LETTERS

PUBLISHED ONLINE: 6 JANUARY 2013 | DOI: 10.1038/NNANO.2012.238

The role of van der Waals forces in the

performance of molecular diodes
Nisachol Nerngchamnong1†, Li Yuan1†, Dong-Chen Qi2,3, Jiang Li1, Damien Thompson4 *
and Christian A. Nijhuis1,5 *

One of the main goals of organic and molecular electronics is to
relate the performance and electronic function of devices to the
chemical structure and intermolecular interactions of the
organic component inside them, which can take the form of
an organic thin film, a self-assembled monolayer or a single
molecule1–7. This goal is difficult to achieve because organic
and molecular electronic devices are complex physical–
organic systems that consist of at least two electrodes, an
organic component and two (different) organic/inorganic inter-
faces. Singling out the contribution of each of these com-
ponents remains challenging. So far, strong p–p interactions
have mainly been considered for the rational design and optim-
ization of the performances of organic electronic devices8–10,
and weaker intermolecular interactions have largely been
ignored. Here, we show experimentally that subtle changes in
the intermolecular van der Waals interactions in the active
component of a molecular diode dramatically impact the per-
formance of the device. In particular, we observe an odd–even
effect as the number of alkyl units is varied in a ferrocene–
alkanethiolate self-assembled monolayer. As a result of a
more favourable van der Waals interaction, junctions made
from an odd number of alkyl units have a lower packing
energy (by ∼0.4–0.6 kcal mol–1), rectify currents 10 times
more efficiently, give a 10% higher yield in working devices,
and can be made two to three times more reproducibly than
junctions made from an even number of alkyl units.
In general, small changes in the chemical structures of molecules
can result in large changes in the overall interaction energy between
them and, consequently, in large changes in macroscopic structure
and orientation11. This effect is crucial in many applications, includ-
ing crystal engineering12, drug design13 and organic electronics14.
The importance of weak intermolecular interactions is evident
from studies in which the physical properties of materials change
as a function of the number n of a small repetitive unit such as
2(CH2)2; materials with neven can have very different properties
from those with nodd. These so-called odd–even effects determine
the properties of both bulk and nanoscopic materials, for example,
the stability and packing densities of self-assembled monolayers
(SAMs)15, the melting points of n-alkanes15 and tunnelling rates16.
To study the role of van der Waals interactions in the perform-
ance of molecular diodes, we used the ‘EGaIn’ technique17. This
technique uses template-stripped silver (AgTS) bottom electrodes
supporting SAMs and a soft liquid metal (a eutectic alloy of
gallium and indium with a 0.7-nm-thick surface layer of predomi-
nantly Ga2O3) as a non-invasive top electrode18. The EGaIn tech-
nique is suitable for conducting physical–organic studies of charge
transport, because it yields junctions with high yield in working
devices (up to 100%), statistically large amounts of data, and is com-
patible with a wide variety of SAMs18–21. Figure 1a presents an
optical micrograph of a cone-shaped tip of Ga2O3/EGaIn in
contact with a ferrocene-alkanethiolate SAM of S(CH2)nFc or
SCnFc (n ¼ 6–15; Fc ¼ ferrocene) on a AgTS bottom electrode,
together with schematic illustrations of ‘ideal’ junctions with
SAMs of SC10Fc (right) and SC11Fc (left). The SAMs of SCnFc are
covalently bound to the AgTS bottom electrodes by Ag–S bonds,
and form van der Waals contact with the Ga2O3/EGaIn top electro-
des. This figure also defines the tilt angles a of the Fc units with
respect to the plane perpendicular to the surface.
The junctions with SAMs of SC11Fc rectify currents with a
log-average rectification ratio (R ; |J(21.0 V)|/|J(þ1.0 V)|) of
1.5 × 102 with a log standard deviation of 2.1. Figure 1b shows
the energy level diagrams when a bias of 21.0 or 1.0 V is applied
across these molecular diodes (defined here as forward and
reverse bias, respectively, in analogy to conventional diodes).
Temperature-dependent measurements indicated that the mechan-
ism of charge transport changes from tunnelling in one direction of
bias to tunnelling followed by hopping in the other21. With positive
bias, the highest occupied molecular orbital (HOMO) of the mol-
ecules does not fall within the energy window of the Fermi levels
of the electrodes, so charges cannot be injected into the HOMO;
both the Fc units, dFc , and the alkyl spacer, d Cn , form a barrier
against tunnelling with a width of dtot,reverse ¼ dFc þ d Cn . At negative
bias, the HOMO of the molecules falls between the Fermi levels of
the electrodes, so charge can hop to the Fc units and, consequently,
reduce the width of the tunnelling barrier to dtot,forward ¼ d Cn . This
reduction in the width of the tunnelling barrier only at forward bias
results in the large observed current rectification.
We formed junctions with SAMs of SCnFc and measured statisti-
cally large numbers of J(V) data (N ¼ 500–700; see Supplementary
Table S2 for all statistics) following previously described pro-
cedures21,22. Figure 2a shows the log-average J(V) curves of junctions
with SAMs of SC10Fc and SC11Fc, and Fig. 2b presents histograms
of the values of R, as well as Gaussian fits to these histograms
(Supplementary Figs S3–S5 show all data). Figure 2c–f summarizes
four characteristics of the junctions with SAMs of n ¼ 6–15 as a
function of n. Junctions with SAMs with n ¼ 9, 11 and 13 had (i)
smaller leakage currents, by a factor of 10 (Fig. 2c), (ii) larger
values of R, by a factor of 10 (Fig. 2d), (iii) 10% higher
yields in working devices (Fig. 2e), and (iv) smaller log-standard
deviations of the R values, by a factor of 2–3 (Fig. 2f ), than junctions
with n ¼ 8, 10 and 12. Junctions with SAMs of n ¼ 6 and 7 have low
yields in working devices (10% and 43%, respectively); these SAMs

1
Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543, 2 Department of Physics, National University of Singapore,
2 Science Drive 3, Singapore, 117551, Singapore, 3 Institute of Materials Research and Engineering, 3 Research Link, Singapore 117602, Singapore, 4 Tyndall
National Institute, University College Cork, Lee Maltings, Dyke Parade, Cork, Ireland, 5 Graphene Research Centre, National University of Singapore, 2 Science
Drive 3, Singapore 117542, Singapore, † These authors contributed equally to this work. *e-mail: christian.nijhuis@nus.edu.sg; damien.thompson@tyndall.ie

NATURE NANOTECHNOLOGY | VOL 8 | FEBRUARY 2013 | www.nature.com/naturenanotechnology 113

LETTERS NATURE NANOTECHNOLOGY DOI: 10.1038/NNANO.2012.238

a
Bulk Ga-In Bulk Ga-In

Ga2O3 Ga2O3

αodd αeven

αodd < αeven

vdW

200 μm
AgTS AgTS

b Hopping
Reverse bias Forward bias
leakage current: current: −3.3 eV
Tunnelling barrier Tunnelling barrier
dtot = dFc + dC dtot = dC
n n
HOMO
−4.3 eV
−4.5 eV −4.5 eV
−5.7 eV −5.3 eV
HOMO

dC dFc dC dFc
n n

S (CH2)n Fe S (CH2)n Fe
Ga2O3− Ga2O3−
Ag EGaIn Ag EGaIn
Ground n = 6−15 6.7 Å Bias Ground n = 6−15 6.7 Å Bias

Figure 1 | Schematic illustration of junctions of the type AgTS–SCnFc//Ga2O3/EGaIn and the mechanism of charge transport across them. a, Left: optical
micrograph image of the tunnelling junction, showing a cone-shaped tip of Ga2O3/EGaIn suspended from a microneedle in contact with a SAM on a AgTS
surface. Middle and right: schematic illustrations of ‘ideal’ tunnelling junctions with SAMs of SCnFc with n ¼ 10 (top right) or 11 (top middle). The difference
in the tilt angle a of the Fc units with respect to the surface normal is also indicated. b, Energy level diagrams of the junctions at a bias of 21.0 V and
þ1.0 V. At negative bias (or forward bias), when the molecular diode allows current to pass through, the HOMO level centred at the Fc units falls between
the energy window of both Fermi levels and can participate in the mechanism of charge transport. The two-step mechanism of charge transport involves
tunnelling of an electron from the HOMO of the Fc across the alkyl chain to the bottom electrode, followed by hopping of an electron to the Fc unit in a
second step. The width of the tunnelling barrier, dtot , is determined by the length of the alkyl chain, dalkyl , or dtot ¼ dalkyl. At positive bias (or reverse bias),
when the diode blocks the current, this HOMO level falls below both Fermi levels and cannot participate in the mechanism of charge transport.
Consequently, the whole length of the molecule forms a barrier against tunnelling of width dtot ¼ dalkyl þ dFc. For ideal diodes, this current would be
infinitesimally small and is called ‘leakage current’ in analogy to conventional diodes.

are disordered, probably because of weak alkyl–alkyl chain inter-
actions. Junctions with SAMs of n ¼ 14 and 15 gave good yields
in working devices (79% and 71%, respectively), but low values of
R; these SAMs are disordered and suffer from back-bending Fc moi-
eties (that is, Fc moieties that fold back, pointing towards the bottom
electrode; see below)23.
Figure 2c shows that the odd–even effect of the leakage current
measured at positive bias, or when J depends on dtot,reverse , is
more pronounced than that of the current measured at negative
bias, or when J depends on dtot,forward. The measured values of J
depend exponentially on the values of d, as described by a simplified
form of the Simmons equation J ¼ J0e2bd, where b is the tunnelling
decay coefficient (Å21) and J0 (A cm22) is the pre-exponential
factor (which depends on several parameters including contact
resistance)24. Thus, only at positive bias can a small variation in
the orientation of the Fc units as a function of n cause large vari-
ations in the measured values of J and, consequently, change the
performance of the molecular diodes.
We have verified this hypothesis by relating the supramolecular
structure of the SAMs—determined by near-edge X-ray absorption
fine structure (NEXAFS) spectroscopy, electrochemistry and
molecular dynamics simulations—to the electrical characteristics
of the junctions. Our molecular diodes perform better on silver sur-
faces than on gold surfaces, but electrochemical characterization of
the SAMs is only possible on gold surfaces (Fig. 3). To be able to
relate the data obtained by these two techniques, we characterized
the SAMs on both silver and gold surfaces using NEXAFS and mol-
ecular dynamics (Fig. 4).
Figures 3 and 4 highlight four important observations. (i) The
values of a as a function of n, determined theoretically by molecular
dynamics (Fig. 3a,b) and experimentally by NEXAFS spectroscopy
(Fig. 3c,d), are on average 58 smaller (that is, the Fc units are
standing up more) for SAMs with nodd on AgTS substrates than
for SAMs with neven , while the reverse is true for SAMs on gold
(Supplementary Figs S7–S9). (ii) SAMs on AuTS with nodd are
more easily oxidized than SAMs with neven , by 27+12 meV (or
0.6+0.3 kcal mol21; Fig. 4a,b). (iii) The Fc–Fc and Fc–alkyl chain
interactions are constant as a function of n (Fig. 4c). (iv) The
alkyl–alkyl chain interactions increase with increasing n and are
more favourable (by 0.4+0.6 kcal mol21) for SAMs on gold
with neven than with nodd , while the opposite is true for SAMs on
silver (Fig. 4d).

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NATURE NANOTECHNOLOGY DOI: 10.1038/NNANO.2012.238 LETTERS
a d
Low Ordered SAMs Back-bending
SC10Fc
10−2 yields SAMs
SC11Fc
100
10−3
Large leakage

Rectification ratio, R
current:
Current (A cm−2)

10−4 R ≈ 17
10
10−5

10−6
1
Small leakage
10−7 current:
R ≈ 151
10−8 0.1
−1 0 1 6 7 8 9 10 11 12 13 14 15
Voltage (V) Chain length, n

b 60 e 100
SAM: SC10Fc
R = 17
50
σR = 5.11
80

Yield in working devices (%)

SAM: SC11Fc
40 R = 151
σlog = 2.14 60
Counts

30
σR σR
40
20

20
10 σR σR

0 0
10−2 10−1 100 101 102 103 104 105 6 7 8 9 10 11 12 13 14 15
Rectification ratio, R Chain length, n

c 10−1 f 7
|J| at −1.0 V (forward bias)
|J| at +1.0 V (reverse bias)
10−2 6
Log-standard deviation of R, σR

10−3
Current (A cm−2)

10−4 4

10−5 3

Small leakage
10−6 2
current
Large leakage current
10−7 1
6 7 8 9 10 11 12 13 14 15 6 7 8 9 10 11 12 13 14 15
Chain length, n Chain length, n

Figure 2 | Electrical characteristics of the tunnelling junctions of AgTS–SCn Fc//Ga2O3/EGaIn with n 5 6–15. a, The J(V) curves of junctions with SAMs of
SCnFc with n ¼ 11 or 10. Error bars are omitted for clarity (see Supplementary Fig. S3 for graphs with error bars). b, Histograms of R, with Gaussian fits (grey
lines), are for junctions with SAMs of SCnFc with n ¼ 11 or 10 (see Supplementary Fig. S4 for all histograms of R). c, Values of J measured at þ1.0 and
21.0 V, as a function of n (see Supplementary Fig. S5 for all histograms of J). Error bars represent one log standard deviation (black) and 95% confidence
level intervals (blue). d, Values of R as a function of n. Error bars represent one log standard (black) deviation and 95% confidence level intervals (blue).
e, Yields of working junctions as a function of n. f, Log standard deviations of the value of R as a function of n. In d–f, vertical dashed lines show how the
junction properties depend on n, with boundaries marking the transition between low yields from devices made from SAMs with n , 8, excellent device
properties for SAMs with nodd in the range n ¼ 8–13, and finally less ordered, back-bending SAMs for n . 13.

It has been reported that oxidation of the Fc units results in com-
plexation of the ClO42 anions to the Fcþ cations, accompanied by
structural changes of the SAMs25. During oxidation of the SAMs,
the ClO4 2 anions bind to the ferrocenium cations, forming
strong ion pairs, and thus break the Fc–Fc and Fc–alkyl interactions.
During this process, the molecules of the SAMs are forced to stand
up more25, which can only be achieved by rearranging the van der
Waals interactions between the alkyl chains. For SAMs on gold,
these alkyl chain interactions are weaker for nodd than for neven
and hence require less energy to rearrange during oxidation,

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LETTERS NATURE NANOTECHNOLOGY DOI: 10.1038/NNANO.2012.238

a b 90
Alkyl chain
Ag H
80
Fc unit C Fe
70

Tilt angle α (°)

S
60
Sulphur

50

40

30
6 7 8 9 10 11 12 13 14 15
Chain length, n

c d 60
Cp π*
(3e2u)
SC7Fc 58
Normalized intensity (a.u.)

Cp π*
(4e1g)
56

Tilt angle α (°)

54
SC6Fc
52

θ = 20°
50
θ = 90°

280 290 300 310 6 7 8 9 10 11 12 13 14 15

Photon energy (eV) Chain length, n

Figure 3 | Structural characterization of the SAMs by molecular dynamics and NEXAFS. a, Zoom-in of chain packing in the centre of a SAM with n ¼ 9,
showing the prevalence of upright chain orientations (hydrogen atoms are omitted for clarity). Inset: structure of the molecule. The full SAM model is shown
in Supplementary Fig. S10, as well as a full description of SAM formation and dynamics on Supplementary Information pages S34–S44. b, Calculated Fc tilt
angles a. An odd–even effect of 58 in a is computed from the average of the calculated tilt angles. c, Near C K-edge NEXAFS spectra for SAMs of SC6Fc and
SC7Fc on AgTS recorded at an incident angle of u ¼ 908 and a grazing angle of u ¼ 208. The signals at 285.4 eV and at 286.9 eV are assigned to C 1s  4e1g
and C 1s  3e2u transitions, respectively, based on previous assignments27. d, Value of a (with an estimated error of approximately +58) as a function of n,
derived from NEXAFS spectra (Supplementary Figs S7 and S8).

lowering the oxidation potential. The electrochemical data, sup-
ported by molecular dynamics simulations and NEXAFS measure-
ments, indicate that these SAMs on AuTS have lower packing energy,
DEpack ¼ 0.6+0.3 kcal mol21, because the Fc units are standing
up more, resulting in more favourable alkyl–alkyl chain interactions
for neven than for nodd.
In general, the odd–even effects for SAMs on gold and silver are
reversed due to the different metal–S–C bond angles (Ag–S–C is
close to 1808 and Au–S–C is close to 1098)15. Thus, we expect
that the SAMs on silver with nodd have better packing than SAMs
with neven , by a similar amount of energy. Indeed, molecular
dynamics simulations and NEXAFS (Supplementary Figs S7–S9)
show that for SAMs on gold the Fc units are standing up
more, with neven allowing better packing (DEpack) of the SAM by
0.4+0.6 kcal mol21 (or 1.2+1.8 kcal nm22), whereas for SAMs
on silver this is true for nodd (Fig. 4d and Supplementary
Fig. S12). These calculations also show that the more stable SAMs
with smaller tilt angles a are slightly thicker and stiffer
(Supplementary Fig. S13); that is, they have smaller root-mean-
square fluctuations in the atom positions.
The more upright Fc units in molecular diodes consisting of
SAMs on AgTS with nodd pack better and are stiffer because of
more favourable molecule–molecule interactions. These SAMs are
stable during fabrication, resulting in working devices with high
yields (Fig. 2e) that block the current efficiently at reverse bias,
resulting in large rectification ratios of R ≈ 100 (Fig. 2d). The
more flat-lying Fc units in SAMs with neven prevent optimal
packing of the molecules, resulting in slightly thinner SAMs that
pack less well and are less stiff. These SAMs are more prone to
defects during fabrication, resulting in working devices with lower
yields (Fig. 2e) that block the current less efficiently at reverse
bias, resulting in large leakage currents (Fig. 2c) and small rectifica-
tion ratios of R ≈ 10 (Fig. 2d). These defects result in variation in the
average values of dtot,reverse from device to device, which, in turn,
causes large error in the rectification ratios (Fig. 2f ).
The calculated SAM structures (Fig. 3a and Supplementary
Fig. S11) confirm the electrochemical data (Supplementary
Fig. S2), which indicate that most of the Fc groups are confined at
the top of the SAMs for n ¼ 6–13, but for n ¼ 14 or 15 the SAMs
are defective due to back-bending of the Fc units23. Hence, control
over the supramolecular structure of the SAMs is essential for the per-
formance of the molecular diodes. Only those devices with well-
defined supramolecular structures—with most of the Fc units
located at the top of the SAM—perform well and rectify current
with R . 100 (ref. 18). In this study, transmission rates26 across the
tunnelling junctions do not change significantly, probably because
of the small change in the average value of a (see Supplementary
Information page S2 for further discussion), which implies that maxi-
mizing the rectification ratio by blocking leakage currents (Fig. 2c) is
perhaps the most important issue for optimal device performance.
In summary, we have shown that control over the supramolecu-
lar structure of SAMs is required to ensure optimal performance of

116 NATURE NANOTECHNOLOGY | VOL 8 | FEBRUARY 2013 | www.nature.com/naturenanotechnology

NATURE NANOTECHNOLOGY DOI: 10.1038/NNANO.2012.238 LETTERS
a b
0.10
Epa
450
Epc

Epeak (meV) vs Ag/AgCl

0.05
400
Current (mA)

0.00
350

−0.05 SC11Fc:
Epa = 392 ± 10 mV 300
SC12Fc:
−0.10 Epa = 419 ± 7 mV Back-bending
250
0.0 0.2 0.4 0.6 0.8 6 7 8 9 10 11 12 13 14 15
Voltage (V) vs Ag/AgCl Chain length, n

c d 0.9
SAMs on AgTS
−5
SAMs on AuTS
0.6
Interactions (kcal mol−1)

−10

ΔEpack (kcal mol−1)

0.3
−15
0.0
−20
Fc–Fc −0.3
Alkyl–alkyl Fctot
−25
Fc–alkyl Molecule
−0.6
6 7 8 9 10 11 12 13 14 15 7 8 9 10 11 12 13 14
Chain length, n Chain length, n

Figure 4 | Packing energies as a function of n derived from electrochemistry and molecular dynamics. a, Cyclic voltammograms of SAMs of SC11Fc and
SC12Fc on AuTS with aqueous 1.0 M HClO4 as electrolyte solution, recorded at a scan rate of 1.0 V s21 (see Supplementary Fig. S2 for all cyclic voltammograms).
b, Peak oxidation (Epa) and reduction potentials (Epc) for SAMs on AuTS as a function of n, with aqueous 1.0 M HClO4 as electrolyte solution, recorded at a scan
rate of 1.0 V s21. c, Computed SAM packing interactions on Ag for alkyl–alkyl chain, Fc–alkyl chain and Fc–Fc head group interactions as a function of n. Also
plotted are the full Fc packing (Fctot , composed of Fc–Fc packing plus Fc–alkyl packing) and the full molecule packing (Molecule, composed of alkyl–alkyl and
Fctot packing). The results for SAMs on Au are given in Supplementary Fig. S14 and plots with error bars (0.220.4 kcal mol21) are given in Supplementary
Fig. S12. d, Odd–even differences DEpack in calculated SAM packing energies on Ag and Au substrates; the DEpack value at each chain length n is the deviation of
the Epack value at n from the average of the Epack values at n 2 1 and n þ 1. An odd–even effect of 0.4 kcal mol21 in molecule packing energies is estimated from
the average of the second derivatives around each Epack data point (Supplementary Information page S39).

SAM-based devices. A seemingly small change of 58, on average, in SAMs, we used cone-shaped tips of Ga2O3/EGaIn as top electrodes using a home-
the tilt angle a of the active component of the SAMs (the Fc units built system (Supplementary Information page S21), because the electrical
characteristics are dominated by the chemical and supramolecular structure of the
in our case) as a function of the number of 2CH22 units in the SAMs inside the junctions, not because of any other asymmetries, nor the Ga2O3
backbone of the SAMs improves the packing of the molecules by layer, present in these junctions. We recorded statistically large numbers of J(V) data,
0.4–0.6 kcal mol21 because of more favourable intermolecular which we analysed using previously reported methods (Supplementary Information
van der Waals interactions. This more stable and stiffer SAM struc- page S23)22. We calculated the structures of the SAMs with molecular dynamics
ture results in a remarkable improvement in the performance of the simulations (440 ns in total) of statistically large numbers of molecules (1,216)
adsorbed on Ag(111) and Ag(111) electrodes with areas of 33 × 13 nm2. We
devices. In the future, to ensure optimal performances, the rational modelled monolayer assembly29,30 followed by metal–S bond formation for SAMs
design of SAM-based junctions (and studies involving charge trans- with n ¼ 6–15. To minimize edge effects, we measured the properties of the SAMs
port across (bio)molecules in general) should take into account van within 250-molecule central disks with a radius of 5 nm (or 79 nm2). Full details of
der Waals interactions, as demonstrated in this work. the molecular simulations are given on Supplementary Information page S34 onwards.

Methods Received 10 August 2012; accepted 20 November 2012;

28 17
The ferrocene derivatives , the SAMs , Au (ref. 17) and the Ag surfaces were TS
prepared following reported procedures (Supplementary Information page S3). We
characterized the SAMs on AuTS with cyclic voltammetry, using a home-built
electrochemical cell equipped with Pt-disk counter electrode and a Ag/AgCl
reference electrode, at a scan rate of 1.0 V s21 in aqueous 1.0 M HClO4 as the
electrolyte solution (Supplementary Information page S18). The NEXAFS spectra at
the C K-edge were recorded using the Surface, Interface and Nanostructure Science
(SINS) beamline at the Singapore Synchrotron Light Source (SSLS) in an ultrahigh-
vacuum (UHV) chamber with a base pressure of 1 × 10210 mbar. We recorded the
angular-dependent NEXAFS spectra in the Auger electron yield (AEY) mode by
collecting the Auger electrons resulting from carbon KVV transitions with a Scienta
R4000 electron energy analyser. To estimate the tilt angle a of the Fc units, we used
the angular dependence of the intensity of the C 1s  4e1g transitions at u ¼ 208 and
908 (Supplementary Information page S29). To form good electrical contacts to the
TS 17 published online 6 January 2013
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Acknowledgements
The Singapore National Research Foundation (NRF award no. NRF-RF2010-03 to C.A.N.)
is acknowledged for supporting this research. D.T. acknowledges financial support from the
Science Foundation Ireland (SFI; grant no. 11/SIRG/B2111) and the use of computing
resources at Tyndall and the SFI/Higher Education Authority Irish Centre for High-End
Computing (ICHEC). The authors thank Su Ying Quek for useful discussions and the
technical support from the Singapore Synchrotron Light Source.
Author contributions
N.N. synthesized the compounds and characterized the SAMs. L.Y. performed the J(V)
measurements. J.L. prepared the template-stripped substrates. Q.D.C. and L.Y. recorded
and analysed the NEXAFS spectra. D.T. performed the molecular dynamics simulations.
C.A.N. supervised the project. All authors contributed to writing the manuscript.
Additional information
Supplementary information is available in the online version of the paper. Reprints and
permission information is available online at http://www.nature.com/reprints. Correspondence
and requests for materials should be addressed to D.T. and C.A.N.
Competing financial interests
The authors declare no competing financial interests.