Langmuir 1996, 12, 2737-2746 2737

Chain Length Dependence of the Striped Phases of

Alkanethiol Monolayers Self-Assembled on Au(111): An
Atomic Beam Diffraction Study
N. Camillone III,†,‡ T. Y. B. Leung,† P. Schwartz,§ P. Eisenberger,| and
G. Scoles*,†
Princeton Materials Institute, Princeton University, Princeton, New Jersey 08544

Received December 1, 1995. In Final Form: February 29, 1996X

Low-energy helium atom diffraction measurements of the surface structure of n-alkanethiol films deposited
from a molecular beam on to the (111) face of gold single crystals (at an impingement rate on the order
of 1011(1 molecules cm-2 s-1) show that the thiols form “striped” overlayers. These structures are similar
to those previously seen by Dubois et al. in a recent low energy electron diffraction (LEED) study of
vapor-deposited overlayers (J. Chem. Phys. 1993, 98, 678), by Poirier et al. in a scanning tunneling microscope
(STM) study of low coverage solution-grown short-chain thiols monolayers (Langmuir 1994, 10, 3383), and
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more recently by us, Poirier, and Tarlov by thermal treatment of the full-coverage c(4x3×2x3)R30° phase
formed in the standard way by self-assembly from solution (J. Chem. Phys. 1994, 101, 11031). The surface
periodicity of the monolayer structures observed in the present study can be described (with respect to
the Au(111) surface lattice) in terms of a rectangular p×x3 unit mesh where p, the periodicity of the
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stripes, scales linearly with the length of the adsorbed thiol. The absolute value of the stripes’ period is,
with a maximum deviation of 3%, 1.9 times the length of the corresponding fully stretched thiolate fragment
which coincides with the length of the corresponding fully stretched dialkyl disulfide. The present results,
analyzed in the context of the others, confirm the presence of coverage-dependent and chain-length-
dependent phase behavior in these systems and suggest that, at the lowest “full” coverages, the molecules
may assume a near-flat configuration on the gold substrate.

I. Introduction This complexity is reflected in both the structure of the

“Self-assembly” methods provide a wet-chemical ap-
proach to the fabrication of highly ordered organic
monolayers.1 Simple immersion of a clean substrate into
a dilute solution of surfactant molecules can, for certain
systems, result in the spontaneous assembly of a mono-
layer film possessing long-range (∼102-103 Å) molecular
order.2-7 During the past few years, n-alkanethiols
(CH3(CH2)n-1SH, referred to as Cn) adsorbed on gold have
served as the archetypical examples of such systems and
are arguably the most intensively studied and best
characterized class of organic thin films.8
The relative simplicity of self-assembly methods con-
ceals the complexity of intermolecular and interfacial
interactions involved in the formation of the monolayers.
†Also Chemistry Department, Princeton University.
‡Present address: Department of Chemistry, University of North
Carolina at Chapel Hill, Chapel Hill, NC 27599.
§ Also Department of Astrophysical Sciences, Princeton Uni-
versity.
| Also Physics Department, Princeton University.
X Abstract published in Advance ACS Abstracts, May 1, 1996.
(1) See, for example: (a) Nuzzo, R. G.; Allara, D. L. J. Am. Chem.
Soc. 1983, 105, 4481. (b) Netzer, L.; Iscovici, R.; Sagiv, J. Thin Solid
Films 1983, 99, 235. (c) Porter, M. D.; Bright, T. B.; Allara, D. L.; Chidsey,
C. E. D. J. Am. Chem. Soc. 1987, 109, 3559. (d) Bain, C. D.; Troughton,
E. B.; Tao, Y. T.; Evall, J.; Whitesides, G.; Nuzzo, R. G. J. Am. Chem.
Soc. 1989, 111, 321. (e) Bain, C. D.; Evall, J.; Whitesides, G. J. Am.
Chem. Soc. 1989, 111, 7155. (f) Wasserman, S. R.; Tao, Y.-T.; Whitesides,
G. M. Langmuir 1989, 5, 1074. (g) Ulman, A. Adv. Mater. 1990, 2, 573.
(h) Whitesides, G. M.; Laibinis, P. Langmuir 1990, 6, 87.
(2) Strong, L.; Whitesides, G. Langmuir 1988, 4, 546.
(3) Camillone, N., III; Chidsey, C. E. D.; Liu, G.-Y.; Scoles, G. J.
Chem. Phys. 1991, 94, 8493.
(4) Camillone, N., III; Chidsey, C. E. D.; Liu, G.-Y.; Scoles, G. J.
Chem. Phys. 1993, 98, 3503.
(5) Camillone, N., III; Chidsey, C. E. D.; Liu, G.-Y.; Scoles, G. J.
Chem. Phys. 1993, 98, 4234.
(6) Camillone, N., III; Chidsey, C. E. D.; Eisenberger, P.; Fenter, P.;
Li, J.; Liang, K. S.; Liu, G.-Y.; Scoles, G. J. Chem. Phys. 1993, 99, 744.
(7) (a) Fenter, P.; Eisenberger, P.; Liang, K. S. Phys. Rev. Lett. 1993,
70, 2447. (b) Fenter, P.; Eberhardt, A.; Eisenberger, P. Science 1994,
266, 1216.
(8) Dubois, L. H.; Nuzzo, R. G. Annu. Rev. Phys. Chem. 1992, 43, 437.
monolayers and the kinetics of their formation. For
example, it is now well documented that the packing of
molecules in the monolayer differs from that expected
based on simple analogy with the structure of bulk
n-alkane crystals.4,7,9,10 The periodicity along one of the
primary unit cell directions of the monolayer is twice that
found in analogous bulk crystal phases.4 The root cause
of this doubling is almost certainly due to interactions at
the organic/inorganic interface and has been attributed
to the formation of a disulfide-like moiety.7b
In this paper we report the results of helium atom
diffraction studies of monolayers, mostly, but not exclu-
sively, prepared in vacuo via molecular beam deposition.
In the context of the complexity of the interactions and
kinetics involved in monolayer formation, in vacuo mo-
lecular beam deposition of n-alkanethiols onto gold
surfaces is of interest for a variety of reasons. First,
molecular beam deposition provides a means to prepare
monolayers of short-chain thiols under very well-controlled
conditions. We have recently focused our attention on
these short-chain monolayers (n e 10), expecting the
ordering to be more strongly influenced by interfacial
forces when compared with that of the longer-chain
homologues. We found that, for short-chain thiols, the
conventional self-assembly methodology results in mono-
layers of irreproducible quality, possibly due to the inferior
ability of the shorter chains to provide protection against
diffusion of atmospheric and solution-borne contaminants
to the interface. Since in vacuo preparation of monolayers
avoids contact with atmosphere and solution, it provides
the means to study short-chain monolayer formation free
from any external contamination. Recently Chailapakul
et al.11 have compared, using nondiffractive techniques,
(9) Poirier, G. E.; Tarlov, M. J. Langmuir 1994, 10, 2853.
(10) (a) Anselmetti, D.; Baratoff, A.; Güntherodt, H.-J.; Delamarche,
E.; Michel, B.; Gerber, Ch.; Kang, H.; Wolf, H.; Ringsdorf, H. Europhys.
Lett. 1994, 27, 365. (b) Delamarche, E.; Michel, B.; Gerber, Ch.;
Anselmetti, D.; Güntherodt, H.-J.; Wolf, H.; Ringsdorf, H. Langmuir
1994, 10, 2869.

S0743-7463(95)01097-3 CCC: $12.00 © 1996 American Chemical Society

2738 Langmuir, Vol. 12, No. 11, 1996
the properties of monolayers self-assembled from solution
to those prepared by equilibrium vapor phase deposition.
While some differences were found, no clear-cut pattern
emerged from that study.
Second, thermal treatment of solution-prepared mono-
layers has recently been observed by us12,13 and others15
to result in the formation of “striped” phases: i.e.,
monolayer structures characterized by rows spaced at
intervals in the range of 7.5-13 times the gold-gold
nearest neighbor separation, dAu-Au, which appear as a
pinstripe pattern in STM images.13,15 Some of the
structures observed in our experiments are similar to the
structures observed by LEED in recent vapor dosing
experiments which have been proposed to be lower in
density relative to the familiar solution-grown
c(4x3×2x3)R30° monolayer.16 The two sets of observa-
tion do overlap in general, but disagree in some details.
Furthermore, n-alkanethiol monolayers are known to
be damaged by electron beam exposure.2 Since the
structure of the striped monolayers may depend on subtle
electronic effects associated with adsorbate-induced re-
construction of the gold surface, they may be even more
sensitive to electron beam exposure than their solution-
grown counterparts. Nonperturbative helium atom dif-
fraction studies of molecular beam deposited striped films
is clearly free from these problems and provides a route
for probing the coverage dependence of the overlayer
structure.
Finally, the preparation of monolayers in vacuo allows
easy access to nonequilibrium routes of monolayer growth.
It is known, for example, that the molecules in a monolayer
in solution are in dynamic equilibrium with the molecules
in the supernatant solution.17,18 This equilibrium is
thought to play a role in the dissolution of the gold
surface.19-22 This process is not present under normal
operating conditions (near room temperature and below)
in the vacuum apparatus, where desorption of chemisorbed
thiols is expected to be negligible at temperatures less
than ∼50 °C.13
The present work shows that the nonequilibrium
molecular beam deposition of short-chain (Cn, 6 e n e 10)
n-alkanethiols on Au(111) single crystal substrates, at
relatively low exposures, results in the formation of striped
phases. Our observation that the period of the stripes is,
within 3%, the same as the length of the corresponding
dialkyl disulfide (see below) and that the same phases
can be obtained by thermal treatment (i.e., evaporation)
of these monolayers indicates that these striped phases
may have a surface density substantially lower than that
corresponding to a fully occupied c(4x3×2x3)R30° over-
layer lattice. Since the observed periodicities are related
(11) Chailapakul, O.; Sun, L.; Xu, C.; Crooks, R. M. J. Am. Chem.
Soc. 1993, 115, 12459.
(12) Camillone, N., III; Leung, T. Y. Becky; Scoles, Giacinto SPIE,
OE/LASE 1994 Proceedings 1994, 2125.
(13) Camillone, N., III; Eisenberger, P.; Leung, T. Y. B.; Schwartz,
P.; Scoles, G.; Poirier, G. E.; Tarlov, M. J. J. Chem. Phys. 1994, 101,
11031.
(14) Schönenberger, C.; Jorritsma, J.; Sondag-Huethorst, J. A. M.;
Fokkink, L. G. J. J. Phys. Chem. 1995, 99, 3259.
(15) Poirier, G. E.; Tarlov, M. J.; Rushmeier, H. E. Langmuir 1994,
10, 3383.
(16) Dubois, L. H.; Zegarski, B. R.; Nuzzo, R. G. J. Chem. Phys. 1993,
98, 678.
(17) Chidsey, C. E. D.; Bertozzi, C. R.; Putvinski, T. M.; Mujsce, A.
M. J. Am. Chem. Soc. 1990, 112, 4301.
(18) Biebuyck, H. A.; Whitesides, G. M. Langmuir 1993, 9, 1766.
(19) Edinger, K.; Gölzhäuser, A.; Demota, K.; Wöll, Ch.; Grunze, M.
Langmuir 1993, 9, 4.
(20) McCarley, R. L.; Dunaway, D. J.; Willicut, R. J. Langmuir 1993,
9, 2775.
(21) Schönenberger, C.; Sondag-Huethorst, J. A. M.; Jorritsma, J.;
Fokkink, L. G. J. Langmuir 1994, 10, 611.
(22) Bucher, J.-P.; Santesson, L.; Kern, K. Langmuir 1994, 10, 979.
Camillone et al.
to the periodicities observed for thermally-treated, solu-
tion-grown monolayers, we complement the results ob-
tained by molecular beam deposition with a few mea-
surements obtained by thermal treatment of solution-
grown phases so to arrive at a rudimentary phase diagram
that relates chain length with monolayer structure and
surface coverage.
II. Experimental Section
(a) Substrate Preparation. Clean gold surfaces were
prepared in the following manner: a gold single crystal cut to
expose the (111) face is cleaned as outlined in our previous work
by repeated cycles of Ar+ sputtering and annealing to ∼800 °C.3-6
Once the surface is confirmed to be clean and well-ordered by
Auger spectroscopy and LEED, the crystal is removed from the
UHV chamber and immersed into a dilute solution of C10, C11,
or C12. The crystal is then installed into the helium atom
diffractometer. (The diffraction apparatus is described in detail
in previous publications.23 ) Upon completing our study of the
solution-grown monolayer, we cleaned the gold surface by
desorbing the monolayer by heating the crystal to ∼190 °C for
∼48 h. During and subsequent to the desorption of the monolayer,
the crystal is maintained within two, concentric, liquid-nitrogen-
cooled enclosures. The cleanliness and order of the gold surface
are confirmed by helium atom diffraction studies. Surfaces are
judged clean when (1) the intensity of the specular reflection is
∼20% of that of the incident beam, (2) a well-resolved first-order
diffraction peak is observed, and (3) evidence of the well-known
23×x3 surface reconstruction is observed. As confirmed by these
criteria, the crystal can be kept clean in our apparatus for at
least 1 month, provided that the crystal enclosures are maintained
at the temperature of boiling nitrogen.
(b) Procedures for in Vacuo Monolayer Growth. To
guarantee the purity of the thiols impinging on the crystal surface,
the beam deposition source (nozzle diameter = 0.5 mm) was
constructed out of Teflon. As early attempts to dose thiols using
a gas manifold of copper and stainless steel construction were
frustrated by nozzle clogs and the accumulation of yellow and
white powders inside the manifold, it became obvious that the
manifold needed to be constructed of less reactive materials. The
manifold used in the present experiments was constructed of
Teflon tubing, nylon connectors, and glass valves with Teflon
plungers. Prior to dosing, the manifold is evacuated by a
mechanical pump through a liquid nitrogen trap. During dosing,
the thiol pressure in the deposition source is typically 200-800
mTorr.
All n-alkanethiols (96-99% purity) were obtained from the
Aldrich Chemical Company and used without further purification.
Monolayer growth was accomplished by exposing the crystal to
a molecular beam extracted from the vapor of liquid thiols
(hexane-, octane-, and decanethiol). From the attenuation rate
of the intensity of the specular reflection during dosing at low
temperatures (where the sticking coefficient can be assumed to
be unity), the thiol flux at the surface during all of the in vacuo
growth experiments is estimated to be of the order of 1011(1
molecules cm-2 s-1.
We have experimented with two methodologies: low-temper-
ature growth and near-room-temperature growth. At crystal
temperatures near 100 K, the sticking probability is much higher,
and it becomes possible to completely cover the gold surface after
2 min, depending on the intensity of the thiol beam. When the
surface is at 100 K, we were able to monitor the intensity of the
specularly-scattered helium beam during the deposition. Upon
exposure to the thiol flux, the specular drops dramatically in the
first 30 s and reaches saturation at I(0,0)/I(0,0),t)0 ∼ 10-2, within
2 min. No surface order is observed subsequent to such low-
temperature depositions. We expect that the molecules simply
stick where they land, and, at 100 K, there are not enough thermal
fluctuations to enable diffusion and reorganization producing a
very rough, disordered surface that has very weak specular
reflectivity. Upon heating, however, the molecules reorganize,
and diffraction patterns are observed. Normally, the crystal is
heated incrementally: the crystal is brought to an elevated
temperature, held there for 1-5 min, and then cooled back down
(23) Danielson, L.; Ruiz, J. C.; Schwartz, C.; Scoles, G.; Hutson, J.
M. Faraday Discuss. Chem. Soc. 1985, 80, 47.
SAM Striped Phases
to 40 or 50 K prior to being probed by helium diffraction. In this
way, the temperature at which reorganization occurs can be
determined, and the dependence of the structure upon annealing
temperature can be monitored. In general we find that a single,
well-defined diffraction pattern develops after annealing to
temperatures between 260 and 350 K. Heating to lower
temperatures leaves the films somewhat disordered, and heating
to higher temperatures (∼400 K) results in desorption.
Near-room-temperature growth involves exposing the crystal
to the thiol beam at elevated temperatures, usually between 280
and 330 K. Since helium diffraction is very sensitive to vertical
(thermal) displacements of the molecules at the surface, obser-
vation of diffraction from these soft organic materials requires
lowering the surface temperature to ∼50 K. Thus, we performed
interrupted growth studies: the crystal is held at temperatures
near 300 K and exposed to the thiol beam for ∼5 min intervals.
The crystal is cooled after each deposition and the surface is
probed by helium diffraction. Since the sticking probability for
the thiols is expected to be quite low at room temperature, at
least one-half hour total exposure time is required to grow a
monolayer in this manner.
In the course of this work we have found that desorption of
self-assembled monolayers results in gold surfaces of varying
degrees of cleanliness. In general, C10 and C12 self-assembled
monolayers which give high-quality helium atom diffraction
patterns desorb leaving behind high-quality gold surfaces (as
evidenced by a >20% specular reflectivity, a well-resolved first-
order diffraction peak, and observation of the well-known 23×x3
surface reconstruction). Most poorly-diffracting self-assembled
monolayers desorb leaving behind only a somewhat contaminated
metal surface (∼5-10% specular reflectivity).
(c) Data Collection. All measurements are done in the in-
plane scattering configuration, i.e., the primary helium beam,
the surface normal, and the detector are all in the same plane.
Diffraction patterns are taken by measuring the intensity of the
scattered helium as a function of polar angle θ as the detector
is rotated in the scattering plane. In order to obtain a detailed
picture of the reciprocal space, polar angle scans are taken at 5°
increments of the azimuthal angle φ spanning a range of 120°.
These data in θ space can be transformed into the momentum
space by the use of the equation
∆K// ) ki(sin θf - sin θi)
where ∆K// is the momentum transfer parallel to the surface, θf
is the detector angle, ki and θi are the incident wavevector and
angle.
The θ resolution is estimated to be 0.5° which corresponds to
1% at ∆K// ) 6 Å-1 and 15% at ∆K// ) 0.2 Å-1. The φ resolution
depends on θ and ranges from 7° to 40° respectively at 90° and
10° from the specular reflection when the latter is located at 60°
from the normal to the surface. The uncertainty in the angular
position of a peak is dependent on the quality of the diffraction
pattern. For the organic surfaces described here, the uncertainty
is typically 0.05°. A worst case analysis shows that this translates
into an uncertainty of less than (1% in ∆K// for any individual
readings. For weak or asymmetrical peaks, the uncertainty in
θ may be as large as 0.2°, which translates into an uncertainty
of (4% in ∆K// in the worst cases. Also, because of the poor
quality of the diffraction patterns obtained for some of the
solution-grown monolayers, the calibration of the sample align-
ment could not be carried out exactly. This may cause an
uncertainty of 4.5% in the observed periodicities. For clarity, all
diffraction peaks described here are indexed according to the
hexagonal unit mesh of either the overlayer or the substrate as
indicated.
III. Results
(a) n-Hexanethiol. Early experiments involving mo-
lecular-beam deposition of n-hexanethiol on Au(111)
produced diffraction patterns consistent with the forma-
tion of a (5x3×x3)R30° overlayer lattice.12 The real space
unit cell and expected reciprocal space (diffraction pattern)
are illustrated in Figure 1a,b. The (5x3×x3)R30° mesh
is the simplest unit mesh capable of explaining the
observed diffraction pattern. However, the resolution
Langmuir, Vol. 12, No. 11, 1996 2739
function of the instrument and the quality of the early
experimental data made it all but impossible to distinguish
unequivocally between a (5x3×x3)R30° pattern and the
rectangular 7.5×x3 pattern shown in Figure 1c,d, or any
of a family of structures characterized by rows of crys-
tallographically identical molecules spaced (along the
rows) at intervals of x3×dAu-Au with the repeat distance
between the rows of 7.5 ×dAu-Au. We shall refer to
structures belonging to this family as 7.5-fold, striped
structures. Since Dubois et al.16 clearly observed a
(5x3×x3)R30° LEED pattern for C6/Au(111), it is rea-
sonable to assume that, when the repeat distance between
equivalent rows is 7.5×dAu-Au, the molecules arrange
themselves according to this unit mesh. With the present
higher-quality data, we will show below that it is in fact
a (5x3×x3)R30° unit mesh.
A more gradual molecular-beam deposition of C6 results
initially in a diffraction pattern along the nearest-neighbor
direction of the gold substrate (hereafter referred to as
the 〈11 h 0〉 direction) comprised of intensity near the
(x3×x3)R30° positions and peaks quite close to the
specular (see Figure 2a), and a pattern along the next
nearest-neighbor direction of the gold substrate (hereafter
referred to as the 〈11 h 2〉 direction) characterized by a
doubling of the bare gold surface periodicity (see Figure
2b). A closer look at the pattern in Figure 2a reveals that
the peaks are not consistent with a (5x3×x3)R30°
overlayer (i.e., a 7.5-fold periodicity relative to dAu-Au).
Rather, as indicated in Figure 2a, they are in good
agreement with an 8-fold periodicity, strongly suggesting
a rectangular 8×x3 lattice. The average over six samples
provides the values of (7.9 ( 0.2)×x3 or 22.8 ( 0.6 Å.
Examination of the 〈11h 2〉 spectrum strongly supports this
conclusion (Figure 2b).
The deviation of these results from both those of our
earlier work, as well as the results of Dubois et al. raises
at least two questions. First, the patterns shown in Figure
2a,b were obtained by dosing at a surface temperature of
100 K, followed by annealing to room temperature, while
the results of Dubois et al. were obtained by growing the
adlayer at 300-350 K (and may be affected by beam
damage which is virtually unavoidable with electrons).
Therefore, we should pose the question whether or not
the 7.5-fold (5x3×x3)R30° pattern can be obtained by
dosing or annealing to higher temperatures. Second, a
larger unit cell (8-fold periodicity instead of 7.5-fold) is
suggestive of a lower-coverage structure. Is it possible
that repeated dosing will eventually lead to production of
a 7.5-fold pattern?
To answer the first question, we carried out interrupted
growth experiments, as described in section II.b, at a
crystal temperature of ∼316 K. (The small sticking
coefficient for C6 on Au(111) at high temperatures made
316 K the highest temperature at which we could carry
out the experiment over reasonable time scales.) Selected
scans taken subsequent to cooling the crystal to 40 K are
presented in Figure 3. We discover two new features of
the growth of C6/Au(111): (1) with repeated exposure the
pattern shifts from agreeing with an 8-fold periodicity to
agreeing with a 7.5-fold periodicity and (2) extra peaks
half-way between the “1/5-order” spacing (see Figure 3)
can be discerned, indicating the possible existence of a
doubling of the unit mesh, i.e., a 15-fold periodicity
(possibly a (10x3×x3)R30° lattice). Due to the relatively
weak intensity of these extra peaks and lack of azimuthal
resolution of the present experimental setup, we cannot
provide unambiguous confirmation of this (10x3×x3)R30°
lattice: the apparent half-order peaks may actually be
diffraction belonging to nearby azimuths (see Figure 1).
We have also observed that annealing a fully-formed,
2740 Langmuir, Vol. 12, No. 11, 1996 Camillone et al.

Figure 1. (a, b) Illustrations of reciprocal-space (a) and real-space (b) for the (5x3×x3)R30° lattice. In (a), the reciprocal-space
unit mesh is outlined by a solid line. The total pattern is the superposition of three identical lattices rotated by 120° with respect
to each other. Each lattice is marked with a different symbol (9, (, and b). The positions coinciding with the reciprocal-space lattice
of the Au(111) surface are also marked (O). The dashed-line box illustrates how, in this case, for a scan along the 〈11 h 0〉 azimuth,
the resolution function of the apparatus can cause off-azimuth diffraction to appear as half-order diffraction. The real space unit
mesh is outlined in (b) (shaded circles) atop the Au(111) surface lattice (open circles). The real space diagram shows that the distance
between equivalent rows in the (5x3×x3)R30° lattice is equal to 7.5 times the gold nearest-neighbor spacing. Coverage should
not be inferred from this diagram. (c, d) Illustrations of reciprocal-space (c) and real-space (d) for a rectangular p×x3 lattice with
p ) 7.5. In (c), the reciprocal-space unit mesh is outlined by a solid line. The total pattern is the superposition of three identical
lattices rotated by 120° with respect to each other. Each lattice is marked with a different symbol (9, (, and b). The positions
coinciding with the reciprocal-space lattice of the Au(111) surface are also marked (O). The dashed-line box is the same as in (a).
Note that the distribution of overlayer spots in the vicinity of the (1,0) substrate spot is markedly different from that in (a). This
region in (a) and (c) forms the basis for Figure 5. Again, coverage should not be inferred from the real-space lattice diagram.

100 K deposited, 7.5-fold, striped structure to ∼400 K
results in a decrease in diffracted intensity and a shift in
peak positions toward the 8-fold periodicity (data not
shown). This observation, as well as those made in the
high-temperature dosing experiment, are consistent with
the picture that the periodicity depends on the coverage
and not simply on the temperature to which the monolayer
has been annealed or heated during growth.
Figure 4 shows that repeated dosing at low temperatures
results in the same shift from an 8-fold to a 7.5-fold
periodicity with increasing coverage as was observed in
the high-temperature dosing experiment. The transition
requires several 100 K dosings followed by room tem-
perature annealings (not all data are shown). The 7.5-
fold structure (Figure 4, trace c) appears to be (at least)
a local minimum in free energy, as further dosing does
not result in continued contraction of the lattice. These
observations are also consistent with the picture that the
periodicity depends on the coverage.
We further note that the improved quality of the data
relative to our earlier measurements12 provides now strong
evidence for the (5x3×x3)R30° structure (Figure 1a,b)
and against the 7.5×x3 rectangular lattice (Figure 1c,d).
This evidence is presented in Figure 5. Detection of off-
azimuth diffraction along the 〈11h 2〉 azimuth near the
position corresponding to the (-1,0) substrate diffraction
(heavy solid vertical line) is consistent with that expected
for a (5x3×x3)R30° overlayer lattice (solid vertical lines).
No evidence for peaks expected for a 7.5×x3 rectangular
lattice (dashed vertical lines) is observed.
There is another interesting observation involving low-
temperature deposition. When, after the initial 100 K
deposition, instead of raising the temperature directly to
300 K, the annealing is done incrementally, we find that
at temperatures of ∼180 K, diffraction consistent with a
7.5-fold periodicity first appears, eventually giving way
to the 8-fold periodic pattern at ∼260 K (see Figure 6).
This low-temperature-annealed structure has the same
periodicity as the “saturation-coverage” structure; how-
ever, it has an entirely different intensity distribution:
the “2/5-order” peak dominates in the 180 K-annealed case,
while it is the weakest of the first 5 orders of diffraction
in the 300 K-annealed case. While a quantitative
understanding of the diffraction intensity distribution is
presently beyond our capabilities, we can safely state that
the two structures clearly have different corrugations.
There are at least two possible explanations for the low-
temperature diffraction pattern: (1) it may correspond to
some sort of bilayer or multilayer structure or (2) it may
correspond to a monolayer similar in coverage and form
to the saturation-coverage structure, only in this case the
molecules are adsorbed physically to the surface, as the
needed activation energy has not yet been supplied to
induce chemisorption.16 Annealing to higher temperature
results in both chemisorption and desorption and, thus,
produces the lower-coverage 8-fold, striped structure. More
careful coverage-dependence studies, or combined helium
diffraction/X-ray photoelectron spectroscopy measure-
ments may yield additional insight into these issues.
SAM Striped Phases
Figure 2. (a) Helium atom diffraction from C6/Au(111) along
〈11h 0〉 azimuth. The C6 was deposited onto the surface at 100
K and annealed to 290 K. The solid vertical line on the left
marks the expected position for first order diffraction from a
simple hexagonal (x3×x3)R30° overlayer. The other solid
vertical line marks the position expected for a peak at ∆K//
equal to 3/5 times that for the (x3×x3)R30° first order peak,
i.e., a peak location consistent with diffraction expected from
a (5x3×x3)R30° adlayer. Instead, the data agree well with
peak positions expected for an 8×x3 lattice, which are marked
by dashed vertical lines. The incident wavevector, ki, was 5.24
Å-1, the crystal temperature, Tc, was 40 K, and the incident
angle, θi, was 61.26°. (b) Diffraction from C6/Au(111) along the
〈112h 〉 azimuth. The C6 was deposited onto the surface at 100
K and annealed to 290 K. The solid vertical lines mark the
expected positions for integer- and half-integer-order diffraction
with respect to the bare Au(111) surface lattice (the first order
is specifically labeled). The dashed vertical lines mark locations
of off-azimuth diffraction expected for a 8×x3 overlayer. The
excellent agreement of the data with the latter strongly supports
our assignment of the unit mesh. ki ) 4.84 Å-1; Tc ) 45 K, and
θi ) 61.26°.
(b) n-Decanethiol. High-quality diffraction patterns
have been obtained from n-decanethiol overlayers depos-
ited either by exposure of a room temperature crystal to
the thiol beam or by exposure of a cold (100 K) surface
followed by annealing to room temperature. The diffrac-
tion patterns obtained in these two cases are nearly
identical to each other. While we have not made a detailed
study of the response of these overlayers to annealing at
higher temperatures, we have observed that heating to
350 K results in an increase in the intensity of the
diffraction peaks.
Figure 7a is an example of diffraction from molecular-
beam-deposited C10/Au(111) taken along the 〈11 h 0〉 direc-
Langmuir, Vol. 12, No. 11, 1996 2741
Figure 3. Selected scans taken from the surface of C6/Au(111)
grown by molecular beam deposition at 316 K. With repeated
exposure, the pattern shifts from agreement with an 8×x3
lattice (marked by dashed lines) to agreement with a 7.5-fold
periodicity (actually a (5x3×x3)R30° lattice, marked by solid
lines). Since there are 5 orders of diffraction up to the peak
corresponding to first-order diffraction from a simple
(x3×x3)R30° overlayer lattice, we refer to the diffraction peaks
in trace d in terms of “1/5-order” diffraction. The predominant
peaks are the 1/5-, 3/5-, and 5/5-orders. Extra peaks half-way
between 1/5-order spacing are observed but may not indicate a
doubling of the unit mesh (see text and Figure 1a). 〈11h 0〉
azimuth, ki ) 4.84 Å-1; Tc ) 40 K, and θi ) 61.5°.
tion. Upon inspection of this diffraction pattern, our
attention is immediately drawn to three important
features: (1) while there is intensity near the positions
expected for a (x3×x3)R30° overlayer, the peaks in the
diffracted intensity are not in good agreement with those
positions, especially at the first order position, (2) the
diffraction features near the (x3×x3)R30° positions are
comprised of a series of diffraction peaks, and (3) there is
a progression of peaks very close to the specular, corre-
sponding to a relatively large real-space periodicity.
Figure 7b is a diffraction scan taken parallel to the 〈112h 〉
direction. Here we find diffraction peaks at spacings 1/2,
3/ , and 5/ times the spacing observed for a clean gold
2 2
substrate, indicating a doubling of the periodicity in the
〈112 h 〉 direction, i.e., a periodicity equal to x3 times the
gold-gold nearest neighbor spacing, dAu-Au. Figure 7c
provides an expanded look at the near-specular diffraction
along the 〈11h 0〉 azimuth from which we extract a periodicity
equal to (11 ( 0.5)×dAu-Au, or 31.7 ( 1.4 Å (average over
six samples). Therefore, the data are consistent with a
rectangular unit mesh with dimensions 11×x3 times
dAu-Au. This unit mesh is illustrated in both real and
reciprocal space in Figure 8.
The structure shown in Figure 8 is quite distinct from
the c(4x3×2x3)R30° structure obtained by conventional
self-assembly in solution. The observed lattice is identical
to the so-called “striped” phases found subsequent to
thermal treatment of solution-grown C10 monolayers (see
Figure 9). We also remind the reader that, as shown in
ref 13, that thermal treatment of C10 produces first a
(5x3×x3)R30° lattice (which corresponds to a p value of
2742 Langmuir, Vol. 12, No. 11, 1996
Figure 4. Selected scans taken from the surface of C6/Au(111)
grown by molecular beam deposition at 100 K followed by
annealing to 290 K. As in Figure 3, with repeated exposure the
pattern shifts from agreement with an 8×x3 lattice (marked
by dashed lines) to agreement with a 7.5-fold periodicity
(actually a (5x3×x3)R30° lattice, marked by solid lines). 〈11h 0〉
azimuth, ki ) 4.84 Å-1; Tc ) 45 K, and θi ) 61.37°.
Figure 5. Diffraction from the same monolayer as that in
Figure 4. These data were collected along the 〈112 h 〉 azimuth.
Close inspection of the region in the vicinity of the position
corresponding to first-order diffraction from bare Au(111)
(marked by the heavy vertical line) reveals agreement with a
(5x3×x3)R30° lattice (positions marked by solid lines) and no
evidence for a rectangular 7.5×x3 lattice (marked by dashed
lines). Also compare parts a and c of Figure 1. ki ) 4.84 Å-1;
Tc ) 45 K, and θi ) 61.08°.
7.5 as shown in Figure 1) followed later by the striped
phase.
(c) Other Chain Lengths. Finally, we report the most
recent results of measurements made on adlayers of C8,
C11 and C12.
n-Octanethiol was deposited onto Au(111) in the same
manner as C6 and C10, dosing at a surface temperature
of 100 K followed by annealing to room temperature to
Camillone et al.
Figure 6. Systematic annealing of a 100 K-deposited C6
overlayer. The top traces were collected subsequent to annealing
to 180 K, while the bottom trace was collected subsequent to
annealing to 260 K. With repeated annealing the pattern shifts
from agreement with a (5x3×x3)R30° lattice (marked by solid
lines) to an 8×x3 lattice (marked by dashed lines). Note the
predominance of the 2/5-order peak in the former case. 〈11h 0〉
azimuth, ki ) 4.84 Å-1; Tc ) 40 K, and θi ) 61.5°.
produce the pattern shown in Figure 10. This pattern is
well-described by a (9.4 ( 0.2)×x3 rectangular lattice
(average over five samples). Alternatively, the pattern is
consistent with an oblique unit mesh described by the
vectors a ) (0, x3×dAu-Au) and b ) (9.5×dAu-Au,
x3×dAu-Au/2), which is the simplest commensurate over-
layer lattice belonging to the family of structures com-
prised of stripes spaced at 9.5×dAu-Au. Similarly to the
case of C6/Au(111), we do not expect that we would be able
to easily distinguish between the two lattices.
The pattern for the C12 overlayer shown in Figure 10
was produced by in vacuo thermal treatment of a solution-
grown monolayer which initially displayed a well-
developed c(4x3×2x3)R30° diffraction pattern. Thermal
treatment consisted of repetitive cycling of the crystal to
increasingly higher temperatures in the vicinity of 100
°C. The pattern shown in the upper trace of Figure 10
was actually obtained subsequent to thermal treatment
followed by approximately 1 week at room temperature.
Similarly long reorganization times have been observed
previously for C10.13 The pattern in Figure 10 is in
excellent agreement with a periodicity described by a (13
( 0.3)×x3 unit mesh.
Finally, very recently, the thermal behavior of two
solution-grown C11 monolayers which initially showed a
c(4x3×2x3)R30° diffraction pattern was studied. Sub-
sequent to thermal cycling the monolayers to ∼180 °C
followed by about 2 days for one sample and 5 days for the
other sample at room temperature, a new diffraction
pattern was observed which can be described by an (11.8
( 0.8)×x3 unit mesh (data not shown).
Since a certain amount of “aging” at room temperature
has been found useful to observe the striped phase, we
feel it useful to summarize here the amount of times during
SAM Striped Phases
Figure 7. (a) Diffraction from the surface of C10/Au(111) grown
by molecular beam deposition. The vertical dashed lines mark
the expected peak locations for a simple hexagonal
(x3×x3)R30° overlayer, i.e., a periodicity equal to 1.5 × 2.885
Å. 〈11h 0〉 azimuth, ki ) 5.239 Å-1; Tc ) 45 K, and θi ) 61.36°.
(b) Diffraction from the surface of C10/Au(111) grown by
molecular beam deposition. The dashed lines mark expected
peak locations for a periodicity of x3 times the gold next-nearest-
neighbor spacing, i.e., x3 × 2.885 Å. Only the peak labeled
(-1,0) is observed in scans taken of the clean gold surface.
〈112h 〉 azimuth, ki ) 5.24 Å-1; Tc ) 45 K, and θi ) 61.71°. (c) An
expanded view of the near-specular region of the 〈11 h 0〉 diffraction
scan shown in (a). The dashed lines mark expected peak
locations for a periodicity equal to 11 gold nearest neighbor
spacings, i.e., 11 × 2.885 Å.
Langmuir, Vol. 12, No. 11, 1996 2743
Figure 8. (a) Reciprocal space diagram of diffraction from the
bare Au(111) surface (O) and from C10/Au(111) (b). Prior to
deposition, only the six equivalent first-order peaks (one is
marked (1,0)) are observed. Subsequent to deposition, half-
order peaks appear along the 〈112 h 〉 azimuth (vertical in the
figure), and a progression of closely spaced peaks appear along
the 〈11h 0〉 azimuth (horizontal). The reciprocal-space unit mesh
is outlined. This unit mesh corresponds to the real space unit
mesh outlined in (b).
Figure 9. A comparison of diffraction from the surface of C10/
Au(111) along the 〈11h 0〉 azimuth: (a) deposited from a molecular
beam and (b) deposited from solution and thermally treated in
vacuo. Both show close agreement with a periodicity that is 11
times the gold nearest-neighbor spacing which is marked by
the dashed lines. ki ) 5.24 Å-1; Tc ) (a) 40 K, (b) 45 K and θi
) (a) 61.47°, (b) 60.70°.
which the different monolayers have been observed since
it will provide the reader with a feeling about the reaching
of equilibrium and about the stability of these systems.
2744 Langmuir, Vol. 12, No. 11, 1996
Figure 10. Helium atom diffraction from Cn/Au(111) along
the 〈11h 0〉 azimuth. The C6, C8, and C10 layers were prepared by
molecular beam deposition and the C12 by partial desorption
of a solution grown monolayer. The intervals δ mark the
characteristic reciprocal lattice spacings, 2π/δ gives the real-
space distance between stripes. C6: ki ) 4.84 Å-1; Tc ) 40 K,
and θi ) 61.51°. C8: ki ) 4.84 Å-1; Tc ) 45 K, and θi ) 61.22°.
C10: ki ) 5.24 Å-1; Tc ) 45 K, and θi ) 60.72°. C12: ki ) 4.84
Å-1; Tc ) 45 K, and θi ) 61.36°.
Several films of C10, C11, and C12 have been found stable
in vacuum at room temperature for times of the order of
5 days. However on this time scale some increase in
specular intensity was observed which may indicate either
a small amount of evaporation or molecular diffusion on
the surface producing larger domains of bare gold. While
a study on the stability of the C6 films has not been carried
out in details, we have observed almost complete des-
orption in one of the samples at room temperature on the
same time scale. For C8, no stability observations were
made.
IV. Discussion
Taking the results for the five molecules, C6, C8, C10,
C11, and C12, together, and including both the present
results as well as those of the earlier thermal treatment
experiments, we find a linear relationship between the
periodicity of the diffraction pattern and the number of
carbons in the thiol (see Figure 11). The slope (0.83 (
0.04) is very nearly equal to twice the distance between
carbon atoms parallel to the molecular backbone (2.55 Å)
expressed in terms of gold lattice constants (2.55/2.885 )
0.884). Furthermore, for these so-called “striped” struc-
tures, the periodicity of the stripes is very nearly equal
to twice the overall length of the molecules forming the
overlayer which is consistent with the possibility that the
molecules are adsorbed as disulfides7b (see Table 1). The
coincidence of these numbers suggests that the striped
structures consist of thiols lying flat, i.e., with their axes
parallel to the gold surface, in a fashion similar to that
found by LEED for normal paraffin vapors deposited on
Pt(111)24 as well as to that found by STM for cyclic alkanes
(24) Firment, L. E.; Somorjai, G. A. J. Chem. Phys. 1977, 66, 2901.
Camillone et al.
Figure 11. A plot of observed periodicity (given in terms of
gold lattice spacings, p ) 2π/2.885δ) of the striped structures
vs the number of carbons in the molecules comprising the layer
(solid circles). The data represent measurements made for layers
prepared as follows: C6 and C8 - molecular beam deposition
only; C10 - molecular beam deposition as well as thermal
treatment; C11 and C12 - thermal treatment only. For the
(5x3×x3)R30° structure observed for C6 and C10, the distance
between equivalent rows is equal to 7.5 times the gold nearest-
neighbor spacing (open circles).
Table 1. Chain Length Dependence of the Lattice
Parameter p of the Striped Phase of SAMs
2π/δ (Å) fragment “disulfide”
n p (experiment) length (Å)a R1b length (Å)c R2d
6 7.9 ( 0.2 22.8 ( 0.6 11.8 1.93 22.1 1.03
8 9.4 ( 0.2 27.1 ( 0.6 14.4 1.88 27.3 0.99
10 11 ( 0.5 31.7 ( 1.4 16.95 1.87 32.4 0.98
11 11.8 ( 0.8 34 ( 2.3 18.25 1.86 35.0 0.97
12 13 ( 0.3 37.5 ( 0.9 19.5 1.92 37.5 1.00
a The length of the thiol fragment, assuming bond angles of 112°,
bond lengths of 1.541 Å for C-C, 1.81 Å for C-S, and 1.073 Å for
C-H, and van der Waals radii of 1.85 Å for sulfur and 1.2 Å for
hydrogen. b The ratio of the observed periodicity and the fragment
length. c The length of disulfide-like moiety at which the sulfur
head groups of the two thiolate fragments dimerized with S-S
length of 2.2 Å. d The ratio of the observed periodicity and the length
of the disulfide moiety.
on graphite.25 (The latter work includes images which
are very similar in appearance to those of Poirier et al.9,13,15)
Each unit mesh would therefore contain two thiols. This
would suggest that the coverage for these structures is
from 0.4 to 0.23 times that of the full-coverage
c(4x3×2x3)R30° phase (as the periodicity of the stripes
ranges from 7.5 to 13, respectively).
It would be, of course, interesting to explore the bonding
environment of the sulfur atoms in the striped phases
using the available methods of electron and X-ray
spectroscopy to confirm or contradict the presence of the
disulfide bonds.
Since we have no direct evidence that the molecules
indeed lie prone on the surface, we must consider other
alternatives. One possibility is that the periodicity of the
striped structures be a consequence of the variation of
adsorbate-adsorbate interaction strength as a function
of chain length. For the case of the thiols, the strength
of the adsorbate-adsorbate interaction varies linearly
with the number of carbons in the chains, so we could
expect, in principle, a linear relationship between the chain
(25) Wawkuschewski, A.; Cantow, H.-J.; Magonov, S. N. Langmuir
1993, 9, 2778.
SAM Striped Phases
Scheme 1. A Rudimentary Phase Diagram Showing
the Relationship among the Observed Phases of
Cn/Au(111) for n ) 6, 8, 10, 11, and 12a
a
The arrows indicate observed transitions.
length and the length scale of a superlattice modulation
responsible for the stripes. In this context, we note that
for all the structures measured the value of p is, within
experimental error, an integer or half-integer number.
Another possible explanation for the structure of the
low coverage phases is related to a quantization of the
magnitude of the tilt of the molecular axis from the surface
normal. It is known that as a consequence of the
interdigitation of methylene groups, hydrocarbon chains
prefer to pack with certain tilt angles and two-dimensional
packing densities,26 explaining why certain structures (in
particular the (5x3×x3)R30° phase) seem to be common
to a number of chain lengths. Interdigitation of closely-
packed methylene groups and tilt quantization have been
observed to result in displacement of chains along their
molecular axes in Langmuir-Blodgett films.27 Such a
displacement would have a marked effect on surface
corrugation and could explain the observed helium dif-
fraction patterns for the thiols on gold system. After
examining these alternative we feel, however, that the
flat-on-the-surface arrangement of the molecules is the
simplest and most likely explanation of our data.
An overall look at our results has led us to the
formulation of a graphic representation for the chain-
length-dependent and coverage-dependent phase behavior
presented in Scheme 1. The (5x3×x3)R30° structure
has so far been observed by us for both C6 and C10. Dubois
et al. observed this same structure for every even-
numbered chain length from C4 to C10.16 One could then
make the hypothesis that at very low coverages the
molecules lie flat and, as the coverage increases, that the
molecules pack more densely giving rise to the
(5x3×x3)R30° structure. This would happen to a critical
coverage where the molecules switch from a prone position
to an orientation directed more parallel to the surface
normal. Thus this particular structure would be common
to several chain lengths.
Neither Dubois et al. nor Poirier et al. observe the linear
relationship between periodicity and chain length de-
scribed here; rather Dubois et al. predominantly observe
the (5x3×x3)R30° structure16 and Poirier and Tarlov
observe a wide variety of periodicities.9,13,15 There are
several possible explanations for this: (1) the periodicity
varies with local coverage, to which the STM measure-
ments may be more sensitive than our technique which
averages over the whole surface, (2) some or all of the
measurements involve nonequilibrium structures, thus
the observations are strongly dependent on the exact
method of preparation of the adlayer and its thermal
(26) Outka, D. A.; Stöhr, J.; Rabe, J. P.; Swalen, J. D.; Rotermund,
H. H. Phys. Rev. Lett. 1987, 59, 1321.
(27) Schwartz, D. K.; Viswanathan, R.; Zasadzinski, J. A. N. Langmuir
1993, 9, 1384.
Langmuir, Vol. 12, No. 11, 1996 2745
history, or (3) the structures observed by us at 40 K differ
from those observed at near room temperature by Dubois
et al. and Poirier et al.
In any case all indications are that the phase vs coverage
behavior of these systems is quite complicated, and, for
a more complete understanding, may require further
study. For example, a grazing incidence X-ray diffraction
measurement of the inclination of the molecules in the
(5x3×x3)R30° structure would serve not only to specify
the structure more completely but also to shed additional
light on the issues raised in this discussion. While the
(5x3×x3)R30° phase has never been seen with grazing
incidence X-rays, by exposing a clean gold substrate to
decanethiol vapor at a background pressure 10-6 Torr,
c(4x3×2x3)R30° diffraction patterns have recently been
observed using this technique.28 The difference between
the present results and those obtained by X-rays may be
due to the substantially lower dosing rate used here.
Efforts are underway in both laboratories to prepare
monolayers under comparable conditions. The achieve-
ment of much larger deposition fluxes is hindered, in our
setup, by the unavoidable presence of the cryopumping
action of the liquid helium cryostat which supports the
bolometer helium beam detector. While background gas
deposition cannot be achieved under any circumstances,
we are presently building a shielded doser located much
nearer to the gold surface, which will be capable of
producing much larger impingement rates for the thiol
deposition.
V. Conclusions
We have shown that molecular beam deposition of
n-decane-, n-octane-, and n-hexanethiol on gold, at the
thiol flux on the order of 1011(1 molecules cm-2 s-1, does
not produce the c(4x3×2x3)R30° structure usually
observed for n-decane-7b,9,13 and n-octane-9 and n-hex-
anethiol9 saturation-coverage monolayers prepared by
self-assembly in solution. Rather, we observe the forma-
tion of striped structures characterized by rows of
molecules. These rows run parallel to the 〈112h 〉 direction
of the Au(111) substrate and the periodicity along the
rows is x3 times the gold nearest-neighbor distance. So
far our observations show that, at surface temperatures
of 40 K, the perpendicular distance between the rows scales
linearly with the length of the molecules which comprise
the adlayer and is, in fact, nearly equal to twice the overall
length of those molecules.
We have seen that molecular beam deposition of C10
results in an 11×x3 structure that is identical to that
ultimately produced by thermal treatment of a
c(4x3×2x3)R30° solution-grown monolayer. C6 has been
seen to form two structures: (1) 7.9×x3 at low coverage
and (2) (5x3×x3)R30° at higher coverage. The latter
has the same periodicity as an intermediate structure
observed for C10 in the thermal treatment experiments13
as well as the structures of a variety of chain lengths
prepared by background gas dosing by Dubois et al.16 The
recurrence of the (5x3×x3)R30° mesh in the different
chain length suggests that this structure may correspond
to a preferred packing density and (non-surface-parallel)
tilt angle at some intermediate coverage. The
(5x3×x3)R30° is bracketed on the one side by the full-
coverage c(4x3×2x3)R30° structure in which the mol-
ecules are tilted about 30° from the surface normal and
on the other side by the lowest coverage monolayers in
which the molecules lie parallel to the surface (as suggested
by the trend shown in Scheme 1). We expect, therefore,
(28) Eberhardt, A.; Fenter, P. Private communication.
2746 Langmuir, Vol. 12, No. 11, 1996
that the “striped” phases are the result of increasing
molecular tilt with decreasing coverage.
The wide variety of periodicities observed by us and
others suggests that the periodicity of the stripes (and,
probably, therefore, the tilt angle) depends on coverage,
chain-length, and thermal history. Once they have been
fully explored, the rich phase diagrams of these intriguing
systems will provide an excellent testing ground for theory.
If intermolecular force field and molecular-dynamics code
can be developed to a level where they are capable of
reproducing this rich variety of structures, it is reasonable
to expect that they will also be able to accurately describe
the properties of cell membranes and other “solution”
Camillone et al.
structures which, by their own nature, cannot provide us
with structural data of equivalent precision.
Acknowledgments. We acknowledge the fruitful
discussions with A. Eberhardt, P. Fenter, and G. Poirier
and Terri Cummings for her participation in the recent
measurements. We also thank Professor C. Chidsey for
giving us the undecanethiol sample used in the measure-
ments. This work has been supported by the Materials
Science Program of the Office of Basic Energy Sciences of
DOE under Grant DE-FG02-93ER45503.
LA951097J