Preparation of gold tips suitable for tip-enhanced Raman spectroscopy and light

emission by electrochemical etching

Bin Ren, Gennaro Picardi, and Bruno Pettinger

Citation: Review of Scientific Instruments 75, 837 (2004); doi: 10.1063/1.1688442

View online: http://dx.doi.org/10.1063/1.1688442
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 REVIEW OF SCIENTIFIC INSTRUMENTS VOLUME 75, NUMBER 4 APRIL 2004

Preparation of gold tips suitable for tip-enhanced Raman spectroscopy

and light emission by electrochemical etching
Bin Rena)
Department of Chemistry, Xiamen University, Xiamen 361005, China
Gennaro Picardi and Bruno Pettingerb)
Fritz-Haber-Institut der Max-Plank-Gesellschaft, Faradayweg 4-6, D-14195 Berlin, Germany
共Received 14 November 2003; accepted 8 January 2004; published 8 March 2004兲
We describe a method of preparing gold scanning tunneling microscopy 共STM兲 tips by direct current
electrochemical etching in concentrated HCl and ethanol solution. Gold tips with tip apex radius
lower than 30 nm can be reproducibly prepared by this method. The influence of the solution
composition, etching voltage on the surface structure, and sharpness has been investigated. These
tips can be efficiently used for STM imaging, tip-enhanced Raman spectroscopy, and light emission
investigations on the same sample. © 2004 American Institute of Physics.
关DOI: 10.1063/1.1688442兴

I. INTRODUCTION 1.6 to 2.0 V14 or by etching in an 10%–35% ammonia solu-

The effort of producing optimal scanning tunneling mi-
croscope 共STM兲 tips has never ended ever since the discov-
ery of STM in 19811 because the tip determines, to a large
extent, the spatial resolution and the image quality of the
STM. Therefore, over more than two decades, at least ten
preparation methods have been developed.2,3 Among these
methods, mechanical cutting is apparently the easiest way,
but it will produce multiple tips and the reproducibility of the
method is poor.4 Ideal tips, with a single atom at the top can
be prepared in field ion microscope in UHV, but this is an
expensive and complicated method not affordable for most
researchers.5 The most practical way of preparing STM tips
is using electrochemical etching. This method provides tips
with sufficient quality in a reproducible and reliable
manner.6,7 W and Pt–Ir tips with a very sharp apex have been
fabricated using this method. For example, extremely small
W tips with radius less than 10 nm can be prepared by dc
etching method.8
Recently, apertureless near-field optical techniques re-
ceived great attraction in the field of subwavelength spec-
troscopies. Among them are light emission from STM-
tunneling junctions and tip-enhanced Raman spectroscopy
共TERS兲 using a variety of tips including Au or Ag STM tips
or Au or Ag coated atomic force microscopy tips.9–13 These
studies point to the additional need of a suitable optical qual-
ity of the tips: presumably, a tip with a smooth surface and a
sharp end is ideal for both the light emission and the tip-
enhanced Raman processes. Only then is the excitation of
localized surface plasmons 共created by the incident electrons
or photons兲 as well as their radiative decay, favored by the
tip-metal cavity alone. Silver tips can now be effectively
made by etching in a solution with a mixture of concentrated
HClO4 and pure methanol 共1:4兲 at an anodic voltage between
a兲
Electronic mail: bren@jingxian.xmu.edu.cn
b兲
Electronic mail: pettinger@fhi-berlin.mpg.de
tion at 10 V.15 However, the fabrication of suitable gold tips
for light emission or TERS studies was not as successful or
the solution used are too toxic. Gold tips have been fabri-
cated by etching in a CaCl2 solution of 10%–50% saturation
at 30 V, or in 3 M NaCl and KCl solution at 10 V.2,16 But the
size of the tip apex is too large for the TERS or light emis-
sion study. Baykul reported a procedure of using a 0.8 M
KCN with a 12 V etching voltage. This produced a tip radius
varying between 200 and 500 nm.17 Recently a recipe was
reported by Abbou, who used a mixture solution of saturated
CaCl2 , water, and ethanol in a proportion of 2:8:1. It takes
only about 2 min at 7 V to produce a tip.18 Since this method
is intended to produce an ultramicroelectrode but not a STM
tip, they did not make an effort for producing a sharp end. A
good gold tip can be obtained by etching in concentrated
HCl solution with a 12 V pulse voltage followed by mi-
cropolishing in CaCl2 /H2 O/ketone solution,19 however the
etching method is complicated. A lower etching voltage 共1.5
to 2.0 V兲 was used to make the gold tip,20 however, this
generally produces a surface with a very rough structure,
which would be ideal for surface-enhanced Raman scattering
studies on the tip itself but not for TERS. A rough tip surface
shows a great affinity for adsorbing carbon even from air,
thus introducing undesirable carbon signals during the TERS
study. It has been reported that the ideal tip for TERS or light
emission studies should have a radius less than 100 nm with
smooth surface.21,22 In the present article we will report a
very simple method to produce sharp gold tips with smooth
surface structure, which can be efficiently used in both light
emission and TERS investigations, as well as for STM im-
aging on the same sample.
II. EXPERIMENT
The setup for etching the Au tip is based on a commonly
used configuration, as shown in Fig. 1, placing a gold ring of
about 8 mm diameter made from 1 mm gold wire on the
surface of the solution 共about 3/4 height of the ring is im-

0034-6748/2004/75(4)/837/5/$22.00 837 © 2004 American Institute of Physics

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18:58:11
 838 Rev. Sci. Instrum., Vol. 75, No. 4, April 2004
FIG. 1. The schematic diagram of the setup for preparing the gold tip.
mersed in the solution兲. A gold wire of 0.25 mm diameter
from Aldrich after a quick flame-annealing was immersed in
the center of the ring. The immersed length is normally about
2–3 mm. In order to well control the shape of the tip apex, a
⫻25 microscope camera was used to monitor the etching
process with proper back white light illumination. The etch-
ing solution was prepared using analytical grade fuming hy-
drochloric acid and ethanol from Merck.
The dc voltage was supplied by a home-made dc voltage
controller, which allows an easy control of the voltage and a
quick switch to open circuit when the lower part of the wire
has fallen down. Alternatively, a potentiostat can be used,
permitting a better control of the applied potential.
The shape of the tip was examined using a Hitachi S-570
SEM operated at an accelerating voltage of 15 kV and a
working distance of 5 to 10 mm.
Dilor X-Y confocal microprobe Raman instrument was
used to perform light emission and TERS studies. The light
was collected with a ⫻50 long working length objective with
a NA of 0.5 at an angle of 60° relative to the surface. The
632.8 nm light from a He–Ne laser was used for TERS in-
vestigations. The STM is a home-made instrument. The de-
tailed experimental setup for the TERS and light emission
has been reported elsewhere.23,24
III. RESULTS AND DISCUSSION
A. Tip preparation
A benign etching method implies the use of nontoxic
etching solutions and operation under a mild condition. As
has been mentioned in the introduction, gold can be etched,
for example, with a CN⫺ or Cl⫺ containing solution. How-
ever, the former requires a high voltage 共⭓10 V兲. Unfortu-
nately, CN⫺ is very toxic although it produces a smooth
surface. The advantage of the HCl etching method is its low
etching voltage, e.g., 3.0 V.
According to the following reactions, gold can be dis-
solved in a concentrated HCl solution applying an appropri-
ate voltage:25
Au⫹4Cl⫺ →AuCl⫺ ⫺
4 ⫹3e , E 0 ⫽1.002 V,
Au⫹2Cl⫺ →AuCl⫺ ⫺
2 ⫹e , E 0 ⫽1.154 V,
AuCl⫺ ⫺ ⫺ ⫺
2 ⫹2Cl →AuCl4 ⫹2e , E 0 ⫽0.926 V.
At a high rate, these reactions consume a large amount of
Cl⫺ near the interface, leading to a depletion of Cl⫺ ions in
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Ren, Picardi, and Pettinger
this region. Subsequently, gold oxides will be formed, which
passivate the gold surface, leading to a dramatic decrease of
the reaction current. The fast resupply of Cl⫺ from the bulk
solution will facilitate the dissolution of the gold oxides as
AuCl⫺ 4 , leading to the reexposure of the bare gold surface to
the HCl solution and, thus, to an increase of the reaction
current. This process occurs again and again, establishing a
current oscillation. Evidence for this is the periodic change
of the reaction current during the etching process.
In our previous study, we observed that a stable current
oscillation only occurs for voltages more positive than 1.4 V
with respect to a saturated calomel electrode.25 Therefore, in
order to etch the gold in HCl solution, the voltage should be
higher than 1.4 V. A higher voltage leads to a faster reaction
rate but also to side reactions including the evolution of Cl2
and O2 . The latter effect causes a severe bubbling resulting
in a rough surface structure. Considering the role of ethanol
in silicon industry, where ethanol was used to reduce the
bubbling and, hence to produce a smooth surface during the
etching process,26 in this study, we added a certain amount of
ethanol to the HCl solution to reduce the bubbling effect with
the aim to obtain a smooth gold surface. It should be noted,
the same strategy has been used in Refs. 14 and 19 to get a
smooth surface.
For the study of the influence of the etching potential,
we select a solution with an equal amount of hydrochloric
acid and ethanol. The SEM images for the etching potentials
at 1.8, 2.2, 2.4, 2.6, and 4.0 V were shown in Fig. 2 共the light
contour or shadow around the tip arises from carbon con-
tamination in the SEM chamber兲. Evidently, there is an op-
timal potential range for producing a smooth and a sharp tip:
for an etching potential of 2.4 V, the surface presents a rela-
tive smooth structure and the tip radius is approximately 20
nm, see the inset of Fig. 2共c兲 共the zig-zag feature is due to
mechanical vibration of the SEM instrument兲. This is re-
markably different from the grainy structures produced at 1.8
and 4.0 V. According to what we have observed during the
etching process, the etching occurs faster in the meniscus
region formed by the gas/solid/liquid interfaces, than in the
bulk solution. Thus, within the meniscus region a necking-in
occurs. When the etched part of the wire becomes too thin to
keep the lower part of the wire attached, it will break and fall
down. At this moment the circuit is manually cut off. A better
control of the end of the electrochemical etching can be re-
alized by designing a current detection device that can cut off
the circuit when the current drops to a preset value. Since the
gold ring is used as the cathode, it will not be etched during
the etching process. However, since porous deposits will
cover the ring surface leading to an electrode of somewhat
lower conductivity, the ring has to be cleaned or polished
periodically.
Next, we investigated the influence of the solution com-
position on the surface structure. Three sets of solution were
used: the mixture of concentrated hydrochloric solution 共con-
taining 37% HCl兲 with ethanol having the following propor-
tions: 2:1, 1:1, and 1:2. In all cases, the etching voltage was
set to 2.4 V. The corresponding SEM images of the tip were
shown in Fig. 3 共for a clear view of the tip apex, Fig. 3共b兲
was enlarged and given as an inset, the tip radius is less than
 Rev. Sci. Instrum., Vol. 75, No. 4, April 2004
30 nm兲. Obviously, a tip with a smooth surface can be ob-
tained for a solution of equal content of hydrochloric acid
and ethanol, while the tips obtained from solutions with dif-
ferent contents also show grainy structures. Therefore, the
solution with equally amount of hydrochloric acid and etha-
nol was used as the etching solution and the voltage of 2.4 V
was selected as the etching voltage in our study. We do not
rule out that other combinations of etching voltage and solu-
tion composition can produce even better tips. However, the
excellent tip shape, the smooth surface structure, a very low
etching voltage, and the nontoxic nature of the etching solu-
tion indicates that we have met the requirement of a benign
etching method.
Generally, under optimal conditions, an efficient Au tip
can be reproducibly produced within 6 to 7 min. The actual
etching time depends on the temperature and freshness of the
etching solution and the relative proportion of HCl to etha-
nol. It should be noted that at the ending point of the etching
process, the most etched portion of the gold wire becomes
very thin. If the gold wire is not very well vertically aligned,
it can result in a gold tip with bended apex.
B. STM study
Using a tip produced by the above described method, an
STM image of a Au共111兲 surface has been recorded, see Fig.
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Electrochemical preparation of Au tips 839
FIG. 2. SEM images of gold tips
etched in a HCl:ethanol 共1:1兲 solution
at different potentials as indicated in
the images.
4共a兲. The clear and sharp step edges of the terraces seen in
Fig. 4共b兲 indicate a high quality of the tip. However, our
present STM system, due to its combination with a Raman
system, has not the mechanical stability for receiving atomic
resolution of the Au共111兲 surface, even when using a sharp
iridium tip prepared by grinding.
C. Light emission study
Reproducible light emission spectra can be obtained us-
ing this tip on different areas of a newly flame-annealed
clean Au共111兲 surface. Figure 5 shows a set of the light emis-
sion spectra obtained at different bias potentials. At poten-
tials as low as 1.2 V, a very weak emission band at 950 nm
can be observed. Increasing the bias potential, the peak in-
tensity rises and the peak position moves to a shorter wave-
length. The cutoff wavelength ␭ is determined by the relation
␭ c (nm)⫽hc/eVbias⫽1238.9/V bias(V). It should be noted
that due to the dramatic decrease of the detection sensitivity
of the Raman instrument at wavelengths longer than 850 nm,
the intensities around the cutoff wavelength and the peak
position in the curve may not reflect the real shape of the
emission spectra. Nevertheless, the present study illustrates
that electrochemically etched tips are also quite useful for
light emission studies.
FIG. 3. SEM images of gold tips
etched at 2.4 V in HCl: ethanol solu-
tions with different contents: 共a兲 1:2,
共b兲 1:1, and 共c兲 2:1.
 840 Rev. Sci. Instrum., Vol. 75, No. 4, April 2004
D. TERS study
There are a number of reports on the influence of tip
apex and tip-sample separation on the tip-enhanced Raman
signal.21,22,27–29 The smaller the tip apex, the larger enhance-
ment should be. From our SEM results, it is obvious that
reproducible gold tips with a diameter around 60 nm can be
easily obtained by the above-described method. Tips of this
type indeed are very suitable for tip-enhanced Raman study.
For an easy comparison of the Raman signals, malachite
green isothiocyanate 共MGITC兲 has been used as an adsorbate
because a large Raman cross section is expected due to the
excitation line centered within the molecular absorption
band. MGITC adsorbed Au共111兲 electrode was prepared by
dropping a drop of 10⫺6 M MGITC ethanolic solution onto a
freshly flame-annealed Au共111兲 single crystal surface and
drying in air followed by washing with a copious amount of
ethanol. The resonance Raman signal for MGITC molecule
at a Au共111兲 surface is very weak; Fig. 6 illustrates this with
a peak signal of about 3 cps. However, when an Au-tip is
brought into tunneling distance with the Au共111兲 surface,
very high Raman intensities can be detected, showing a 130-
fold net-increase共q兲 of the signal. This effect is due to the
enhancement of the electromagnetic field within the Au-tip-
Au共111兲 cavity. Taking into account the area difference be-
tween the enhanced field produced by the tip and the laser
focus, a TERS enhancement 共g兲 of about 1.6⫻105 can be
FIG. 5. Light emission spectra obtained at the junction of the gold tip and
the Au共111兲 surface. The tunneling voltage is marked on the curve. The
tunneling current is 2.5 nA. Acquisition time: 30 s.
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Ren, Picardi, and Pettinger
FIG. 4. STM image 共a兲 and the profile
共b兲 along the a-b line of 共a兲 of a
freshly flame-annealed Au共111兲 sur-
face 共area 100⫻100 nm兲. Tip to sub-
strate voltage is ⫺150 mV and the tun-
neling current is 1 nA. The image is
presented with plane correction on the
raw data.
obtained using the relation: q⫽I TERS /I RRS⫽g 4 a 2 /R 2f , where
a and R f being the radii of the enhanced field 共for rough
estimation, we assume the field radius being equal to the tip
radius of 30 nm兲 and the laser focus.23,24
This result proves that gold tips with a small tip apex can
have an excellent performance, significantly greater than so-
far reported. This is a crucial requirement for TERS becom-
ing more generally applicable.
A benign method for an easy and quick production of
smooth gold tips with a sharp apex, evidently very suitable
for tip enhanced Raman study and light emission studies, has
been described. Tips with radii around or smaller than 30 nm
and smooth surfaces can be reproducibly produced by etch-
ing in solutions mixed by fuming HCl and ethanol 共1:1兲 us-
ing dc electrochemical method at 2.2 to 2.4 V. As a addi-
tional advantage, the chemical inertness of Au allows the tip
to be used for several sets of experiments.
ACKNOWLEDGMENTS
B.R. thanks the Alexander von Humboldt Foundation for
a research fellowship at the Fritz–Haber Institute and the
National Science Foundation of China 共NSFC, No.
90206039兲.
FIG. 6. 共a兲 Resonance Raman spectrum and 共b兲 tip-enhanced resonance
Raman spectrum of the malachite green isothiocyanate monolayer on a
freshly flame-annealed Au共111兲 surface. STM condition: tunneling voltage
⫺150 mV, tunneling current 1 nA. The acquisition time for curve a is 30 s
and the spectrum has been enlarged by 60-fold for a clear view of the peaks
and positioned in order to fit in the figure. The acquisition time for curve b
is 10 s and presented as it is.
 Rev. Sci. Instrum., Vol. 75, No. 4, April 2004 Electrochemical preparation of Au tips 841

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