Note: Production of sharp gold tips with high surface quality

Max Eisele, Michael Krüger, Markus Schenk, Alexander Ziegler, and Peter Hommelhoff

Citation: Review of Scientific Instruments 82, 026101 (2011); doi: 10.1063/1.3534078

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 REVIEW OF SCIENTIFIC INSTRUMENTS 82, 026101 (2011)

Note: Production of sharp gold tips with high surface quality

Max Eisele,1 Michael Krüger,1 Markus Schenk,1 Alexander Ziegler,2 and Peter
Hommelhoff1,a)
1
Max-Planck-Institut für Quantenoptik, Hans-Kopfermann-Str. 1, D-85748 Garching, Germany
2
Max-Planck-Institut für Biochemie, Am Klopferspitz 18, D-82152 Martinsried, Germany
(Received 9 November 2010; accepted 11 December 2010; published online 4 February 2011)
We present a simple method to produce sharp gold tips with excellent surface quality based on elec-
trochemical etching with potassium chloride. Radii of curvature lie in the range of 20–40 nm and the
surface roughness is measured to less than 0.8 nm. The tips are well suited for field emission, field ion
microscopy, and likely for tip-enhanced Raman scattering as well as tip-enhanced near-field imaging.
© 2011 American Institute of Physics. [doi:10.1063/1.3534078]

Gold tips exhibit a broad and strong plasmonic response
at visible and near-infrared frequencies, which together with
their chemical inertness have made them the preferred choice
for a variety of applications such as tip-enhanced Raman
spectroscopy, scanning near-field optical imaging, and laser-
assisted field emission. Over the last 50 years a variety of
methods has been developed to obtain sharp gold tips.1–13 All
but one rely on electrochemical etching of a thin gold wire.
The results differ in the typical minimum tip radius obtain-
able, in surface roughness, and in the general shape of the tip.
We found that either hazardous etchants like perchloric acid
have to be used, that rather sophisticated multistep procedures
are required, that the method did either produce tips of too
poor quality, and/or that the method did not work reliably in
our (nonchemistry but physics) laboratory.
Here we show that dc voltage electrochemical etching
with KCl combined with the lamella-drop-off technique pro-
duces very sharp gold tips with small efforts. The method is
simple, reliable, and fast and produces gold tips with excel-
lent surface quality and tip radii in the range of 20–40 nm.
The etchant is benign and resistant to contamination as it can
be used and stored for several months in a closed plastic con-
tainer at regular laboratory atmosphere.
Although gold tips have been successfully produced with
KCl in a two-step ac voltage electropolishing process more
than a decade ago,4 this process appears to be too com-
plicated so that in many laboratories other techniques have
been developed aiming at reducing the setup’s and process’s
complexity.
The method described here is based on the lamella-drop-
off technique14–16 with a fast electronic switch-off of the
applied voltage. We checked that the switching time is not
critical up to a duration of roughly 100 ms, which is why we
consider it unnecessary to mention any details about the elec-
tronics. The setup comprises two 0.5 mm diameter platinum
cathode wires bent into rings with diameters of 7 mm. The
ring axes are aligned vertically and the rings are arranged on
top of each other with a distance of 8 mm between them. Each
wire ring holds an etchant lamella. The lamella in the upper
a) Electronic mail: peter.hommelhoff@mpq.mpg.de.
ring serves for etching, the one in the lower ring for measur-
ing when the wire is etched through. It triggers the switch-off
of the etching voltage.
Before etching, we clean the rings by submerging them
in the etchant and applying a voltage of +10 V to both rings
until the adhesions at the rings are dissolved. Here another
electrode (Ni) serves as ground. For etching we use 90%
saturated aqueous solution of KCl [Alfa Aesar potassium
chloride, 99.0%–100.5% (ACS)], prepared with in-house
deionized water or ultrapure water (Carl Roth H2 O Rotipu-
ran), both of which delivered good results. The gold wire
(0.1 mm diameter, polycrystalline, 99.95% purity, Alfa Ae-
sar) to be etched is arranged vertically and centered through
the two platinum rings. About 20 mm of the wire extend be-
low the bottom platinum ring.
For etching, we briefly immerse the platinum rings into
the KCl solution to form a lamella within each ring. The etch-
ing process is started by applying a dc voltage of +10 V to the
gold wire in reference to the upper platinum ring. During the
etching process a strong bubble formation at the upper plat-
inum ring occurs as well as a separation of the dissolved KCl
from the solution. Thus, KCl crystals form, leading to the rup-
ture of the upper lamella. Hence, the etching setup has to be
redipped into the etchant. This can happen between one and
eight times during a single tip etching process. We could not
observe any influence of the bubble formation or the rupture
of the lamella onto the quality of the etched tips. The cur-
rent during etching is around 25–40 mA. After approximately
10 min the wire is etched through, and the lower part drops
down. While still in the mount, we rinse the tip first with ul-
trapure water and then with acetone to remove the remnants
of the etchant. (For applications that do not include another
cleaning step [such as in field-ion microscope (FIM), see be-
low], it might be advisable to clean the tip with a more ag-
gressive procedure as described in, e.g.,5 .) We usually only
work with the upper part of the wire, which does not drop af-
ter etching, but the lower part of the wire can of course also
be used.
Figure 1 shows images of a typical resulting tip. The ra-
dius of curvature is usually around 30 nm (20–40 nm) inferred
from scanning electron microscope (SEM) and transmission
electron microscope (TEM) images. The shank opens into a

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 026101-2 Eisele et al.
a) b)
100µm 60nm
c) d)
7nm 100µm
FIG. 1. (Color online) (a) Scanning-electron microscope image of a gold tip
etched with KCl. (b) TEM image. The transparent film seen on the surface
arises from passivation layers. (c) TEM image of the tip’s apex. (d) Optical
microscope image.
cone with ∼10◦ full opening angle, extending over ∼300 μm.
The surface roughness is estimated to be less than 0.8 nm in-
ferred from the TEM image shown in Fig. 1(c). Note that the
surface quality is excellent not only at the apex but also up to
300 μm up the shank.
We found that in order to judge if the tips are sharp and
smooth, it suffices to inspect them with an optical microscope
after etching. If the surface looks shiny and the tip ends in a
rotationally symmetric and undistorted cone [see Fig. 1(d)],
the tip turned out to be sharp and smooth under SEM and
TEM inspection. We have not seen incremental effects, for ex-
ample, that the tip radius is larger than in other tips, but rather
a bimodal distribution. If the tip looks good optically, the tip
radius is around 30 nm with good surface quality. From ex-
aminations with the optical microscope we infer that around
90% of etching attempts are successful.
Figure 2(a) shows a typical room temperature FIM im-
age of a gold tip with neon as image gas. Figure 2(b)
shows a face-centered-cubic (fcc) ball model image. Clearly,
a fourfold symmetry is visible in the FIM image as well
as several crystal facets. The same symmetry is visible in
the fcc ball model, indicating an atomically smooth tip sur-
face. The radius of curvature of the Au tip of Fig. 2(a) is
∼65 nm measured with the Fowler–Nordheim method.17 The
increase of the radius is due to field evaporation of the surface
atoms, which is a good cleaning method in FIM applications.
Interestingly, all of the five gold tips we inspected with FIM
showed a crystallographic orientation of the apex in the (100)
direction.
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Rev. Sci. Instrum. 82, 026101 (2011)
FIG. 2. (Color online) (a) Field-ion microscope image. Bright spots indicate
protruding atoms at crystallographic kinks and edges. (b) Ball model of fcc
structure with one atom per lattice site at (100) orientation. The color map
indicates the deviation of the surface atoms from an ideal hemisphere.
Summarizing, we have given a recipe for obtaining reli-
ably, fast, and with a benign etchant sharp gold tips with radii
of curvature of around 30 nm and with excellent surface qual-
ity. Field ion microscope images demonstrate the usefulness
and quality of the so produced gold tips.
We gratefully acknowledge A. Holleitner (WSI, Technis-
che Universität München) for providing SEM access to us,
and J. Hoffrogge for establishing contact. This project was
partially supported by the EU (FP7 IRG) and by the Munich-
Centre for Advanced Photonics (MAP).
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