e., without the need for experimental
current-thickness relations?
In molecular electronics8,9,14,17-21 Simmons’ inelastic tun-
neling model22-24 (see section 2 for a summary) is used often,
due to its simplicity, even though, in most cases it is likely
oversimplified as it ignores important contributions such as
super-exchange17,21 or hopping.9,25 Fitting the Simmons model
to I-V data (instead of I-l, current-thickness data) was found
to be useful for evaluating the contribution of chemical
modifications at bilayer interfaces17 and was shown to produce
parameters in good agreement with I-l extracted parameters.14
Wang et al. also reported on negligible temperature dependence
of the measured current, indicating transport by tunneling rather
than hopping14,15 (on tunneling vs hopping see also ref 25).
Aswal et al. distinguished between three different bias ranges
(low, medium, and very high), using simplifications for each
of these ranges.20 The present work focuses on the intermediate
bias range.
However, as noted by Cui et al.18 and Wang et al.,14,15 fitting
over different voltage intervals yields quite different results. A
discussion on the problematic interdependence between the
different parameters controlling the Simmons relations was given
in ref 26. In addition, our own experience27 shows that a visually
reasonable fit to the Simmons model can be reached fairly easily,
but the resulting extracted parameters are extremely unstable
and sensitive to the initial choice of starting values. Such
parameters can hardly be regarded as “characteristic”.
This is the reason for reconsidering the limitations inherent
in, and the possibilities for using, the Simmons approach (2.1).
We can understand the problem of multiple fits of the Simmons
relations to a data set, within which no length-dependent data
are available, by using a “scaled” analysis (2.2). The idea is to
separate between the magnitude of the current (2.2.3) and the
shape of the I-V curve (2.2.2). The magnitude is character-
ized by the equilibrium conductance, G0 (in Ω-1), rather than
by an absolute current value (in Ampere, at a specific bias).
Vilan
The shape of the I-V curve is characterized by a parameter
which we will call the “shape factor” (F), the ratio between the
width and the height of the tunneling barrier. These para-
meters reflect the product of the height and the width of the
tunnel barrier, which dictates the current magnitude, G0,
(see section 2.2.3, below) and the ratio between these two, (F),
which dictates the shape of the I-V curve (see section 2.2.2).
Note that G0 and F are functional parameters within which are
contained several physical parameters, such as the junction’s
barrier height, width, and contact area. In this manuscript, we
will occasionally refer to them as lumped parameters so as to
contrast them to the more familiar parameters that describe the
junction.
Although the combination of these two parameters enables
us to unravel the known coupling between barrier height and
effective mass,18 we show that this is possible only if the contact
area is known or if data with systematic length variation are
available (i.e., at least one spatial parameter is required). Another
basic limitation of the Simmons model is the fundamental
assumption that the potential profile across the molecule(s)
between the electrodes is linear (section 2.1). We show, for three
quite different experimental data sets, that this so-called “linear
model” is not applicable to real systems (4.1). We suggest that
this problem can be overcome by limiting the analysis to low
bias voltages, because at those voltages such a linear potential
profile is mostly a reasonable approximation (2.3.1). This
approach has as further benefit that a much simpler polynomial
I-V relations result (2.3.2) along the lines originally suggested
by Simmons24 and used later by Brinkman et al.28
Both the scaled analysis and the polynomial approximation
converge to the same characteristic magnitude and shape
parameters (2.3.3 and 2.3.4). The proposed analysis is tested
for analysis of I-V data measured across junctions of alkyl thiols
at three very different contacting configurations (3). Alkyl chains
are by far the cleanest and most reproducible of all molecular
junctions and thus serve as a basic model system for molecular
electronics studies. In addition, tunneling is expected to dominate
charge transport across alkyl chains.14 Extracting characteristic
parameters from actual data is tested (4.2) and compared to
traditional numerical fits (4.3). Finally, it is shown that a model
which allows for a slightly nonlinear potential profile provides
an excellent fit over the full bias range (4.4).
The discussion section reviews the possible merits in using
the lumped parameters under typical experimental conditions
where the junction area29-31 and width are not well-known. In
cases of a roughly known contact area (within an order of
magnitude), the product β0l can be extracted from G0, and the
ratio (β0l/F) provides the barrier height. Alternatively, if length-
dependent data (I-V-l) are available, we show that the intercept
of ln(G0·F) vs F plot can be used to extract experimentally the
contact area, A, of a molecular junction.
2. Revisiting the Simmons Model: Power Expansion,
Linear Presentation, and Scaling
This section starts with the formal definitions of the Simmons
model and its characteristic equilibrium parameters (2.1). Then
the full model is reduced to its commonly used linear form (2.2),
and, finally, a polynomial approximation to the Simmons model
is presented (2.3).
2.1. Basic Underlying Assumptions. The Simmons model
describes inelastic, nonresonant tunneling through an insulating
barrier and was formulated by J.G. Simmons in three successive
papers in 1963.22-24 This model has found wide acceptance and
use in the analysis of oxide tunnel barriers as well as barriers
Analyzing Molecular Current-Voltage Characteristics
Figure 1. Schematic illustration for different barrier types and
characteristic parameters. Barrier within the linear Simmons model
include the symmetric rectangular barrier (a) and the asymmetric,
trapezoidal barrier (b) where the variation of potential profile is linear
following eq 1 (dark and light gray for equilibrium and biased potential
profiles). Equation 1 is incorrect for nonlinear cases such as image
force lowering (c) or traps within the barrier (d). The averaged potential
is given by φ, and its equilibrium value (φ0) for the linear cases (a and
b) equals to the average of the difference in work function at the two
interfaces (eq 1). Panel e illustrates the characteristics parameters of a
rectangular barrier: dimensionless thickness (βl) and the equilibrium
barrier height (φ0). High and low shape factors (F ) β0l/φ0) are
demonstrated on the two rows of panel e (constant φ0 at each column).
The width ratio (R ≡ L/l) is shown on the top-right barrier: L is the
width of the potential barrier above the Fermi level, which can be
narrower than the molecular length (l) due to packing tilt or more
fundamentally due to, e.g., image force lowering (c) or contact
resistance.
formed by molecular films, since the very early days of this
field32,33 and also recently.14,17,18 The underlying assumptions
of the model are essential for defining the range of conditions
over which it can be applied and its limitations, viz.
• the potential is spatially averaged (2.1.1) and
• the potential varies linearly with space and applied voltage
(2.1.2).
We discuss both these assumptions next.
2.1.1. AVeraged Potential. The Simmons model is based on
averaging the potential-thickness profile of the tunnel barrier,
ψ(V,x) resulting in a single characteristic parameter, which is
the averaged barrier potential, ψ h (V). The “Simmons view” of a
potential barrier for tunneling is shown schematically in Figure
1a,b where the dark and light gray depict the barrier at
equilibrium (V ≡ 0) and under arbitrary applied bias, respec-
tively. The averaged potentials for the two cases (φ0 and φ(V),
respectively) are also shown. One consequence of the averaged
potential assumption is that asymmetry between the height of
the barrier at the two ends (Figure 1b) almost does not play a
role (as long as the bias does not exceed the smaller of the two
barriers). To account for asymmetry, Brinkman et al. revised
the Simmons model by integrating over transmission prob-
abilities rather than over the potential profile,28 allowing a direct
J. Phys. Chem. C, Vol. 111, No. 11, 2007 4433
expression of asymmetry in the barrier height. The price is a
significantly more complicated mathematical formulation.
2.1.2. Linearity of the Simmons Relations. The widely used
form of the Simmons relations (equation a3 in the Appendix)
represents only a special case of the general Simmons model.22
This form is based on two very stringent assumptions:
1. The potential profile is spatially linear, meaning that it
has either a rectangular or a trapezoidal shape, for symmetric
(Figure 1a) and asymmetric (Figure 1b) electrodes respectively.
2. The applied bias adds linearly to the potential profile.
The formal form of the linearity requirement is written as
follows:
φleft + φright (Wleft + Wright)/e + V V
h)
ψ ) ) φ0 + (1)
2 2 2
where ψ h is the averaged potential, φ is the potential difference
(barrier height) at each electrode (left and right), W is the work
function, e is the electron charge, and the subscript 0 emphasizes
that this is an equilibrium (V ≡ 0) property.
Thus, the so-called Simmons model really is the “linear
Simmons model” as it is based on the assumption that the
potential profile is linear in space and responds linearly to
applied bias. A nonlinear potential profile was originally
included by Simmons for describing the effect of the image
force.22,23 Recently Hansen and Brandbyge used a parabolic
potential profile,34 as shown schematically in Figure 1c, to
improve modeling of experimental data. The first assumption
of averaging could be wrong for cases where traps contribute
dominantly to the transport, as considered by Probst35 and
schematically shown in Figure 1d.
Despite these limitations, the Simmons model has the great
merit of simplicity, whereas the alternatives mentioned above
have generally much more complicated mathematical forms.
Keeping this in mind, we will show how we can use the
Simmons model to analyze I-V characteristics to yield unique
parameters, while at the same time maintaining simplicity. To
achieve this, we will explore two independent approaches, that
of scaling (2.2) and linearization (2.3).
2.2. Scaled Nature of the Simmons Relations.
2.2.1. Modified Simmons Relations. The relation describing
the tunneling current (I) as a function of the applied bias (V)
originally defined by Simmons22,23 (see equation a3, Appendix)
includes five unknown barrier characteristics, namely:
• equilibrium barrier height (φ0)
• nominal barrier width (l)
• contact area (A)
• effective mass (m*)
• ratio of the barrier width over the molecular length (R)
However, mathematically there are only three distinguishable
parameters. One of these is obviously the barrier height (φ0),
which scales the voltage. Several alternatives can be conceived
of to define the other two parameters. As will be justified below,
we suggest rewriting the original Simmons relations (see
equations a3 to a5 in the Appendix) in the following manner:
I)
2G0φ0
Fφ0 - 2 {(
‚ 1-
V
2φ0 ) [ ( x )]
exp Fφ0 1 - 1-
V
2φ0
-
) [ ( x )]}
( 1+
V
2φ0
exp Fφ0 1 - 1+
V
2φ0
(2)
for |V | e φ0, where the three independent parameters are
• φ0, the averaged, equilibrium (V ≡ 0) barrier height
(eq 1 above)
4434 J. Phys. Chem. C, Vol. 111, No. 11, 2007 Vilan

• F, the equilibrium shape factor, defined as follows:

x x
4π 2m*m0e m*
F) Rl ) 1.025Rl (3)
h φ0 φ0

which (see equation a1 in the appendix) implies F ≡ β0l/φ0.

• G0 the equilibrium conductance, defined as follows:

e2 A 4π
G0 ) (
4πh R2l2 h
Rl x2m*m0eφ0 - 2 × )
4π
exp -
h x(
Rl 2m*m0eφ0 (4a) )
A
G0 ) 310 (Fφ0 - 2) exp(-Fφ0) (4b)
R2l2

(Fφ0 - 2)
G0 ) 325Am* exp(-Fφ0) ≈
F2φ0
Am*
325 exp(-Fφ0) (4c)
F

where h is Planck’s constant and e, m0, and m* are the electron

charge, mass, and effective mass, respectively. R is the ratio
between the true junction width (L) and the experimentally
known molecular length (l), as schematically shown in the top
right of Figure 1e (see section 2.2.4). The numerical coefficients
in the short forms have the following units: 310 in Ω-1 [Å/µm2],
325 in [Ω-1 V-1 µm-2], and 1.025 (eq 3) in [Å-1 V-0.5].
Note that both F and G0 (eqs 3 and 4) are by definition
equilibrium parameters as no bias term is included. Because,
by definition, Fφ0 ≡ β0l, eq 2 is equivalent to equation a4 in
the Appendix, the two products will be occasionally exchanged,
as (β0l) is a more familiar expression than (Fφ0).
2.2.2. Shape Factor, F. The importance of the shape factor,
F,36 is demonstrated schematically in Figure 1e, as the ratio
between the width and the height of the barrier.37 Figure 2a
illustrates the effect of varying F on simulated I-V curves for
junctions with constant β0l and G0. The dotted line (labeled G0)
reflects the simple Ohmic relation (I ) G0V), which provides
the current “magnitude”, and all curves converge to this curve
at very low bias. At higher bias, the tunneling current rises faster
than the Ohmic one, and the higher F is, the steeper the curve
is. The problem of using β0l and φ0 as parameters is illustrated
in the inset of Figure 2a, where we see a blown-up section of
three I-V curves for junctions with constant F and G0. Hence,
the inset shows that for a set of curves where β0l and φ0 differ
but their ratio (F) is constant, the I-V curves cannot be
distinguished visually, even at strong magnification (a range of
0.1 V is shown, at intermediate bias).
Varying F has a minor effect on the total G0, but this is
compensated for by having the contact area (A) vary between
250 and 700 µm2 (Figure 2a main panel) However, keeping
F constant and varying β0l (φ0) affects G0 exponentially. Thus,
the three curves in the inset to Figure 2a represent 13 orders of
magnitude change in contact area, A (this is equivalent to
keeping A constant and normalizing the curves by a 13 orders
of magnitude change in G0).
Figure 2a also allows us to illustrate visually the effect of
the term in braces of eq 2. That effect is expressed as the ratio
between any of curves I-IV and the dotted line, the asymptotic
Ohmic relation (G0). This behavior differs from that of the
common version of the Simmons relations (equations a3 and
a4 in the appendix) where the term in braces includes also a
Figure 2. Illustration of the scaled nature of the Simmons I-V relation.
(a) The effect of the shape factor, F on the shape of Simmons’ tunneling
I-V curves is demonstrated on simulated I-V curves of identical
dimensionless thickness (β0l ) 30) and varying shape factor, F and,
accordingly, varying barrier height, φ0 (numbers in brackets), i.e., F
(φ0): (I) 7.5 (4); (II) 10 (3); (III) 15 (2); and (IV) 20 (1.5). For all
curves, a constant equilibrium conductance was used, G0 ) 10-9 Ω-1
(meaning that the nominal contact area varied between 250 and 700
µm2). The dotted line marked as G0 gives the Ohmic relation (I ) G0V).
The inset shows the strong similarity between curves for systems with
constant shape factor (F ) 15) and varying barrier height (β0l). Shown
are a blow-up of curve III from the main panel and curves for two
systems with identical F and varying φ0, i.e., φ0 (β0l): (III) 2 (30); (V)
1(15); and (VI) 3 (45). In this case, the contact area varied between
170 nm2 to 17 cm2 to be able to keep the same G0 ) 10-9 Ω-1 (b and
c) Maps showing the sensitivity of numerical fitting process to the
choice of free variables. The gray level of a pixel represents the MSE
(mean square error, eq a9) between a “target” I-V curve and the I-V
curve, based on the parameters given in the X-Y coordinates for that
pixel. The third parameter is either the correct G0 (b) or the correct
A/L2 (c). The varying fitting parameters were the barrier height
(Y coordinate) and either the shape factor or dimensionless thickness
(X coordinate) for panels b and c, respectively. The choice of specific
coordinates is explained in the text. Maps of other combinations of
coordinates appear in the Suppl. Mater. (S2).50 The “correct” minimal
point is the central pixel. The gray levels are linear with log(MSE)
and normalized to the span of MSE, with white and black equal to
maximal and minimal MSE respectively. The fitting is derived by the
strength of the gradient along the variables’ coordinates. Thus, a
direction of low gradient (constant gray level) means large tolerance
for variation in this parameter. “Target” I-V data were calculated
from equation a4 (Simmons’ model) using φ0 ) 2 V, β0l ) 15, and
A/L2 ) 106.
Analyzing Molecular Current-Voltage Characteristics
strong contribution from the current magnitude, because the
argument of the exponent in eq 2 will be between 0 and 1, in
contrast to that of eq a4 which is close to β0l (and similarly for
a3). Thus, the name “shape factor” reflects both the “aspect
ratio” of the barrier (cf. Figure 1e) and the shape of the I-V
curve (cf. Figure 2.a). Furthermore, considering that to a first
approximation only the potential barrier is affected by the
applied bias and the kinetic energy of the electrons is rather
constant, it becomes clear that F, instead of the more common
β0 parameter, is the natural parameter for describing the bias-
dependent current transport. In contrast, β0 is the characteristic
length-dependent parameter, dictating primarily the magnitude
of the current.
2.2.3. Equilibrium Conductance, G0. The equilibrium con-
ductance (G0) is the first derivative of the current with respect
to voltage near 0 V (G0 ) dI/dV|V f0, see section 2.3.2). As
such it includes information on the current magnitude, as
demonstrated by the dotted asymptotic line in Figure 2a
(simulated I-V’s) and in Figure 3 (experimentally measured
I-V’s, see section 4 for details).
The use of G0 as a characteristic parameter is fairly com-
mon,12,18,21,26,38 though it was not related to analyses within the
Simmons model. The uniqueness of the G0 concept within the
Simmons model is that, in principle, it allows reducing the
number of numerically fitted parameters, by extracting G0 (from
a linear fit of the low-bias range) and then using G0 as a fixed
parameter in a subsequent numerical fit over the full bias
range.
This idea was tested by simulations shown in Figure 2b,c,
which are maps illustrating numerical curve fitting to the
Simmons model (eqs 2 or a4). First, a fictitious I-V data set
was constructed from eqs 2 or a4 with arbitrary junction
parameters. We then calculated the current (for the same voltage
array) for a large matrix of φ0-F values (with eq 2, assuming
that G0 is known, Figure 2b) or of φ0-βl values (with eq a4,
assuming that the contact area, A, is known Figure 2c), and the
mean squared error (MSE; see appendix A4) between the
new current array and the target current array was calculated.
These MSE values are shown as gray levels, where the φ0-F
(φ0-βl) matrices are used as X-Y coordinates.
Figure 2b shows that for a fixed G0 the numerical fit is very
sensitive to the shape factor parameter (the dark valley along F
) 7.5 in Figure 2b) and rather insensitive to the barrier height
(the weak vertical contrast along the F ) 7.5 valley in Figure
2b; vertical contrast reflects variation in φ0.
Figure 2c illustrates the common fitting approach,14,17,18,21
where the contact area (A) is used as a known quantity. In that
case, the convergence of the numerical search (Figure 2c) is
much sharper than for fixed G0 (Figure 2b), with a shallow
valley along a constant β0l value.39 The reason for this difference
between parts b and c of Figure 2 is that in Figure 2c we
optimize two properties: the current magnitude (dictated by β0l)
and the shape of the curve (dictated by φ0). In contrast, in Figure
2b, the magnitude of the current is almost completely accounted
for by the known G0, and the numerical search looks mostly
for the shape of the curve (up to the very fine differences as in
the inset to Figure 2a). As can be seen, F is by far the dominant
factor, and for each φ0, a complementary A value can be found
to give the same (constant) G0 (see eqs 4b and 4c, A varies
exponentially with φ0, if F is fixed).
The choice of the independent parameter on the X axis for
the two maps (Figure 2b, c) comes from this insight, and was
also verified by constructing maps for other possible permuta-
tions (see S2 of the Supporting Information), producing a
J. Phys. Chem. C, Vol. 111, No. 11, 2007 4435
diagonal valley (cf. orthogonal one in Figure 2b,c), which is an
indication for correlation between the two fitting parameters.
To summarize, Figure 2b shows that, although F is a very
robust characteristic of the Simmons I-V relations (for known
G0), φ0 becomes well defined only if we know the contact area
(A). Naturally, the question that remains is how well we know
the true contact area (see section 5.3).29-31
2.2.4. Width Ratio, R, and EffectiVe Mass, m*. Historically,
there was a direct translation from β0 (or F in our present
terminology) to the barrier height, as β0 included only universal
constants and the barrier height. However, attempts to fit
molecular I-V data with the Simmons model always encoun-
tered the problem that the experimentally measured currents
were larger than those expected theoretically.17,18,21 As can be
seen from substituting eq 4 into eq 2, the current scales
exponentially as well as inversely with the product Fφ0 (≡β0l),
so that the high observed currents correspond to a reduced value
for β0l. However, φ0 cannot vary much as it scales the bias
(see eq 2) or dictates the shape of the curve.
To compensate between these contradicting requirements to
fit to the experimental magnitude and shape of the I-V curve,
further parameters were introduced in β0 (F). Holmlin et al. used
an asymmetry parameter (R) to yield a reduced decay param-
eter.17 However, the work of Simmons22,23 does not provide
justification for such asymmetry effect (see eq 1 above). An
effective mass, smaller than the free electron mass that appears
in the original Simmons model, was introduced by Cui et al.18
They extracted a value of m* ∼ 0.16, in reasonable agreement
with theoretical calculations that were based on the spectrum
of the electronic states of the molecular wire.40
Another possible cause for a reduced F value is the uncertainty
regarding the actual width of the potential profile (L, shown
schematically in Figure 1c,e). Although L is the relevant
tunneling property, it can differ from the experimentally known
parameter, which is the molecular length (l), possibly modified
by the tilt (Figure 1e), if that value is actually known. This is
why we have interpreted R as a ratio of widths, R ) L/l. Such
reduction in effective width can be due to image force narrowing
of the potential22,23 (Figure 1c), to high contact resistance, which
considerably alters the shape of the potential profile,7 or to
significant molecule-electrode orbital hybridization at the
interfaces.41 Through-space, rather than through-bond, transport
can also reduce the actual width (L), compared to the nominal
molecular length (l) for tilted molecules10 (Figure 1e). The
presence of oxide layer on the electrode20 or of residual water
(a distinct possibility if the top contact is evaporated on a cooled
substrate, in the absence of a separate cold finger in the
evaporation chamber that is at a temperature, well below that
of the cooled sample) could lead to an actual thickness larger
than the nominal one.
Because of their different physical meanings, both R and m*
are used here, but it is clear that they are coupled and lumped
together in F. The two parameters contribute differently only
to the pre-exponent in G0 (eq 4b vs eq 4c), which is expected
to be negligible compared to the exponential term. Thus, whether
to interpret the data in terms of R or m* is a matter of choice,
as they cannot be distinguished based on analyses of experi-
mental I-V data in the frame of the Simmons model.
In summary, introducing the G0 and F as parameters allows
to fit experimental I-V data in such a way that one can sepa-
rate the magnitude of the current from the shape of the
current-voltage curve. The importance of this parameter couple
emerges also from the linearized analysis, as is discussed
next.
4436 J. Phys. Chem. C, Vol. 111, No. 11, 2007
2.3. Linearization.
2.3.1. Assuming a Linear Potential Profile near Equilibrium
is Justified. Section 2.1.2 above emphasized that the common
“Simmons model” refers only to linear potential profiles (eq 1,
Figure 1a,b). Similarly, using β2-V plots (for β extracted from
thickness dependent data, see, e.g., ref 18 and equation a2) relies
on the same linearity assumption (eq 1). It is, however, very
reasonable to assume that molecules (especially incompletely
conjugated molecules, the ones of most interest for analysis with
tunneling models) develop nonlinear potential profiles across
them (such as those of, e.g., Figure 1c,d), if only because of
their varying atomic composition or the spatial localization of
the molecular orbitals.
Nevertheless, even nonlinear profiles can be approximated
with the linear model over small intervals, such as near
equilibrium. Namely, we assume the potential varies linearly
with the applied bias (eq 1) and with negligible bias effect on
the net shape of the profile. Thus, linear (common) Simmons
model should properly be used only near equilibrium where,
for the small biases, quasiequilibrium conditions can be as-
sumed, instead of forcing it over a large bias range, where its
applicability will, to say the least, be questionable. Accepting
this logic, we can, with the small signal assumption, replace
the highly nonlinear eq 2 with its power expansion.24,28
2.3.2. Polynomial Approximation to the Linear Simmons
Model. In a paper24 lesser known than his later ones, Simmons
showed that eq a3 can be rewritten using a polynomial expansion
(with V/2φ0 as the expansion variable), to give
I = G0(V + CV3 + PV5 + ‚‚‚) (5)
Equation 5 can be further rearranged (ignoring the fifth order
term) to get a linearized presentation of experimental I-V data
I
= G0 (1 + CV2) (6)
V dependent information, we will now briefly consider how the
Thus, plotting I/V (the integral conductance) vs the square of
the bias will yield two functional parameters, G0 and C (see
eq 8.b below). Equation 6 is very similar to the parabolic
expression developed by Brinkman et al.28 but with two
significant differences, namely that eq 6 gives the integral
conductance (in contrast to the differential one in ref 28) and
the absence of a linear term in eq 6.42
The I/V vs V2 relations (eq 6) are expected to be linear, as
long as (1) the error in the power expansion is small; (2) the
averaged potential decreases as V/2 (linearity in bias, eq 1); (3)
the (low) bias has a negligible effect on the width of the barrier
(linear profile, see section 4.4); and (4) the asymmetry between
the barriers at the two sides of the junction is negligible.28
2.3.3. Relating Polynomial Coefficients to Barrier Param-
eters. The coefficients of eq 5 are directly related to those of
eq 2. The equilibrium conductance, G0, is identical (eqs 4). The
cubic coefficient (C) is closely related to the shape factor, F
( )
β0l + 3
F2 F2
C) ‚ 1- ≈ (7a)
96 β0l(β0l - 2) 96
where, for convenience, the dimensionless thickness, β0l, is used,
instead of Fφ0.
The expansion was continued until the fifth order (P)
coefficient, attempting to extract more independent information
(see section 4.3)
Vilan
-1 -2 -3
F4 β0l/15 - (β0l) - 3(β0l) - 3(β0l)
P) ‚ ≈ 0.3C2
2048 β 0l - 2
(7b)
However, practically, it was very difficult to extract a robust P
coefficient even from simulations. First, it is almost a direct
function of C (see approximated term in eq 7b, right-hand side),
and second, at small bias, the fifth order contribution is very
small, and at large bias, it is incorrect to approximate the original
expression (eq 2) by a power series (eq 5).
The approximated relations (right-hand side of eqs 7) follow
Simmons24 and Brinkman et al.,28 where it was assumed that
β0l . 2, which allows one to neglect all powers of β0l apart
from the highest one. Similarly, with this approximation also
the (Fφ0 - 2) term in the G0 expression (eq 4) reduces to Fφ0.
The β0l . 2 approximation is questionable for molecules, where
∼0.5 < β0 < ∼1 Å-1 and ∼15 < l < ∼30 Å are typical values,
which yield a β0l product that is not much larger than 2.
Nevertheless, the β0l . 2 approximation has a major merit that
it allows to extract F without knowing β0l (i.e., directly from
C), something that requires knowing the contact area, A (see
eqs a6 and a7). We will show later (section 4.2) that practically
the β0l . 2 approximation does not introduce large errors.
Equation 5 can be solved analytically, in contrast to eqs 2 or
a3-a5 that can be solved only numerically. However, the
accuracy of the approximation (eq 5) deteriorates as V f φ0,
and the fifth order parameter (P) is rather useless. Therefore,
from here onward, we shall consider only the graphical
extraction of G0 and C from plots following eq 6. The
polynomial coefficients can then be translated into junction
parameters (e.g., barrier height and effective mass or width ratio)
by combining eqs 4, 7a, and 7b (for a full glossary see S1 of
the Supporting Information).
2.3.4. Linearized Approach Combined with Thickness Varia-
tion. Even though the main purpose of our analysis is to find
ways to analyze I-V data from experiments without thickness-
linearized analyses discussed here can also be useful for data
sets that include length information.
The terms for G0 can be related to plots of G0 vs length
(l).18,21,38 Substituting for Fφ0 ≡ β0l in eq 4, neglecting the “-2”
term and rearranging we get
(
ln(G0l) ≈ ln 310
Aβ
R2 )
- βl (8a)
ln(G0F) ≈ ln(325Am*) - φ0F (8b)
where, as noted above, the units of the numerical factor 310 is
[Ω-1(Å/µm)2] and that of 325 is [Ω-1 V-1 µm-2].
Thus, for a system of varying barrier thickness, the decay
parameter (β0) can be extracted from the slope of a plot of ln-
(G0l) vs the molecular length, l, as is well-known. Yet eq 8
provides also an interpretation for the pre-exponential term (or
the intercept) of the semilogarithmic fit, which can be used to
extract the effective electrical contact area for transport, A scaled
by either β0/R2 or m*.
In eq 8b, the independent parameter is now the extracted one,
F, rather than the assumed length, l. A linear ln(G0F) vs F plot
indicates a constant barrier height that can be extracted from
the slope. The effective electrical contact area can be extracted
from the intercept as above. If the plot is not linear, it could
indicate that the barrier height varies between the different
junctions. Clearly eq 8b could be useful for cases where there
is uncertainty about the exact barrier width (Rl). It also allows
Analyzing Molecular Current-Voltage Characteristics
Figure 3. Curve fitting to typical molecular I-V data (a) single
alkyldithiol;18 (b) alkylthiol monolayer;14 and alkylthiol bilayer.27 Dots
represent measured data (diluted for clarity) and curves are different
fits to the Simmons model, including (I) full-range numerical fitting
with two free variables (gray line) (eq 2); (II) quasi-equilibrium
approximation (dotted line, eq 6; see Figure 4); (III) bias dependent
barrier width (green line, eq 9; see Figure 5); and (0) linear (Ohmic)
fit over 10 mV (dashed line). Because the measured interval for (b)
was 20 mV, the linear fit was done over the (50 mV range. The inset
to each panel shows a blow-up of the (30 mV range, except for (b)
where the inset covers the (200 mV range. The inset tables show the
fitting parameters for each curve: equilibrium conductance (G0 in nS);
barrier height (BH in V); shape factor (SF, in V-1); and decay parameter
(beta in Å-1). The width ratio (R) was unity for curves I and II, and
equals the following cubic polynomial for curve III: (a) R ) 1.00 -
0.03|V| + 0.23V2; (b) R ) 1.00 - 0.05|V| + 0.23V2; (c) RV>0 ) 1.00
- 0.03V + 0.31V2, and RV<0 ) 1.00 - 0.03|V| + 0.27V2. The nominal
thickness and contact area for the different junctions are
(a) l ) 17.6 Å, A ) 22 Å2; (b) l ) 18.2 Å, A ) 1600 nm2; (c) l ) 53.2
Å, A ) 50 µm2.
a direct extraction of the equilibrium barrier height (φ0), without
plotting β2 vs V (eq a2). A complementary test is a plot of F vs
l, which should be linear through the origin (eq 3). In the results
section (4), the expressions that have been derived here are tested
on three experimental data sets.
3. Experimental Section
The use of the proposed analysis approach is tested on the
well-studied Au/alkylthiol/Au system, prepared with different
contacting methods. Two of these junctions refer to published
data.14,18 The third set was measured using a “ready-made”
contacting method of gold flakes floated over pre-patterned gold
electrodes.27 It was added here to verify the generality of the
analysis.
Generally, alkyl molecular junctions are not expected to
benefit much from the proposed analysis approach, as their
length can be easily varied. However, they were chosen as a
J. Phys. Chem. C, Vol. 111, No. 11, 2007 4437
test case since these molecular junctions are well established
and the results of our test analyses can then be compared with
those obtained in a more conventional manner, from the length
dependence.
The first type of molecular junction was formed by a single
dithioloctane (HS-(CH2)8-SH), bound chemically on one side
to a Au substrate and on the other side to a Au nanoparticle.
The molecule is embedded in a monolayer of monothioloctane,
i.e., all of the other molecules are bound only to the Au substrate.
Transport was measured with a conductive probe atomic force
microscope (CP-AFM; Figure 2a of ref 18).
The second type of junction contained a monolayer of
a several thousands of monothiol dodecane molecules,
(HS(CH2)12H), chemically bound to a Au electrode, in a
nanopore configuration, with no chemical bond to the other Au
electrode, that was evaporated onto the nanopore structure
(Figure 5 of ref 14).
The last junction was formed by a bilayer of ∼108 monothiol
docosane molecules (HS(CH2)22H), with the bottom layer bound
chemically to lithographically patterned gold electrodes and the
top layer bound chemically to a micrometer-sized floated gold
flake.27 Further details on that system are given in the Supporting
Information (S4) and will also be part of a separate publication.
Graphical fitting, numerical searches, and simulations were
done using MATLAB software. The specific functions employed
are given in Appendix A4. The voltage array for simulated I-V
data ranged from -φ0 to +φ0, with steps of 1 and 10 mV below
and above φ0/10, respectively.
4. Extracting Characteristic Tunneling Parameters with
Revised Simmons Model
We will now review how we can extract characteristic
tunneling parameters from experimental current-voltage curves
of molecular junctions. We start by describing the problems,
inherent in how the Simmons model is commonly used (4.1).
We then introduce an alternative way to extract parameters from
near-equilibrium data (4.2). This approach can be expanded so
as to be applicable also to data, farther away from equilibrium,
either by finding bias-independent parameters that are valid over
the full measurement range (4.3) or by calculating bias-
dependent parameters (4.4).
4.1. Fitting Experimental I-V’s Depends on Voltage
Range. Curve fits over part or all of the data ranges are shown
in Figure 3. In the three panels, we reproduce the experimental
I-V curves, which were measured for the three types of
molecular junctions, viz. single embedded molecule with two
chemicontacts18 (Figure 3a; “single molecule”), a small area
monolayer with one chemicontact (∼104 molecules per junction;
“monolayer”)14 (Figure 3.b), and a large area (∼108 molecules)
bilayer junction, with chemicontacts to the electrodes but not
between the monolayers27 (Figure 3c; “bilayer”).
The dots in Figure 3 are the experimental data, and the lines
represent fits to these data. The common numerical fit over the
full bias range is labeled “I” (gray solid line, see section 4.3
for details on the fitting). The insets to each panel are
magnifications of the low signal range, showing a sever
disagreement between this numerical fit (I) and the data at this
low bias range (as well as at very high bias, except for 3b).
Limiting the fitting range to a (0.1 V (II, dotted line, parameters
were extracted from the fitting of Figure 4 discussed next, yet
similar fits were received also by common numerical search)
produces a good fit over that range, which strongly deviates at
higher bias. This problem was noticed already by Wang et al.14
and by Cui et al.18
4438 J. Phys. Chem. C, Vol. 111, No. 11, 2007 Vilan

Clearly the graphical differences between fits to different bias

ranges translate into considerably different tunneling parameters
corresponding to these fits, which are given in the Tables that
appear as insets to Figure 3. Such parameters are thus not unique
and change with the choice of bias range for the fits. In the
following sections, we present alternative ways to extract
characteristic parameters.
4.2. Extracting Equilibrium Parameters using Power
Expansion. This is a practical implementation of sections
2.3.2 and 2.3.3. Generally one can use eq 5 with increasing
degree of complexity to extract more information from
the data. Fitting to only one coefficient, i.e., imposing linearity
on the I-V relation (I ≈ G0V) is the well-known equilibrium
conductance approach.12 This approach is presented by the
dashed lines (“0” numbered) in the main part of Figure 3.
Clearly, G0 is the most robust parameter (cf., G0 values in the
tables that appear as insets to Figure 3 and Tables s2-s4 in the
Supporting Information). Unfortunately, it contains only infor-
mation on β0l (≡Fφ0; eq a7 of appendix). If more information
is needed, we need to find ways to extract more parameters
from the data.
Imposing cubic relations (eqs 5 and 6) on the I-V’s pro-
vides G0 and C, and with the knowledge of contact area
(A, for which an approximate value will suffice) allows
extracting two parameters: β0l and F (eqs a6 and a8, respec-
tively). The barrier height (φ0) is the ratio between these
parameters (β0l/F) and can be extracted without knowing the
exact barrier width (l). Note that the translation of G0 into β0l
relies on knowing the contact area (A). We checked if it is
possible to use the fifth order parameter (P of eq 5) to provide
one more experimental parameter, which would allow extracting
β0l independently of A. Yet, as explained in section 2.3.3 above,
and confirmed by simulations, mathematically this is not
possible.
The cubic relations can be presented in a linearized manner
by plotting I/V (the integral conductance) vs V2 (eq 6). Figure
4 shows a linearized presentation of the data (symbols) from
Figure 3, where the lines are linear fits to the data. This
linearization shows clearly the relevant fitting ranges, or
“quasiequilibrium” regions,43,44 which can vary from junction
to junction. For example, the monolayer (Figure 4b) shows some
asymmetry in the I-V since the forward bias (black dots) and
reverse bias (gray dots) data are slightly shifted. For a first
approximation, these differences were ignored and the linear Figure 4. Linearized presentation of molecular I-V data (a) single
fit considers all data. For the bilayer (Figure 4c), the asymmetry alkyldithiol;18 (b) alkylthiol monolayer;14 and (c) alkylthiol bilayer.27
was fairly large, and in this case, the reverse bias data were As emerges from the power expansion (eq 6), a plot of the (integral)
omitted for clarity. Furthermore, this junction shows a clear conductance (I/V) against the squared bias (V2) should be linear for
low enough bias. The black and gray dots represent data measured in
change of slope at ∼175 mV (0.03 V2). The definition of the forward and reverse bias, respectively, and lines are linear fits. In panels
proper fitting range was somewhat questionable also for the a and c, two slopes are evident and expressed by two fitting lines.
single molecule data (Figure 4a), where there is a fairly steep The linear coefficients are: (a/I) G0 ) 9.33 × 10-10; C ) 35.4; (a/II)
slope at very low bias (<80 mV), which becomes more G0 ) 9.74 × 10-10; C ) 11.0; (b) G0 ) 4.35 × 10-9; C ) 10.7; (c/I)
moderate at higher biases (80 < V < 250 mV). G0 ) 1.26 × 10-7; C ) 15.3; (c/II) G0 ) 1.75 × 10-7; C ) 1.35.
The coefficients C and G0 of the fits to Figure 4 were
translated into barrier parameters (using eqs a6 and a8) by junction the extracted β0 ()0.84) reproduces fairly well the
assuming a potential width that equals the molecular length published results,14 whereas for the other two junctions
(i.e., R ≡ 1, and literature values for molecular length) and (Figure 3a,c), β0 was ∼0.4, much lower than the published
the nominal (geometric) contact area (A, for alternatives see value18 and also well below the values for alkyl chains,
Table s1 of the Supporting Information). The corresponding commonly extracted from length-dependent data. Interestingly,
barrier parameters were inserted into eq 2 to produce the dotted notwithstanding the very different contacting environments of
curves (labeled II) in Figure 3. the single molecule and bilayer junctions, the linearized
The parameters extracted from the linearized presentation approach yields similar β0 values for these two types of
(Figure 4, eq 6) can be compared to those extracted using a junctions.
numerical fit, to check their reproducibility and robustness. As The quasi-equilibrium shape factors (F), extracted from the
can be seen from the inset to Figure 3b, for the monolayer data, were 38, 34, and 40 V-1 for the single molecule (line II
Analyzing Molecular Current-Voltage Characteristics
of Figure 4a), monolayer and bilayer (line I of Figure 4c)
junctions, respectively. These values could be up to 10 times
larger than the F, calculated from numerically fitting of data to
eq 2 over the full measurement range (curves I, see below).
The shape factor, F, can be extracted independently of an
assumed contact area, by using the β0l . 2 approximation. This
procedure generally yields only a few percent decrease in
F compared to the values given above, thus confirming the
validity of the extracted numbers and showing the scaled nature
of the analysis.
The extracted barrier heights (φ0) were 0.18, 0.46, and 0.52
V, and the extracted effective mass values (m*) were 0.83, 1.49,
and 0.27 for single molecule, monolayer, and bilayer junctions,
respectively. The resulting φ0 values are rather low compared
to what is commonly accepted (1-2 eV). We note, though, that
a 50% reduction in barrier height was also observed by Dorneles
et al., after accounting for the effective electrical contact area,
compared to the barrier height that was extracted, using the
nominal contact area.31 The extracted effective mass values are
reasonable, except for the monolayer, as m* > 1 for molecular
junctions is unusual, though recently m* ) 1.6 was reported
for Hg/alkyl thiols/GaAs junctions.45 Note that m* > 1 can also
be interpreted as R > 1, meaning a thicker barrier than what
was assumed in the analysis (although a narrower barrier than
what is assumed from physical measurements and modeling is
the more common scenario).
To overcome the need to know the contact area, we can try
to extract more information from the data (i.e., extract three
parameters), using a numerical fit to the original eq 2, as
described next.
4.3. Equilibrium Approach, Compared to Numerical Fits
over a Large Bias Range. The gray curves (I) of Figure 3
represent the common fitting approach,14,17 based on a (presum-
ably) known contact area (A), with φ0 and β0l (or m*)39 as two
free fitting parameters. This procedure also uses the full
measurement range for fitting.44 It gives a β0 value that is rather
similar to the one that is extracted at quasiequilibrium, reflecting
mainly the magnitude of the current. However, the barrier height,
extracted from fitting the data over the large bias range, is larger
than that extracted from quasi equilibrium data, expressing the
much slower increase in current at high bias (gray curves, I)
than that expected, based on the quasiequilibrium fit (dotted
curves, II).
The small change in β0 between the low and full measured
bias ranges suggests that β0 can be considered as a constant,
dictated by the current magnitude (G0, provided that A is
known). Thus, the fitting is mainly one of the barrier height,
and, instead of letting β0 vary freely it can be fixed to its value
extracted from G0 (extracted graphically from the data in a
preceding step). We tested such fitting procedure (see Tables
s2-s4 of the Supporting Information) and found only minor
differences between the parameters, extracted by optimizing
solely on φ0 or on both φ0 and β0l. We conclude that there is
no need for a numerical fitting approach to find β0 as it is a
direct function of G0 and A (cf. eqs a6 and a7).39
Alternatively, a known G0 can be introduced into the fitting
search, combined with φ0 and A as free fitting parameters (where
β0l ) f(G0, φ0, A)), to extract the contact area from the I-V
data. However, as shown in Figure 2b, in such case, the fitting
becomes very insensitive to the barrier height, which translates
into changes of orders of magnitude in the (now) extracted
contact area. For the single molecule junction such procedure
yielded a contact area of only 4 Å2 (cf. nominal alkyl thiol
footprint of 22 Å2, see Table s3 of the Supporting Information),
J. Phys. Chem. C, Vol. 111, No. 11, 2007 4439
which we consider as a reasonable accuracy. However, for the
monolayer junction, the extracted contact area was ∼3 nm2
(cf. nominal value of 1600 nm2), which could be taken as an
indication for defect-mediated transport. For the bilayer junction,
the numerical search completely diverged. We take this result
to reflect the inability of this fitting procedure, in this case, to
match the shape of the curve, if the current magnitude is dictated
by the value of G0, derived from the low bias fit. Interestingly,
despite this huge divergence, it was still possible to extract a
reasonable value for the shape factor, which again emerges as
a robust parameter. However, we find that, by limiting the bias
range over which we fit the data, we can extract a set of
parameters with a contact area of the order of a few defects in
the layer.
Low A values are accompanied by low β0 and φ0 values,
because G0 cannot change much since it reflects the current
magnitude (see eq 4). Considering which of the various possible
extracted parameters is the most characteristic one, it clearly
emerges that G0 is the most robust one. The variation in F
increases if high bias ranges are included, but considerably
improves if only low bias ranges are taken. The reproducibility
in β0 was similar to that in G0, but the conventional characteristic
junction parameters (i.e., the nonlumped parameters φ0, m*, A)
showed much poorer reproducibility.
As noted before, extending the voltage range toward
high bias could produce erroneous parameters simply be-
cause the linearity assumption does not hold there. The next
section considers the possibility of recovering the bias
dependence of the potential profile from experimental I-V
characteristics.
4.4. Potential Profile across a Molecular Junction is
Nonlinear. Information on the bias variation of the barrier
characteristics is of major interest18 and commonly expressed
as bias variation of the decay parameter, β (see eq a2, in con-
trast to the equilibrium β0 of eq a1). Engelkes et al. found a
bias-independent β parameter but a strongly bias-dependent
residual resistance (the reciprocal of the pre-exponential term
in eq 4).26 As described in section 2.1, the commonly used
version of the Simmons model assumes that the shape of the
barrier is linear, instead of a more realistic parabolic shape22,23,34
(see Figure 1, panels a and b vs c and d). In such a case, both
the averaged potential (ψ h ) and the barrier thickness (R(V)l) are
expected to vary with the applied bias (see eq a5). This variation
will be different from the linear dependence of ψ h predicted by
eq 1.
We will show now that accounting for the bias variation of
the barrier width (R(V)l) can produce a good fit to the data over
the full measured bias range, as shown by the green curves in
Figure 3 (an equivalent approach is to use ψ h (V) as a bias-
dependent parameter). The potential width-bias (R-V) relations
are extracted from the I-V data by assuming that all of the
other parameters of eq 2 are independent of bias and equal their
equilibrium values as extracted from Figure 4. This is done by
defining a bias-dependent shape factor F(V) ) R(V)F(0),
where,for simplicity, we assume R(0) ≡ 1. Substituting F(V)
for F into eq 2 yields
I)
2G0φ0
R(V) (Fφ0 - 2)
2 {(
‚ 1-
V
2φ0
×)
[ ( )] (
exp Fφ0 1 - R(V)
x 1-
V
2φ0
- 1+
V
2φ0
×)
[ ( )]}
x
V
exp Fφ0 1 - R(V) 1+ (9)
2φ0
4440 J. Phys. Chem. C, Vol. 111, No. 11, 2007
Figure 5. Bias variation of the width ratio (R) plotted for the monolayer
junction14 for different equilibrium barrier height (φ0 ) 1, 1.6, and 2
eV, see curve labels) and constant shape factor (F ) 10.1) (a); or
constant dimensionless thickness (β0l ) 16.16) (b). At each I-V point,
the width ratio was extracted by numerically solving eq 9 using
G0 ) 4.67 nS, and other parameters specified in the figure.
Thus, at each I-V data point, R(V) can be extracted by solving
(numerically) eq 9 for R(V). The results for such calculation
for the monolayer junction (Figure 3b) are shown in Figure 5.
The extraction procedure was repeated for several sets of
equilibrium parameters (reflecting a possible uncertainty in
β0l due to the fact that the actual contact area is not known, see
eq a7).
Figure 5 compares the shape of the R-V relations obtained
for three different barrier height values and either the same shape
factor (Figure 5a) or the same dimensionless thickness (Figure
5b). The figure shows that the R parameter varies by ∼6% with
the applied bias, which can be fit very well to a quadratic
parabola (on each side of |V| ) 0). Interestingly, this 6%
variation is equivalent to the error that Simmons predicted in
his model (eq a5) if the integration correction factor (termed
there β, yet equivalent to R in the symbols used here and
nowadays) is set equal to 1.22 Varying φ0 with a constant F,
changes only the scaling of the curve but not its shape (Figure
5a). In contrast, varying φ0 for fixed β0l drastically changes
the shape of the R-V curve (Figure 5b). The strong increase of
R away from equilibrium (for φ0 ) 1; Figure 5b), which reflects
a significant widening of the barrier, appears to be an artifact
due to an incorrect choice of β0l and φ0. This type of sensitivity
to F (≡β0l/φ0) further demonstrates the importance of F as the
characteristic parameter in bias-dependent analyses.
Vilan
Similar parabolic R-V curves were found for the other two
data sets, confirming the general behavior of a bias-dependent
potential profile. The green curves (III) in Figure 3 were
calculated from eq 9 using G0 and F values of curve II. However,
the low barrier height extracted for curves II could not be used
for fitting the whole bias range (note that both eqs 2 and 9 are
limited to V e φ0). In view of the insensitivity to the exact
barrier height, shown in Figure 5a, we arbitrarily set φ0 ) 1V
to allow fitting the whole bias range.
Figure 5 is thus a phenomenological proof that fitting
molecular I-V data over large bias ranges44 must consider
nonlinear potential profiles. Naturally, a meaningful parameter
extraction should rely on a physical model rather than use the
empirical approach employed in eq 9. A physical model could
be the detailed image force model by Simmons22,23 or the
parabolic model by Hansen and Brandbyge.34 Adding G0 as a
fitting constraint (see section 4.3, above) can be useful in
decreasing the large number of fitting variables in these
advanced models.
We will now discuss how we can use the quasiequilibrium
Simmons model, rather than the commonly used version, for
analyzing molecular I-V characteristics.
5. Discussion
5.1. Why Use the Simmons Model? We conclude from the
results presented in section 4 that formally the (linear) Simmons
model cannot describe real molecular current-voltage charac-
teristics. As reasons we note the lack of robustness of the
extracted barrier parameters and the inability to find bias-
independent parameters to cover all bias ranges, the low, near-
equilibrium, and the high bias one, far from equilibrium44
(Figure 3). This bias dependence (Figure 5) explains the
inadequacy of the linear Simmons model in describing charge
transfer via molecular junctions. This conclusion is a fairly
general one, as it was found for three very different molecular
junctions.
Because, at present, there is no convenient adequate alterna-
tive, we need to find ways to use the model, while being aware
of its limitation, rather than forego using it altogether and we
will do so in the following sections:
• The deviations from linearity at high bias can be taken care
of largely by limiting the range of fitting as will be discussed
in the next section (5.2).
• The critical issue of contact area will be addressed in the
following section (5.3).
• In the last two sections of this chapter, we suggest ways to
analyze the experimental transport data within the linear
Simmons model by using G0 and F as phenomenological
parameters (5.4 and 5.5).
5.2. Simplifying Parameter Extraction by Linear Presen-
tation of the Experimental Data. Presenting molecular I-V
data in the form of Figure 4, rather than as numerical fits to
eq 2 (cf. curves I in Figure 3), enables a simple visible evaluation
of the relevance of the model to a given experimental data set.
This is in clear contrast to the multiple possible solutions to
eq 2 shown in Figure 3. Hence, presenting molecular I-V data
as I/V vs V2 allows determining the bias range where the
Simmons model is relevant or identifying a change in conduction
behavior, as was evident for the bilayer junction (Figure 4.c).
Recently, Beebe et al. used a linearized presentation for Fowler-
Nordheim field emission transport to evaluate the onset of this
transport mechanism.43 The linear I-V presentation, suggested
here, completes this approach by covering the intermediate
range, between the linear behavior at very low bias and the
Analyzing Molecular Current-Voltage Characteristics
Fowler-Nordheim relations at very high bias, as used earlier
by Aswal et al.20 A transition to Fowler-Nordheim tunneling
will appear as curving down of the linear trend in a presentation
such as that shown in Figure 4. Applying this presentation to
the experimental data-sets tested here, reveals no transition to
field emission for the monolayer14 and bilayer27 junctions. The
single molecule junction18 does show a possible turning point
at V ∼ 0.4 V, which is just outside the scale of Figure 4a
(V2 ∼ 0.16). Indeed the data of Figure 4a start deviating below
the linear trend line at ∼0.06 V2.
The mathematical approximation (eq 5) is scientifically
justified as it follows directly from the assumption of a linear
potential profile (eq 1). If we limit the voltage range that we
use to extract parameters to low bias quasiequilibrium condi-
tions,44 we can compare consistently and in a standardized
fashion between different experiments. However, such limitation
leads to loss of important information regarding the bias
variation of the potential barrier. At the same time, extending
the linear assumption to bias ranges where the barrier depends
nonlinearly on the bias merely increases the inaccuracy of
extracted parameters (even if it appears to provide a visually
good fit; cf. curves I in Figure 3, see main figures vs insets).
Although the analysis of section 4.4 and Figure 5 is a
qualitative one, it shows clearly that the potential profile over
a molecule or over molecular layers is nonlinear, and not only
the barrier height but also the barrier shape varies with applied
bias. Therefore, analysis over a bias range beyond the near-
equilibrium range44 must account for nonlinearity, by either
using existing models or developing new ones. Such models
are naturally more complicated than the one expressed by eq 2
and require extraction of the parameters numerically. The
concept of separating the magnitude issue (using G0) from the
shape of the curve (using numerical search), as suggested here
can simplify the application of these models.
5.3. Do We Really Know the Contact Area? The ambiguity
regarding whether the charge transport is attenuated by the
length of the molecules or by the reduced contact area for
transport (e.g., via defects in the monolayer) has been a worry
for molecular (or monolayer) electronics since its early days29
and is relevant also for other fields that involve charge tunneling,
such as spintronics.30,31 Remarkably, though, the issue is not
considered in most molecular electronics publications, which
use the nominal (geometrical) area of the electrical contact.
Recently, Engelkes et al. tried to identify the actual contact area
in conducting AFM measurements of Au/decanethiol/Au junc-
tions. They found that the measured zero resistance (equivalent
to reciprocal G0, see eq 4) was insensitive to the diameter of
the AFM tip, suggesting that the current is confined to the
narrowest path between a rough protrusion of the substrate
electrode and the very end of the tip.46
The critical effect of the contact area on the extracted barrier
parameters is clear from Figure 2c, which shows the sharp
minimum if the data are fitted, using a known contact area, in
contrast to the shallow valley that we get if we fit, using a known
equilibrium conductance (Figure 2b). Allowing the contact area
to be a free fitting parameter for the monolayer and bilayer
(Tables s3 and s4 of the Supporting Information) results mostly
in values that are much smaller than the nominal one. The view
of a junction that is controlled by pinholes/defects is consistent
with the low barrier height (approximately tens of mV) that we
extract for fits that yield small contact areas, as such small
barriers are reasonable for two metals at very near proximity
(note, however, that the magnitude of φ0 and A decrease
J. Phys. Chem. C, Vol. 111, No. 11, 2007 4441
(increase) together if G0 is kept constant, as explained in section
2.2.2 and inset to Figure 2a).
This suggests that the result obtained, using the contact area
as a free parameter, has physical value. Nevertheless, our
confidence in the “pinholes” results is not better than in the
“nominal contact area” results, as there is not much difference
in the accuracy of the two numerical fitting approaches. This is
in contrast to the work of Dorneles et al., on Al/Al2O3/Al
junctions where the accuracy of the fit improved drastically if
the contact area was allowed to vary (i.e., three free fitting
variables).31 The difference in achieving a good fit could be
explained by that the behavior of the inorganic insulator fits
the Simmons model closer than does that of molecular barriers.
Possible deviations from the Simmons model are the major
problem, if one wants to distinguish between transport via
pinholes and tunneling across all of the area occupied by the
molecules, solely based on a single I-V data set. Thus, it is
critical to have an independent determination of the actual
contact area, which can be done in cases were also length-
dependent data are available, as described in section 5.5 below.
Even in cases where we have direct evidence for tunneling
from temperature-independent currents or inelastic electron
tunneling spectroscopy (IETS) that shows characteristic mo-
lecular vibronic modes involved in the charge transport,15,25,47
we cannot assume that the geometric (nominal) contact area is
the effective one for electronic transport. This was demonstrated
clearly for Al/Al2O3/Al junctions where the effective area for
electronic transport was found to be 5 orders of magnitude
smaller than the nominal contact area. This was explained by
arguing that the current flux was limited to “hot-spots” in the
insulator film. Transport across a “hot-spots” is still by tunneling
but the tunneling length is now much shorter, resulting in
exponentially higher conductance, and thus, most of the current
will flow there.31
5.4. Use of G0 and F as Phenomenological Parameters.
Figure 2, panels a and b, show that G0 and F, rather than β and
φ0, are the fundamental, independent properties characterizing
the Simmons tunneling model in terms of scaled relations
(magnitude and shape). Moreover, these parameters have a
natural presentation of data (Figure 4) allowing their linear
(analytical) extraction, without knowing any other parameters.
Extraction of the approximated F (i.e., F ) x96C, from eq a4,
with C defined in eqs 5-7) bypasses the contact area ambiguity,
discussed in the previous section (as it is independent of
β0l, which necessarily depends on A).
Wold and Frisbie12 already suggested G0 as a phenomeno-
logical characteristic parameter for comparing net current
magnitude. We propose that the shape factor, F can be used
similarly for comparative purposes, to indicate how fast the
current increases away from equilibrium. The physical meaning
of the equilibrium conductance (G0) is straightforward as it
scales exponentially with the effective tunneling length or
dimensionless thickness (β0l). The historical origin for allowing
F36 as a free parameter (equivalent to R or m* as a free
parameter) instead of being a fixed function of φ0 and l is that
the measured currents were higher than expected or the barrier
was narrower than expected.14,17,18
Clearly, transport across a barrier is affected by both the
barrier’s height and width (see Figure 1e). The “width” of the
barrier can be related to its geometrical width (l) possibly
narrowed by image forces22,23 or wave function hybridization41
(R) and to coupling between the molecular orbitals and the
electrode (m*). The barrier width scales the current exponen-
tially, with only minor bias dependence (slightly stronger
4442 J. Phys. Chem. C, Vol. 111, No. 11, 2007
dependence if a nonlinear potential barrier is assumed, see
Figure 5 and eq 9). This is in contrast to the effect of the barrier
height which directly varies with bias (eq 1). F reflects the ratio
of these two contributions, in contrast to the decay parameter,
β0 which is related to their product. Thus, the “heavier” the
charge carrier (m*) is or the wider the barrier (Rl) is, the larger
F is and the steeper the I-V curve is away from equilibrium
(Figure 2a). Increasing the height of the tunneling barrier will
have the opposite effect (smaller F and shallower, more linear
I-V).
This can serve as a partial answer to the introductory example
of how to interpret a set of systematic changes in a molecular
junction. If a systematic structural change leads only to an
increase in barrier height, it will be expressed as a decrease in
both F and G0 (increase in β0). However, if either the net
junction width or the effective mass increases, then F is expected
to increase while G0 should decrease (β0l increases). Naturally,
a combination of these effects will be more difficult to interpret.
If, by comparing a series of junctions, we find a constant
F (i.e., β0l is also constant) and a changing G0, this can indicate
that pinholes dominate conduction and that their density changes.
In addition, the linearized presentation of Figure 4 is a straight
forward tool for evaluating the bias range where the (linear)
Simmons model is applicable and for a possible change in
mechanism as indicated by the kink in Figure 4c.
The numerical values extracted here and presented in the
insert Tables to Figure 3 (and in Tables s2-s4 in the Supporting
Information) cannot provide an answer to the question what
are the junction parameters. Rather, they stress the ambiguity
in the extraction of these parameters. Nevertheless, we can
characterize junctions in an acceptable manner as described next.
5.5. Suggested Routine for Parameter Extraction. In view
of the discussion in the previous sections, I suggest the following
guidelines for analyzing molecular I-V characteristics:
(a) Predetermine the contact area by testing the specific
contacting method on a known molecular system of varying
length (e.g., alkyls), using eq 8a.
(b) Measure as many data at low bias (eφ0/3) as possible.
Logarithmic bias intervals are convenient for this.18 Naturally,
this requires a low-level meter capable of measuring the
expected low currents.
(c) Use the presentation of Figure 4 and eq 6 to extract the
characteristic G0 and C parameters and to validate if the
Simmons model is at all relevant for analyzing the data. A
complementary linearized presentation (e.g., Fowler-Nordheim,
see ref 43) can be added to map the high bias range of the
measured data.
(d) In the case of deviation from the model (nonlinear I/V vs
V2 presentation), only G0 can be regarded as a characteristic
parameter and can be translated to β0 ) f(G0, l, A) (eq a7).
Only if the I/V vs V2 plots are linear, can one use the following
recommendations:
(e) Extract approximate F value from C (eq a8).
(f) In the case of high confidence in the effective electrical
contact area (see point a above), translate G0 into β0l (using C
and A, eq a6) and calculate F more accurately (F ) f(C, β0l),
eq a8).
(g) Combining F and β0l (eqs 3 and a1) yields φ0 ) β0l/F
and lRxm* ) 1.025(Fβ0l)1/2, where the last product can be
further interpreted depending on the experimental framework
(e.g., systematic change in molecular length, conjugation or
electrode work function).
(h) Achieving a linear plot in any of the versions of eq 8 is
required for extracting believable absolute numbers. Still, even
Vilan
if linearity is not achieved, such a presentation can be very
informative about qualitative differences between different
junctions.
6. Summary
The possibility for extracting information on transport
characteristics from analyses of molecular current-voltage (cf.
current-length) data was considered. For this purpose, the
accepted Simmons model was reconsidered. Major failures are
(1) the strong dependence of extracted parameters on the
assumed contact area for transport, and (2) the strong deviation
of experimental current-voltage data from the assumptions that
underlie the Simmons model, viz., the barrier profile is linear
with distance, and the barrier profile varies linearly with bias.
The seemingly good graphical correlation between raw data
and numerical fits to the Simmons model probably results from
the scaled nature of the model, without proving its validity or
accuracy. The applicability of the Simmons tunneling model to
a specific I-V should be tested using the linearized version (I/V
vs V2) rather than using the direct form (I vs V).
The relevant range for the Simmons model is near equilib-
rium, and based on this, an alternative parametrization procedure
was suggested. This procedure emphasizes the equilibrium
conductance and shape factor as robust characteristics of the
junctions, independent of any further information about the
junction. These two parameters can be related to more common
barrier characteristics, such as the decay parameter and barrier
height but only if the contact area is known or from data where
the molecular length (barrier width) is varied systematically.
Thus, the proposed approach is complementary to the common
thickness-dependent analysis, to which it can be added to allow
separating the contribution of barrier height from that of an
effective mass parameter.
The quasiequilibrium I-V analysis will be especially useful
for analyses of chemically unique molecular junctions, the
thickness of which cannot be varied. Despite the gross over-
simplification of the Simmons model, the justification for using
it originates from the need for quantifying imperfect molecular
junctions. Such quantification is crucial for achieving more
controlled, reliable, and reproducible experiments, as well as
acquiring a predictive power toward a more realistic description
of transport across molecular junctions and more adequate
interpretation for extracted averaged characteristic parameters.
Acknowledgment. I thank the Kreitman foundation for a
fellowship at Ben Gurion University of the Negev; M. Reed
and S. Lindsay for kindly providing their I-V data; Y. Selzer
and A. Solomon for discussions; and N. Kalisman for helpful
remarks on numerical analyses. I am grateful to D. Cahen for
numerous discussions, especially on contact area issues, and
critical readings of, and constructive remarks on, the manuscript.
Appendix
A1. Glossary of Terms
A ) contact area [µm2]
C ) cubic polynomial coefficient [V-2]
I ) current [A]
G0 ) equilibrium conductance [Ω-1]
L ) (true) junction width [Å]
P ) fifth order polynomial coefficient [V-4]
V ) bias [V]
W ) work function [eV]
e ) electron charge [C]
h ) Plank’s constant [Js]
Analyzing Molecular Current-Voltage Characteristics J. Phys. Chem. C, Vol. 111, No. 11, 2007 4443

l ) molecular length [Å] A3. Conversion Equations.

The two quasi-equilibrium coefficients can be combined to
m0 ) free electron mass [kg]
extract β0l, under a priori known effective mass, m*, and contact
m* ) electron effective mass area, A, by combining eqs 4c and 7a
R ) width ratio ()L/l)
β0 ) decay parameter [Å-1]
1
β0l - ln 1 -
2 ( 5
+
3
+
6
β0l β 2l2 β 3l3
) )
( )
0 0
φ0 ) barrier height [V] G0x6C
F ) shape factor [V-1] ln(2πm0e3/h3) - ln (a6)
Am*
ψ ) potential [V] Note that second term on the left ∼0 and can be neglected to
A2. Other Forms of the Simmons Model. get an explicit expression for β0l. In addition, any uncertainty
in the effective mass, m*, has little effect on β0l, as these
a. Equilibrium (V ≡ 0) expression for the decay parameter, parameters are logarithmically related.
β0 In case of extracting G0 only, it can be translated to β0l, if
the junction width (Rl) and real contact area, A, are known by
4π rearranging eq 4b and substituting β0l ≡ Fφ
h x
β0 ) R 2m*m0eφ0 ) 1.025Rxm*φ0 (a1)
β0l - ln(β0l - 2) ) ln(e2/4πh) - ln(G0R2l2/A) (a7)
Although the logarithmic term on the left cannot be ignored
The numerical constant is valid for β0 in [Å-1], φ0 in [V], and (∼3), it is still possible, though, to calculate β0l without
dimensionless R and m* values (1.025 is in units of [Å-1 V-0.5]). considering that term, to arrive at an initial guess.
b. Nonequilibrium (V * 0) expression for the decay Rearranging eq 7a provides an explicit term for the shape
parameter, β0 factor, F, or the barrier height, φ0, as a function of the cubic
coefficient, C, and the dimensionless thickness, β0l, extracted
from G0 (eq a6)
4π
h x
β) R 2m*m0e(φ0 - V/2) ) β0x1 - V/2φ0 (a2)

x
β0l 1 - 2/β0l
F) ) 4‚ 6C ≈ 4x6C (a8)
φ0 1 - 3/β0l - 3/β02l2
c. The widely accepted form of the linear Simmons relations

x 1 (β0l) - 3/β0l - 3
2
is 1 β 0l
φ0 ) ≈ (a9)
4 6C 1 - 2/β0l 4x6C

I)
e2 A
2πh (Rl)2 {(V
φ0 - ×
2 )
where the approximated equality refers to the condition of β0l
. 2.

[ x ( )] (
A4. Mathematical Tools.
4πRl V V Mean square error (MSE) fitting was done by a MATLAB
exp -
h
2m*m0e φ0 -
2
- φ0 + ×
2 ) function named “fminsearch” which uses the Nelder-Mead

exp - [ x ( )]}
4πRl
h
2m*m0e φ0 +
V
2
(|V| e φ0) (a3)
simplex48 direct searching algorithm to find a parameter array,
p, that minimizes the MSE defined as49
N
1
The same relations, expressed in terms of the equilibrium decay
MSE ) ∑ [f (Vi, p) - Ii]2
N i)1
(a10)
parameter, β0, are
where p ) (G0, F, φ0), [Vi] and [Ii] are N long arrays of

{( ) ( x )
voltage and current, and f represents eq 2 (or any variation of
e2 Aφ0 V V it).
I) 1- exp - β0l 1- - Implicit equations (e.g., eq a6) were solved using the
2πh (Rl)2 2φ0 2φ0

( ) ( x )}
MATLAB function “fzero” or “fminsearch”.
V V
1+ exp - β0l 1+ (a4)
2φ0 2φ0 Supporting Information Available: Glossary of translation
functions from polynomial coefficients into tunneling parameters
(S1); additional maps of mean square error as function of fitting
d. The general Simmons relation including a bias-dependent variables (S2); summary tables comparing the tunneling pa-
potential, ψ(V), and profile (width ratio), R(V), indicated by a rameters extracted by various fitting procedures (S3); and a
subscript V detailed experimental section for the bilayer junction (S4). This
material is available free of charge via the Internet at http://
pubs.acs.org.
e2 A 4π
I)( ‚ψ [
h exp -lRV
2πh R 2l2 V
V
(
h x
hV -
2m*m0eψ ) References and Notes
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h V + |V|)
2m*m0e(ψ )] (a5) Sampaio, J.; Raymo, F. M.; Stoddart, J. F.; Heath, J. R. Science 2000, 289,
1172.
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(49) In comparison, the Microcal Origin nonlinear search algorithm relies
on derivatives rather than on direct search. Yet the MSE function is
similar to the χ2 function of Microcal Origin for a single independent
variable (Vi).
(50) Similar maps were produced also for the experimental data
providing fairly irregular contours, thus not presented. A comparable
example can be found in Figure 6 of ref 15.