Langmuir 2007, 23, 509-516 509

Gold Film Surface Preparation for Self-Assembled Monolayer Studies

Jing Kang and Paul A. Rowntree*
Department of Chemistry, UniVersity of Guelph, Guelph, Ontario, Canada N1G 2W1

ReceiVed July 11, 2005. In Final Form: September 14, 2006

Evaporated gold films are frequently used as substrates for the study of biomolecular adsorbates, nanoparticle
systems, amd partial and full monolayer films. These studies often benefit from a predeposition cleaning of the surface
that removes adventitiously adsorbed material from laboratory contaminants. Scanning tunneling microscopy (STM)
is used in this study to explore the microscopic consequences of two pretreatment protocols used in literature reports
of self-assembled monolayers, based on sulfochromic and piranha acid solutions. These measurements show that
treatment of the Au/mica surface with piranha acid can lead to extensive and uncontrolled etching of the surface and
severe disruption of the surface topography; extended exposure causes the precipitation of crystallites on the surface
that are highly mobile during STM imaging processes. Exposure of Au/mica surfaces to sulfochromic acid leads to
the formation of permanent etch pits of the surface that are exclusively one Au layer deep; extended exposure leads
to progressive etching and oxidation of the surface, ultimately leading to the formation of 0.33-0.36 nm high islands
on the otherwise flat Au/mica surface. The piranha acid solutions are significantly more likely to cause the Au film
to delaminate from the mica support than are the sulfochromic acid solutions. These results show that sulfochromic
surface preparation is a direct and reliable method for the elimination of organic residues from Au(111)-textured
surfaces, while causing a minimum of structural and chemical surface damage.

Introduction growing number of works employ other crystalline faces3-5 (and

Ultraflat metal surfaces have applications in a wide variety of
technological and surface science related studies ranging from
device fabrication to adsorption studies. The key requirements
for these applications include surface uniformity, cleanliness,
and structural integrity. Modern diffraction and scanning probe
surface studies impose few constraints on the sample dimensions,
and state-of-the-art measurements with these techniques often
use single-crystal surfaces, with the resulting uniformity of surface
structure that this entails. However, quantitative structural
investigations of the surface and subsurface regions of adsorbed
films that are performed with grazing incidence infrared
reflection-absorption spectroscopy (IR-RAS) benefit by the use
of relatively large samples extending along the direction of
propagation of the IR beam; for example, with the commonly
used incident angle of 85° from the surface normal, the full
projection of a ∼7 mm diameter IR beam onto the substrate
produces an illuminated ellipse with a long axis of ∼80 mm. In
the case of IR-RAS spectra of weakly absorbing or submonolayer
species, it is clearly advantageous to employ large samples of
as high quality as possible to maximize the absolute differences
in the reflected intensities caused by the presence of the adsorbates.
In all quantitative analyses, it is absolutely essential to minimize
the quantity of adventitiously adsorbed impurities on this surface,
since such species may impede the adsorption of the film
constituents, as well as interfere with the spectral analysis of the
data.
The study of self-assembled organic monolayers1,2 deposited
onto Au(111) surfaces is a rapidly growing application of thin
film substrates. In these studies, organic species are chemisorbed
to the Au surface by a terminal thiol group, presumably with the
simultaneous evolution of molecular hydrogen; although a
* To whom correspondence should be addressed. E-mail: Rowntree@
UoGuelph.ca.
(1) Porter, M. D.; Bright, T. B.; Allara, D. L.; Chidsey, C. E. D. J. Am. Chem.
Soc. 1987, 109, 3559.
(2) Bain, C. D.; Troughton, E. B.; Tao, Y.-T.; Evall, J.; Whitesides, G. M.;
Nuzzo, R. G. J. Am. Chem. Soc. 1989, 111, 321.
occasionally other substrate metals6,7), the vast majority of
published studies are based on thiols adsorbed on Au(111)
surfaces:
R-SH + Au(111) f R-S-Au(111) + 1/2H2
The most common preparative method involves immersion of
the Au surfaces into ∼10-3 M solutions of the selected thiol in
an appropriate solvent (usually ethanol or methanol) for ∼24 h.
Working solutions at these concentrations contain many orders
of magnitude of excess thiol with respect to the saturation surface
coverage of 4.6 × 1014 molecules/cm2 (∼7.6 × 10-10 mol/cm2)
calculated for a x3×x3R30° superlattice of the Au(111) surface
structure. Self-assembled monolayers (SAMs) prepared in this
manner have been shown to be highly structured and well ordered
and have been extensively studied using infrared,1,8 scanning
probe,9-11 electrochemical,12,13 and diffraction3,5,14-17 methods.
Several thin film substrates have been employed for the study
of the chemisorbed thiol systems, most notably Au/Cr/Si, Au/
mica, and Au/glass; Hegner et al.18 have shown that the surfaces
(3) Camillone, N., III; Chidsey, C. E. D.; Liu, G.-Y.; Scoles, G. J. Chem. Phys.
1993, 98, 4234.
(4) Poirier, G. E. J. Vac. Sci. Technol. 1996, B14, 1453.
(5) Dubois, L. H.; Zegarski, B. R.; Nuzzo, R. G. J. Chem. Phys. 1993, 98, 678.
(6) Bensebaa, F.; Ellis, T. H.; Badia, A.; Lennox, R. B. J. Vac. Sci. Technol.
1995, A13, 1331.
(7) Bryant, M. A.; Pemberton, J. E. J. Am. Chem. Soc. 1991, 113, 8284.
(8) Truong, K. D.; Rowntree, P. A. J. Phys. Chem. 1996, 100, 19917.
(9) Widrig, C. A.; Alves, C. A.; Porter, M. D. J. Am. Chem. Soc. 1991, 113,
2805.
(10) Poirier, G. E.; Tarlov, M. J. J. Phys. Chem. 1995, 99, 10966.
(11) Kang, J.; Rowntree, P. Langmuir 1996, 12, 2813.
(12) Chidsey, C. E. D. Science 1991, 251, 919.
(13) Widrig, C. A.; Chung, C.; Porter, M. D. J. Electroanal. Chem. 1991, 310,
335.
(14) Chidsey, C. E. D.; Liu, G.-Y.; Rowntree, P.; Scoles, G. J. Chem. Phys.
1989, 91, 4421.
(15) Fenter, P.; Eberhardt, A.; Eisenberger, P. Science 1994, 266, 1216.
(16) Camillone, N., III; Chidsey, C. E. D.; Liu, G.-Y.; Scoles, G. J. Chem.
Phys. 1993, 98, 3503.
(17) 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.

10.1021/la0518804 CCC: $37.00 © 2007 American Chemical Society

Published on Web 12/08/2006
510 Langmuir, Vol. 23, No. 2, 2007
of “template-stripped” Au/mica samples (in which the experi-
mental surface is that which was deposited directly onto the
mica, rather than the exterior surface of the ∼100-150 nm thick
metal film) can also provide large flat surfaces for surface
adsorption studies, most notably of biomolecular species such
as DNA and proteins. Au/mica substrates remain widely used
because of the ease of preparation, the extremely flat surfaces,
and the absence of “binder” layers (e.g., Cr) that can diffuse into
the Au films. In our efforts to optimize Au/mica substrate
preparation methods, we have found that sample quality and
reproducibility are sensitive to both the quality of the substrate
and the presence of organic impurities on the surface. Short-
chain alkanethiols are particularly sensitive to the substrate quality,
due to the relatively weak intermolecular forces that stabilize the
3D structure of the system;19 our STM measurements of
butanethiol/Au have shown that the lowest energy c(4 × 2)
reconstruction of the monolayer structure19 requires the coopera-
tive organization of at least 103 molecules in a single defect-free
domain (∼300 nm2),20 which imposes severe constraints on the
defect density of the substrate and on the sample preparation
procedures. The susceptibility of Au substrates to organic
contamination has been documented2 using ellipsometry; it is
often presumed that weakly adsorbed organic species from the
ambient environment of the laboratory will eventually be
displaced2 by the strongly binding (∼44 kcal/mol21) thiolates.
The situation is more complicated in the case of submonolayer
film formation or studies of film deposition dynamics; in the
case of deposition conditions without large excesses of thiol in
solution, it is not certain that the thiol adsorption will quantitatively
remove all contaminants from the surface, nor at what rate. In
the study of the temporal evolution of the absorption spectra, the
kinetics for thiol adsorption2,8,22,23 will be influenced by the
kinetics for the displacement of the contaminants, thus affecting
the reproducibility (and physical interpretation) of the time scales
measured. Furthermore, in the case of submonolayers of short-
chain alkanethiolates, the infrared spectrum for the chemisorbed
adsorbates is necessarily weak (<1 milli absorbance unit (mAU)),
and this can be easily overwhelmed by the optical absorbances
of larger hydrocarbon species that may be physisorbed to the
surface, even in low abundances. This is particularly problematic
in the aliphatic C-H stretch region of the IR spectrum (2800-
3000 cm-1) where most hydrocarbon species have strongly
overlapping absorbance bands.
These requirements have led us to explore preparation methods
by which the surfaces can be reliably cleaned without introducing
extensive surface damage that interferes with molecular adsorption
or that may compromise the quality of the final adsorbed film.
In this paper we report the effects of acidic (oxidizing) solutions
(in the absence of specific etchants such as Cl- and CN-) on the
surface topologies of Au/mica films. The first method uses
“piranha acid” solutions (heretofore referred to as P), as proposed
by several papers on SAM formation;22-24 the second procedure
uses sulfochromic acid (chromium trioxide/H2SO4, heretofore
referred to as S). Although both solutions can remove organic
surface impurities via oxidation (as observed using infrared
spectroscopy), results of this study show that P treatments can
cause delamination of the Au/mica interface and the introduction
of pinholes into the gold layer. Most importantly, the scanning
(18) Hegner, M.; Wagner, P.; Semenza, G. Surf. Sci. 1993, 291, 39.
(19) Zhang, L.; Goddard, W. A., III; Jiang, S. J. Chem. Phys. 2002, 117, 7342.
(20) Paradis, E.; Rowntree, P. J. Electroanal. Chem. 2003, 550-551, 175.
(21) Sellers, H.; Ulman, A.; Shnidman, Y.; Eilers, J. E. J. Am. Chem. Soc.
1993, 115, 9389.
(22) Pan, W.; Durning, C. J.; Turro, N. J. Langmuir 1996, 12, 4469.
(23) Karpovich, D. S.; Blanchard, G. J. Langmuir 1994, 10, 3315.
(24) Anderson, M. R.; Evaniak, M. N.; Zhang, M. Langmuir 1996, 12, 2327.
Kang and Rowntree
tunneling microscopy (STM) results presented herein show that
P can cause significant and uncontrolled damage to the surface
topography of the surface; this damage would lead to poor
reproducibility in the adsorption of submonolayers, due to the
large defect density of the Au substrate. This is in sharp contrast
to the minor and controllable substrate modifications induced by
S. Adoption of the S-based cleaning procedure has resulted in
a significant improvement in the reproducibility of our infrared
data of chemisorbed organic films as compared to as-deposited
Au/mica substrates, especially with submonolayer coverages of
systems whose optical absorbances are weak.8 In view of the
increasing number of structurally detailed studies and applications
of self-assembled monolayers, the use of a reliable preparation
procedure that preserves the structural integrity of the substrate
is highly desirable.
Experimental Section
Procedure A. Au/mica deposition was performed following the
method described by DeRose et al. Freshly cleaved muscovite mica
(TechniGlas/ProScience, ASTM V-2) was placed in an all-metal
evaporation chamber and the system evacuated for several hours
using a 170 L/s turbomolecular pump. The mica surfaces were heated
to 300-350 °C for 6-12 h to degas the substrates and the chamber
walls; the upper temperature limit for this heating cycle is imposed
by the stability of the mica, with higher temperatures leading to a
visibly “fractured” surface. A 100-150 nm film of gold (Johnson-
Mathey, 99.999%) was thermally evaporated from a resistively heated
tungsten boat onto the mica substrate at a rate of ∼0.1 nm/s. The
Au/mica substrates were annealed in a vacuum for another 1-4 h,
leading to large terraces of Au surfaces; as described elsewhere, the
surfaces of these substrates are strongly Au(111) textured.25 STM
images of these films show the anticipated Au(111) planar structure
with lateral terrace dimensions of 100-200 nm; we frequently observe
the 23 × x3 reconstruction of the Au(111) surface, again showing
that these surfaces are well-structured. Samples were stored in sealed
polycarbonate dishes under Ar prior to use.
Procedure B. STM images were obtained using a home-built
STM instrument based on a four-quadrant piezoelectric tube scanner
and an analogue electronic control system. Tips were prepared by
electrochemical etching of Pt/Ir wire in a 2 N KOH/6 N KCN solution
or of W wire in 1 N NaOH; no significant differences were observed
using the different tip materials, although the yield of Pt/Ir tips was
slightly greater than that of the W wire. The lateral sensitivity of
the scanner was calibrated using atomically resolved images of HOPG
graphite (Advanced Ceramics/XYB grade), while the vertical
sensitivity was calibrated using the 0.236 nm step height of the
Au(111)/mica surface. The uncertainty of the lateral calibration on
small scan areas is 1-5% and is due principally to the slight
nonorthogonality of the X and Y electrodes of the scan tube. All
images presented herein were obtained in the constant-current mode
(0.03-1 nA tunneling current, 0.1-1.0 V sample bias) and are
conventionally shaded with darker regions corresponding to lower
surface elevations. No filtering has been applied to these images;
digital background plane subtraction has been used to make the
terraced structures of the gold films more clearly visible. In all
cases, images obtained during the return sweep of the tip across the
surface were identical to those presented here, with no evidence of
double tips or other imaging artifacts.
Procedure C. IR-RAS spectra were measured with a commercial
optical bench (Nicolet Magna 550/560) using a grazing incidence
reflection accessory (Harrick) installed within the spectrometer and
a double-diamond polarizer or coupled to a UHV system without
the polarizer. The plane-parallel modulated beam from the bench
was focused and directed to the surface with an incident angle of
85° from the surface normal. Data were measured using a moving
mirror velocity of 1.98 cm/s and a resolution of 1.0 cm-1. For spectra
(25) DeRose, J. A.; Thundat, T.; Nagahara, L. A.; Lindsay, S. M. Surf. Sci.
1991, 256, 102.
Gold Film Surface Preparation for SAM Studies
Figure 1. STM image of a freshly prepared Au/mica surface (scan
size 100 nm × 100 nm, z range is 0.8 nm).
presented herein, the background scan was collected as the reflectance
data using freshly cleaned Au/mica.
Procedure D. P was prepared by addition of 1 part 30% H2O2
(Anachemia, <2 ppm Cl-) to 4 parts concentrated H2SO4 (BDH/
ACS grade). Warning: Piranha acid solutions react Violently with
many organic materials and should be handled with great care! S
solutions were prepared by dissolution of 5 mL of Chromerge (anisole,
Anachemia) in 4.0 L of concentrated H2SO4 (BDH, ACS grade). All
solutions were stored in glass containers prior to use. Solutions that
showed any evidence of suspended solids or abnormal coloration
following refrigeration were discarded, although we have noted that
the optical density of S can vary by a factor of 2 among the various
preparations; more highly colored S solutions were found to produce
slightly accelerated surface etching. Both acid solutions were
employed in the same manner: Au/mica slides (2.5 cm × 10 cm)
were secured horizontally by the edges of the mica substrate, and
the cleaning solution was applied to the upward facing Au surface.
The surfaces were exposed to the acid solutions for 30 s to 15 min,
after which time the acid was removed, and the surfaces were rinsed
with copious quantities of ultrapure H2O (Millipore Nanopure, R )
18 MΩ‚cm, Milli-Q UV-conditioned). The samples were then rinsed
in freshly distilled methanol and dried under a gentle stream of dry
N2 prior to characterization by STM or IR-RAS. We have observed
the surface modifications of the P-treated surfaces with at least 10
Au/mica substrates and three P preparations, while the effects of S
have been observed with approximately 50 Au/mica samples and
10 S preparations.
Results and Discussion
Figure 1 shows a 100 nm × 100 nm STM image of a freshly
prepared Au/mica surface. As expected, the surface is composed
of terrace-topped Au domains of 75-200 nm lateral extent,
separated by grain boundaries ∼15 nm across and several
nanometers deep. Previous X-ray diffraction studies have
shown26,27 that these individual domains are composed of Au
crystallites, with the exposed terrace surfaces showing largely
Au(111) texture. Close inspection of the flat terraces frequently
reveals the 23 × x3 reconstruction that is characteristic of well-
(26) Chidsey, C. E. D.; Loiacono, D. N.; Sleator, T.; Nakahara, S. Surf. Sci.
1988, 200, 45.
(27) Reichelt, K.; Lutz, H. O. J. Cryst. Growth 1971, 10, 103.
Langmuir, Vol. 23, No. 2, 2007 511
Figure 2. STM images of Au/mica films after progressive exposure
to P solutions. Exposure time: (a) 30 s, (b) 60 s, (c) 135 s, (d) 195
s. Scan size: (a-c) 150 nm × 150 nm, (d) 300 nm × 300 nm. z
range: (a-c) 1.4 nm, (d) 2.5 nm.
prepared Au(111) surfaces.28,29 This topography is consistently
observed using the evaporation of Au onto heated freshly cleaved
mica surfaces. These freshly prepared surface structures are
exceedingly stable and show no tendency to be displaced by the
scanning action of the tip under the present experimental
conditions or by spontaneous diffusion; Holland-Moritz et al.
have shown that structural instabilities of Au/mica surfaces during
imaging can be caused by hydrocarbon contamination of the
vacuum environment used for Au deposition.31 In the case of
gross organic contamination (e.g., oil from diffusion-pumped
systems), the topography of the Au/mica surface can become
highly convoluted and irregular, without well-defined flat regions
of Au(111) texture. Images taken of Au/mica exposed to pure
concentrated H2SO4 are indistinguishable from that of Figure 1,
with no evidence of surface modifications or enhanced step
mobility. Pure concentrated H2SO4 had a negligible effect on the
infrared absorption bands of adsorbed hydrocarbon contaminants.
Parts a-d of Figure 2 show the Au/mica topography produced
by progressively longer exposure to the P acid solutions (recall
that every acid treatment stage was followed by extensive rinsing
in ultrapure water); images a-c are 150 nm × 150 nm, while
image d is 300 nm × 300 nm. A 30 s exposure (Figure 2a) leads
to the formation of isolated islandlike features on the Au(111)
terraces. These near-circular flat-topped features are typically
less than ∼10 nm in diameter, with heights that correspond closely
to the step height of the Au(111) surface (0.24 ( 0.023 nm,
based on 26 individual measurements on 4 substrates). These
islands appear to be randomly distributed across the Au surface,
with no apparent preference for edges. The vertical dimensions
of these features strongly suggest that they are Au islands arranged
in layers one atom high to produce a Au(111)-textured structure;
the lateral dimensions correspond to collections of ∼1000 atoms
per island. The edges of the large terrace structures are frequently
(28) Barth, J. V.; Burne, H.; Ertl, G.; Behm, R. J. Phys. ReV. 1990, B42, 9307.
(29) Harten, U.; Lahee, A. M.; Toennies, J. P.; Wöll, Ch. Phys. ReV. Lett. 1985,
54, 2619.
(30) Hasegawa, Y.; Avouris, Ph. Science 1992, 258, 1763.
(31) Holland-Moritz, E.; Ii, J. G.; Borges, G.; Sonnenfeld, R. Langmuir 1991,
7, 301.
512 Langmuir, Vol. 23, No. 2, 2007
more convoluted than found with “as-deposited” Au films,
indicating that the surface has been eroded by the exposure to
P, presumably by an oxidation process that leads to preferential
substrate dissolution from step edges. Occasionally, the substrate
dissolution can start at points other than the step edges, creating
atomic holes on the terraces. It can be imagined that the islands
on the surface either are additional material that has been deposited
onto the Au terraces or may be the remains of an almost completely
removed layer. We favor the former possibility, since it is unlikely
that the highly aggressive P solutions (see below) would cleanly
remove almost a complete Au layer with minimal (or no) etching
into additional layers of the surface. At this stage of the evolution,
it is unusual to find other forms of surface modifications.
After 60 s of exposure, the Au surface topography is
dramatically different (Figure 2b). The step edges of the large
terrace structures have become much rougher than before,
indicating the rapid progress of the P etching. More one-atom-
deep holes appear in the middle of the large terraces, with lateral
dimensions of ∼5-15 nm. The edges of the larger holes and the
edges of the large terrace structures are significantly rougher
than shown in Figure 2a. Meantime, the smaller holes have
relatively smooth edges, consistent with the observation that the
progressive etching preferentially starts at step edges. The near-
circular islands are no longer found on the surfaces; in their
place, we find that numerous elongated objects are distributed
randomly on the topmost gold layer, with lengths of ∼5-15 nm
and widths of ∼2-3 nm. The heights of these objects are 0.3-
0.7 nm, which does not correspond to integer multiples of the
fundamental step height of the Au(111) surface. No preferential
orientation for these objects with respect to the substrate or scan
direction was observed. It is possible that the islands in Figure
2a are the favorable sites for later depositions from the solutions
to form noncrystalline three-dimensional aggregates. We do not
believe that these three-dimensional objects are directly deposited
“as is” from solution since they are never observed during the
initial stages of Au(111) exposure to the P solutions. Furthermore,
the size distribution of these objects is clearly a function of time,
as shown below. The sticklike objects are reproducibly observed
even when direct contact between the P solution and the mica
edges of the gold film is avoided, demonstrating that the observed
structures are not silicates or aluminates removed from the mineral
substrates.
The surface morphology continues to degrade during extended
exposure of the Au surface to the P solution. A ∼140 s acid
exposure leads to “cigarlike” objects as shown in Figure 2c.
These objects are distributed on the surface randomly, with no
objects appearing to cross step edges. The measurements of the
vertical dimension show that they are ∼0.5-1.0 nm high (i.e.,
∼0.2-0.3 nm higher than the objects in Figure 2b), indicating
continuing deposition onto the preexisting structures. It is
interesting to note that the size distribution of these particles is
remarkably narrow, with typical length:width:height ratios of
∼10:2:1. This anisotropic three-dimensional growth is in clear
contrast with the normal two-dimensional growth of gold on
gold and indicates that the composition of the particles differs
significantly from that of the substrate. Figure 2d is a typical
large-scale (300 nm × 300 nm) image of the Au surface after
195 s of P etching. The objects on the surface are progressively
larger and higher, ∼10-25 nm in length and ∼0.7-0.9 nm in
height. Moreover, the scanning process now clearly mechanically
destabilizes these larger objects; the center region of this image
(within the marked frame) has fewer structures because previous
imaging in this region has displaced many of them. In these later
stages, the etching principally took place on the middle of the
Kang and Rowntree
terraces rather than the step edges, as indicated by the relatively
smooth step edges and numerous etching holes on the terraces.
This leads us to propose that the gold aggregates and the terrace
edges have been chemically modified (perhaps oxidized), but
this needs to be confirmed by further study with spectroscopic
methods such as ESCA.
The infrared results for P-treated Au/mica surfaces are not
encouraging. Due to the very weak adhesion of epitaxially grown
gold to mica surfaces, these films are relatively fragile with respect
to loss of metal film integrity; Au/SiOx surfaces and Au/Cr/SiOx
systems are significantly more robust, yet less uniform. P
treatment often leads to at least partial delamination at the Au-
mica interface within ∼2-5 min, such that there are significant
portions of the mica exposed in small pinhole perforations or by
blister formation. Karpovich and Blanchard23 have found that
gold electrodes deposited onto quartz microbalance crystals are
also damaged by prolonged exposure to P solutions, such that
individual crystals could only be used for about three experiments.
Pinhole defects in the P-treated Au/mica surfaces produce
significant background oscillations in the infrared reflectivity
due to multiple internal reflections in the thin mica substrates.
The magnitude of these oscillations can easily exceed the ∼1-5
mAU normally measured with organic monolayers. Among the
gold films that remain well-secured to the mica substrates (i.e.,
with very short exposures to P), the infrared spectra typically
show that the optical absorbance of adventitiously adsorbed
hydrocarbon contaminants in the 2800-3000 cm-1 C-H stretch
region remains ∼1-2 mAU and is therefore unacceptably high
for low-coverage work.
These results show that the P-based cleaning process is
aggressive and difficult to control. While exposed to P solutions,
the Au(111) surfaces change their morphology quickly and usually
develop numerous adsorbed particles with heights several times
larger than the monatomic step height of Au(111) surface. The
anisotropic structure of these aggregates strongly suggests that
the forces binding the objects to the surface are significantly
weaker than the cohesion forces within the aggregate and that
these particles are not pure gold. These surfaces are obviously
unacceptable for deposition studies. For these reasons, we have
explored (and adopted) the use of S solutions to remove organic
contaminations; we have found that the surface etching process
of the Au/mica surfaces is far more controlled and less aggressive
than that in P solutions. Figure 3 presents a similar series of
images measured for progressively longer contact times of S
with the Au/mica surface; images a and b are 200 nm × 200 nm,
image c is 100 nm × 100 nm, and image d is 300 nm × 300 nm.
Figure 3a shows the topology of the Au/mica surface after 1 min
of S etching. The large, flat terraces of the Au(111) surface are
still clearly visible, with one-atom-deep etching pits spreading
on them. Unlike P treatment, there is apparently no preferential
step etching of gold in S solutions, as indicated by the relatively
smooth step edges and the striking differences between Figures
2a and 3a. It is possible that if such edge etch sites were created,
they could be rapidly refilled if there were a sufficiently large
number of mobile gold atoms available. However, the mechanical
stability of the Au/mica surfaces at this stage (as evidenced by
a lack of imaging-related structural changes, regardless of the
tunneling resistance in the 500-3000 MΩ regime) indicates that
there are very few mobile gold atoms at this point and that the
step edges are relatively insensitive to the S solution. The etch
pits are irregularly shaped, with no specific orientations observed
with respect to the crystal lattice, as was reported for Au(111)
surface reactions with aqueous CN-.32 The pits have a mean
(32) McCarley, R. L.; Bard, A. J. J. Phys. Chem. 1992, 96, 7410.
Gold Film Surface Preparation for SAM Studies
Figure 3. STM images of Au/mica films after progressive exposure
to S solutions. Exposure time: (a) 60 s, (b) 120 s, (c) 300 s, (d) 600
s. Scan size: (a, b) 200 nm × 200 nm, (c) 100 nm × 100 nm, (d)
300 nm × 300 nm. z range: (a) 2.5 nm, (b) 4.0 nm, (c, d) 0.8 nm.
Regions identified in (d) by arrows have elevations of ∼0.12-0.16
nm above the terrace. (a) is adapted from ref 8.
diameter of ∼5 nm, and remarkably, they are exclusiVely one
atom deep (i.e., there are no “holes in holes”). They are almost
uniformly distributed on the topmost terraces, with a slightly
reduced propensity for pit formation on terraces above the step
edges. Analysis of frame 1 of Figure 3a showed that the pits
cover an area of ∼10% of this terrace area. Although these pits
appear to be quasi-randomly distributed across the topmost layers,
this is clearly not true for successively lower levels of the
topography. For example, the lower terrace in frame 2 of Figure
3a (five gold step levels below frame 1) has significantly fewer
etching holes near the steep step edges leading up to the main
terrace region. The pits in these lower surface regions remain
one atom deep, but the mean diameter is now ∼2-3 nm and
smaller yet for pits located near the step edges. Furthermore,
there are virtually no etching pits in the trench area on the terraces
at still lower elevations as shown in frame 3 of Figure 3a (six
to nine step levels below frame 1). These propensities have been
reproducibly observed for many Au/mica surfaces and several
S preparations. It is interesting to note that although P-treated
Au/mica shows extensive deposition of island structures within
30 s (Figure 2a), no additional material deposition was observed
on S-treated gold surfaces in the first ∼5 min of exposure. One
possible explanation is that the dissolved gold is better solvated
by the chromic acid solution and is therefore less reactive to the
gold surface in S solutions than when dissolved in P solutions.
These solvated species would remain in S solutions and not
return to the surface, preserving the well-defined surface
morphology.
If the exposure time is extended to 2 min, these small etching
pits grow to have lateral dimensions ranging from several
nanometers to dozens of nanometers (Figure 3b). The depth of
these holes remains equal to the 0.236 nm Au(111) step height.
Since there is still no preferential etching at the step edges, we
believe that these larger holes result from the aggregation of the
randomly distributed smaller etching pits shown in Figure 3a.
The dissolved portion has increased to about 50% of the total
Langmuir, Vol. 23, No. 2, 2007 513
surface area, leading to a “netlike” appearance. The anisotropic
etching rates of the various surface terraces are also shown in
this image, as observed previously in Figure 3a. The trench area
within the identified region is 5-8 atomic levels below the main
terrace structure, and it has a significantly lower etching rate
than other parts, as indicated by fewer etching pits found in the
deeper regions of the Au/mica surface. We consistently find that
there are fewer etching pits for the steeper steps leading down
to narrow trench regions. Apparently, the geometry of the surface
structure leads to this anisotropic surface etching. There are two
possibilities for this observation: (1) since the trench area is
formed as a nearly closed basin with ∼1-3 nm height, the
diffusion of the acid may be reduced in this region, leading to
reduced dissolution, or (2) there may be some residual air trapped
in this trench area while the acid covers the surface, and this may
retard the wetting of the surface by the acid, thus retarding the
etching procedure. The absence of holes in holes in all of these
images is consistent with this observed anisotropic etching, since
each hole can be regarded as a very small trench.
The surface morphology continues to evolve after 5 min of
etching in S solutions as shown in Figure 3c. The etch pits have
continued their aggregation/growth, breaking many links of the
netlike structures and leading to highly convoluted topologies.
It is difficult to measure how much of the Au layer was dissolved
at this stage because near the steps, the second layer which was
completely exposed after etching cannot be distinguished from
the other parts of the same terrace. Surprisingly, the step heights
of these structures are not uniform; although some are less than
or equal to the Au(111) step height, most varied from 0.28 to
0.31 nm. This is the first evidence of a chemical modification
within the surface layers; specifically adsorbed anions or
physisorbed species on the surface would be found with equal
probability on and within the net structures, leading to no
discernible variations in step height. It can be imagined that the
chemical modification (e.g., oxidation) of the surface results in
a physically different step height, or it may modify the electronic
structure of the surface to decrease the barrier to electron-
tunneling, thus increasing the junction width (i.e., the probe height)
in a constant-current imaging mode. However, we note that the
work function of the oxidized surface would be greater than that
of the pure gold surface, thus decreasing the tunneling probability
for a fixed tip-surface separation and causing the tip to approach
the surface more closely for a fixed tunnel current; we observe
the opposite behavior. We thus conclude that the apparent height
increase of the netlike structures above the sublevel gold planes
is the result of a topographically thicker single-layer structure,
presumably due to the incorporation of oxygen into the gold
lattice; it is highly unlikely that it is an underestimated thickness
of a bilayer structure, since as discussed above, we have never
observed hole-in-hole structures that would be required to produce
such bilayer structures.
Increased exposure to S solutions can result in a more complete
and highly anisotropic dissolution of the Au(111) surface. Figure
3d shows that although most of the top terraces have been
dissolved after ∼10 min of exposure to the S solution, the etching
does not continue into the sublayers; this results in a highly
planar topography with small isolated islandlike structures. These
structures are nearly circular, with typical diameters of ∼10-15
nm. Although this topography appears to be very similar to that
produced by very short exposure of the Au/mica surfaces to P
solutions (Figure 2a), the vertical dimensions of these surfaces
are significantly and systematically different in three aspects.
First, the islands are 0.33-0.36 nm high, which is 40-50%
higher than the Au(111) step height. This height discrepancy
514 Langmuir, Vol. 23, No. 2, 2007
cannot be the result of calibration error, since the vertical
calibration uncertainty of the scanner is better than 5% and images
of freshly prepared Au(111) surfaces measured immediately
before and after these experiments found the expected 0.24 nm
vertical step height. The progressively increasing height of the
superstructures confirms that these island structures are the result
of the continued erosion of the netlike structures shown in Figure
3b,c, rather than being the result of material deposition from
solution onto the gold surface, as postulated for the initial stages
of the P-etching process shown in Figure 2a. The second difference
with respect to Figure 2a (and with respect to fresh Au/mica
surfaces) is the presence of small protrusions on the surface with
elevations of only ∼0.12-0.16 nm; examples of these structures
are identified with the arrows and outlines in Figure 3d. Although
small, irregular, and never comprising more than ∼5% of the
total surface area, these features are very reproducible and are
equally visible in data taken on the reverse passage of the STM
tip across the surface. The tunneling current (measured simul-
taneously with the topographic data) shows no anomalous
behavior that would indicate an unstable tunneling junction in
these regions. Third, it is interesting to note that the topmost
terrace of Figure 3d is separated from the next-lower level by
the same 0.33-0.36 nm observed for the island heights, indicating
that the etching of the remnants of the top layer that produces
the island structures has also modified the planar regions of the
main terrace levels, leading to physically thicker layers. The
steps within the trench area (the center-top region of Figure 3d)
are consistently ∼0.24 nm high, indicating that these regions are
relatively unaffected by S. Just as the etching process is
demonstrably slower in the trench area, the chemical modifications
that lead to anomalous step heights in inaccessible regions of the
surface are also slower with respect to the relatively exposed
regions. Although the main terrace shown in Figure 3d is
extremely flat, it is difficult to determine conclusively that this
terrace is planar (within 0.12 nm elevation) across the entire 300
nm surface; this makes it difficult to ascertain whether the
increased step heights seen at the edges of the topmost terrace
imply that the layer itself is uniformly 0.33-0.36 nm thick or
whether the terrace layer expansion is restricted to the vicinity
of the edges. Nonetheless, these observations show that extended
exposure of the Au/mica surface to the S solutions leads to
chemical changes of the islands, most of the step edges, and at
least some localized regions of the terraces.
The irregular structure heights observed in the later stages of
the gold etching (Figure 3c,d) indicate that the chemical
composition of the gold surface has been chemically modified
by the S solutions, presumably by oxidation. The structures
observed in Figure 3c are remarkably similar to the topographies
found by Vitus and Davenport33 in their in situ STM study of
electrochemical oxidation/reduction of Au(111) single crystals.
The electrochemical oxidation of Au(111) surfaces in acidic media
involves two successive one-electron steps:
Au + H3O+ f
AuOH + 2H+ +1e- (E ) +1.35 V vs RHE)
AuOH f AuO + H+ +1e- (E ) +1.55 V vs RHE)
Although no structural modifications were reported for the
formation of AuOH, Vitus and Davenport33 observed that the
apparent heights of monatomic step structures decrease by ∼0.12
nm during the second AuOH f AuO reaction and suggested that
this was due to electronic modifications to the surface instead
(33) Vitus, C. M.; Davenport, A. J. J. Electrochem. Soc. 1994, 141, 1291.
Kang and Rowntree
of true contraction of the layer thickness; Honbo et al.34 also
observed this apparent decrease in step height during AuO
formation, but did not explicitly consider electronic structural
effects in the interpretation of the STM results. Our observation
of small regions with elevations of ∼0.12-0.16 nm in Figure
3d indicates that these could be patches of AuO. The chemical
identity of the more prevalent regions with ∼0.33-0.36 nm
elevations is uncertain, but it is clear that the composition of the
Au/mica surface has been affected by extended treatment with
S solutions, since the new terrace levels are remarkably resistant
to further chemical etching by S (Figure 3d) and, of course,
because of the unusually large step heights themselves. We
speculate that the increased step heights observed in Figure 3c,d
could show the presence of AuOH in the islands and in the
terrace layers; the progressive increase in the average island
height is consistent with the progressive formation of the
hydroxide-bearing species. We cannot explain why our measure-
ments would reveal step heights of the chemically modified AuOH
surfaces that are higher than those of the electrochemically
prepared surfaces, although it should be noted that the applied
potential in the electrochemical experiment is capable of inducing
surface and subsurface oxidation by the place-exchange
mechanism,33-37 and this may result in more extensive surface
modifications than are possible using our surface treatments.
Alternatively, our AuOH- and AuO-bearing surfaces may be
significantly less compact than those prepared in the electro-
chemical experiments. Although there are extensive studies of
electrochemical gold oxidation, we are unaware of very precise
data available on the structure and dimensions of these oxides
in the monolayer domain.
Continued exposure to S does not change the surface
topography significantly: i.e., the islandlike structures remain
with 0.33-0.36 nm heights, and the step heights leading to the
topmost terrace are consistently greater than that of the original
Au(111) steps. The apparent stability with respect to further
dissolution shows that the oxidized surface is chemically stable
and increasingly difficult to etch in the S solutions. However,
the new surface morphology is mechanically unstable if the
tunneling resistance is reduced below 3-4 GΩ. Parts a-d of
Figure 4 show a sequence of 200 nm × 200 nm images taken
over a region of a Au/mica film in a 30 min experiment following
∼15 min of S treatment; all images were obtained using a sample
bias of +0.25 V and a tunneling current of 0.3 nA (R ≈ 800
MΩ). Under these relatively low-resistance tunneling conditions,
we find that the islands aggregate or are displaced to step edges
during scanning, while at the same time the step edges become
crenulated, similar to those observed on an organic SAM on
gold.38,39 There is a tendency for the island/edge structures to
extend approximately along the horizontal rapid-raster scanning
direction, although the lack of perfect alignment along the raster
direction shows that the high-symmetry directions of the (111)
substrate lattice probably lead to preferential alignments of the
rearranged island structures. The step heights do not change
during this series of images, but it is clear that there is significant
mass transport along the surface under these conditions. The
evolution of the surface includes the elimination of pits and, in
some cases, the preparation of more uniform surfaces than
observed at this stage of the treatment in the absence of low-
(34) Honbo, H.; Sugawara, S.; Itaya, K. Anal. Chem. 1990, 62, 2424.
(35) Angerstein-Kozlowska, H.; Conway, B. E.; Hamelin, A.; Stoicoviciu, L.
Electrochim. Acta 1986, 31, 1051.
(36) Angerstein-Kozlowska, H.; Conway, B. E.; Hamelin, A.; Stoicoviciu, L.
J. Electroanal. Chem. 1987, 228, 429.
(37) Bruckenstein, S.; Shay, M. J. Electroanal. Chem. 1985, 188, 131.
(38) Bucher, J. P.; Santesson, L.; Kern, K. Langmuir 1994, 10, 979.
(39) McCarley, R. L.; Dunaway, D. J.; Willicut, R. J. Langmuir 1993, 9, 2775.
Gold Film Surface Preparation for SAM Studies
Figure 4. Successive STM images of a single Au/mica film after
15 min of exposure to S solution. The scan size is 200 nm × 200
nm. The z range is 0.8 nm. Each image required approximately 160
s to acquire, and the total elapsed time shown in this sequence is
30 min.
resistance imaging. This type of surface mobility is not observed
for freshly prepared clean Au/mica films nor for films subjected
to short (<5 min) exposure to S solutions.
The lateral mass transport characterized in Figure 4 is induced
by the scanning of the tip across the surface; in the absence of
the raster motion of the tip, no evolution of the surface structures
is observed. Figure 5 shows a 400 nm × 400 nm image measured
under high-resistance conditions (sample bias +1.0 V, 0.3 nA,
R ) 3.6 GΩ). Before this image was measured, the regions
marked by frame 1 and frame 2 were scanned three and eight
times, respectively, under low-resistance conditions (sample bias
0.25 V, 0.3 nA, R ) 830 MΩ). In the absence of terrace steps
(e.g., in frame 2) scanning induces island elongation into 10-30
nm wide bands, while scanning in the vicinity of edges (e.g.,
frame 1) produces “cleanly swept” areas of the surface by efficient
mass transport to the terrace edges. It is interesting to note that
there is no evidence of elevated bands at the terrace edges that
would show where the oxidized gold of the islands has been
displaced to, confirming our observation that the terraces edges
themselves are oxidized at this stage of the S treatment. No such
structural changes were detected using high-resistance imaging
parameters or in regions not previously scanned, as shown by
the stability of the surface features outside the repetitively scanned
areas. All the structures observed are stable while stored in glass
dishes for over 24 h.32,40 Under the same tunneling conditions,
the eroded netlike structures of Figure 3c are less affected by
scanning than the island structures of Figure 3d; the instability
of these three surfaces (gold, slightly oxidized gold, and heavily
oxidized gold) is proportional to the quantity of the surface
oxidized, as judged from the structural height information
discussed above. This could reflect (1) the relative mechanical
instability of the increasingly oxidized metal, (2) the relative
mechanical instability of the increasingly disconnected topology,
or (3) increased tip-sample interactions for the heavily oxidized
(40) Venkataraman, B.; Breen, J. J.; Flynn, G. W. J. Phys. Chem. 1995, 99,
6608.
Langmuir, Vol. 23, No. 2, 2007 515
Figure 5. Au/mica surface after 15 min of exposure to S solutions
(scan size 400 nm × 400 nm, z range 3.0 nm, bias 1.0 V, current
0.3 nA). Before this image was acquired, three and eight images for
the center and upper-right regions, respectively, were measured under
a sample bias of 0.25 V and tunneling current of ∼0.3 nA, which
corresponds to a tunneling resistance of ∼830 MΩ.
surfaces caused by the reduced tip-sample separation implicit
in the imaging of materials with higher work functions.
As mentioned in the Introduction, one of our applications is
in preparing self-assembled monolayers on substrates with well-
preserved structural integrity. The infrared spectra taken of the
S-treated Au/mica surfaces show significant reductions in the
2800-3000 cm-1 region within ∼60 s. Increasing exposure can
occasionally lead to further reductions in hydrocarbon-based
absorptions, but the initial contact with the S solutions appears
to be sufficient in most applications. The resistance of the Au/
mica samples to delamination in the S solutions is clearly
beneficial at this point, since additional acid treatments rarely
degrade the adhesion of the metal film. In our IR-RAS studies
of butanethiol submonolayers,8 the S pretreatment proved to be
an essential step in sample preparation, affording high baseline
stability and highly reproducible intensity information. The
infrared spectra of complete monolayers of long-chain thiols
(e.g., hexadecanethiol) can also be significantly influenced by
the S pretreatment protocol. As an example, Figure 6 compares
the IR-RAS spectra of hexadecanethiol self-assembled mono-
layers adsorbed on Au/mica with and without the surface
pretreatment in S, as described above. Both spectra are referenced
to the same S-treated Au/mica surface. The substrates were
prepared in the same evaporation cycle, and the organic
monolayers were prepared under identical conditions from the
same deposition solution. Although the intensities of the
absorption bands associated with the methylene stretching modes
(d+, ∼2850 cm-1; d-, 2921 cm-1) are not significantly affected
by the pretreatment, they are broader and often observed at higher
frequencies in the absence of the pretreatment, indicating that
the internal structural order of these films is inferior to that of
the S-treated substrates.5,6,41 The bands associated with the
terminal methyl groups (r+, 2875 cm-1; r+FR, 2935 cm-1; r-,
(41) Garand, E.; Rowntree, P. J. Phys. Chem. B 2004, 108, 8182.
516 Langmuir, Vol. 23, No. 2, 2007
Figure 6. Grazing incidence infrared spectra of hexadecanethiol
monolayers adsorbed on Au/mica surfaces without (A) and with (B)
a pretreatment with the S solution prior to immersion of the substrate
into the 1 mM thiol/methanol solution. Spectra were measured at
an approximately 85° incident angle under UHV conditions, without
an external polarizer.
2965 cm-1) are markedly sharper and more intense on the
pretreated substrates, indicating that the film-vacuum interface
is also more homogeneous for these samples.8 The impact of
oxides on the adsorption of thiols is an interesting and important
question; under typical preparation conditions the surface
coverage of the oxide is very low, and these oxides are readily
reduced by simple alcohols (i.e., the standard solvents used for
thiol depositions). Ron et al.42 have shown that adsorption of
octadecanethiol onto ozone-oxidized gold can protect the oxide
regions from reduction, but that the spectroscopic and contact
angle results are not sensitive to the prior oxidized state of the
surface. Adsorption of thiols onto electrochemically formed
oxides under potentiostatically controlled (anodic) conditions
can lead to the formation of high-quality SAMs and the reduction
of the substrate to pure Au.43 It is not known whether residual
sulfate or chromate would influence the thiol adsorption; we
anticipate that all weakly bound species would be readily displaced
by the growing SAM or react with the excess thiol in the deposition
solution.
Although it is customary to develop surface preparation and
cleaning procedures that minimize the introduction of defects,
we have found that the atomic-scale “roughening” shown in
Figure 3a,b following ∼2 min of S treatment can assist in the
deposition of biomolecular targets such as DNA and short
plasmids. The low barriers to lateral diffusion on smooth
crystalline surfaces such as graphite and Au(111) often lead to
the accumulation of the molecules of interest at steps and extended
defects, where they can be difficult to distinguish from the surface
topography.44 The minor defects introduced using the S solutions
can serve to increase the barrier to diffusion, while maintaining
atomically “flat” substrates that facilitate scanning probe studies
of adsorbed species. Furthermore, these defects are predominantly
located upon the upper terraces, such that the microscopic
“roughness” is selectiVely increased on those regions that are the
most useful in scanning probe experiments without increasing
the trapping of adsorbates within troughlike structures as seen
in Figure 3a,b,d. S-treated surfaces have facilitated the detection
(42) Ron, H.; Matlis, S.; Rubinstein, I. Langmuir 1998, 14, 1116.
(43) Ron, H.; Rubinstein, I. J. Am. Chem. Soc. 1998, 120, 13444.
(44) Clemmer, C. R.; Beebe, T. P., Jr. Science 1991, 251, 640.
Kang and Rowntree
of short-chain DNA species (e.g., ladder-100 DNA) by increasing
the probability of finding (and identifying) the target species,
while minimizing the displacement of these species by the
scanning action of the STM tip.
Conclusions
We have studied the morphological modifications of Au/mica
substrates after exposure to piranha and sulfochromic acid
solutions using STM methods. While both acid treatments could
remove the organic contaminants from the surface with similar
efficiencies, defects were inevitably introduced into the surface
structures. The exposure of Au/mica films to piranha acid leads
to extensive and uncontrolled etching of the surface within 30
s and severe disruption of the surface topography; extended
exposure causes the precipitation of material on the surface that
is easily displaced by the STM instrument. Au/mica films are
also readily delaminated using the P treatment solutions. Exposure
of Au/mica surfaces to sulfochromic acid for less than ∼300 s
creates permanent etch pits on the surface that are exclusively
one Au layer deep; extended exposure leads to progressive etching
of the surface, ultimately leading to the formation of 0.33-0.36
nm high islands on the otherwise flat Au/mica surface, increasing
levels of surface oxidation, and mechanical instabilities under
the scanning action of the STM tip. Our IR-RAS results indicate
that exposure of Au/mica surfaces to sulfochromic acid for 1-5
min is a highly effective cleaning procedure for the elimination
of hydrocarbon contaminants, while minimizing the chemical
and structural modifications of these substrates. Infrared spec-
troscopic studies of self-assembled organothiol monolayers using
substrates treated with sulfochromic acid have confirmed that
this substrate preparation technique is highly reproducible, and
the resulting low quantity of impurity adsorbates permits the
quantitative study of species with exceedingly low optical
absorbances such as short-chain thiols (e.g., butanethiol) adsorbed
in submonolayer quantities.
It is interesting to note that Bienner et al.45 have recently
observed complex topological and chemical modifications to
Au(111) surfaces upon exposure to SO2 gas, some of which
decomposes to form atomic S. At low coverages of S (0.05-0.1
monolayer (ML)) the 22 × x3 reconstructed pattern is
progressively eliminated due to an expansion of the Au lattice
by 4%. For S coverages between 0.1 and 0.3 ML there is no
apparent perturbation of the surface geometry, but beyond this
critical abundance the Au surface becomes sharply etched, with
structures resembling that shown herein for Au/mica exposed to
the P solutions (i.e., Figure 2). Annealing to 450 K transforms
this into a network-like structure that resembles the images of
Figure 3a,b. These large-scale structural transformations were
attributed to the formation of a 2D stoichiometrically exact AuS
phase. Thus, while we have considered the activity of the S and
P solutions in terms of oxidation processes, incorporation of
sulfur into the Au/mica surface is also a possibility. It is not
known whether this would be consistent with the anomalous
step heights and surface features reported in this work. It seems
unlikely however that such a AuS surface would be conducive
to the formation of a well-formed organic monolayer of
1-alkanethiols.
Acknowledgment. This research was supported by the Natural
Sciences and Engineering Research Council (Canada). We thank
E. Garand for his assistance with the infrared measurements of
the hexadecanethiol surfaces.
LA0518804
(45) Biener, M. M.; Biener, J.; Friend, C. M. Langmuir 2005, 21, 1668.