A reproducible method to fabricate atomically sharp tips for scanning tunneling

microscopy
Yoshiaki Nakamura, Yutaka Mera, and Koji Maeda

Citation: Review of Scientific Instruments 70, 3373 (1999); doi: 10.1063/1.1149921

View online: http://dx.doi.org/10.1063/1.1149921
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 REVIEW OF SCIENTIFIC INSTRUMENTS VOLUME 70, NUMBER 8 AUGUST 1999

A reproducible method to fabricate atomically sharp tips for scanning

tunneling microscopy
Yoshiaki Nakamura, Yutaka Mera, and Koji Maedaa)
Department of Applied Physics, Graduate School of Engineering, The University of Tokyo, Bunkyo-ku,
Tokyo 1136856, Japan
Received 8 March 1999; accepted for publication 19 April 1999
The electrochemical etching method by Ibe et al. J. Vac. Sci. Technol. A 8, 3570 1990 to
fabricate sharp tips for scanning tunneling microscopy was modified by shortening the cutoff time
of the etching current after the material wire drops off at the air-electrolyte interface. The tip radius
measured by field ion microscopy was successfully reduced to 8 nm when the cutoff time was
shortened to 50 ns. The dependence of the field-emitting electron current from the sharpest tips was
close to one expected from the FowlerNordheim formula with a reasonable value for the emitting
area of the tip. 1999 American Institute of Physics. S0034-67489901408-2

I. INTRODUCTION an etching current, thereby eliminating the ad hoc factor re-

garding the reference level. In their circuit, the differentiated
The sharpness of the tips in scanning tunneling micros-
signal is reshaped by a comparator whose output is fed to
copy STM is one of the important factors that affect the
control a couple of analog switches. One of them shuts off
resolution of STM images. A standard technique for fabri-
the voltage supplied to the electrochemical cell, and the other
cating sharp STM tips has been the drop off method,110
simultaneously shunts the two electrodes conforming the
based on electrochemical etching in which the etching cur-
cell. No matter what the absolute magnitude of the etching
rent is cut off immediately after the part of the material wire
current is, the etching reaction is stopped very soon after the
immersed in the electrolyte drops off due to its own weight.
wire breaks apart. However, the differentiator and the com-
Ibe et al.3 showed that the cutoff time has the most signifi-
parator in their circuit cause a significant delay that prevents
cant effect on the sharpness of the tip; a shorter cutoff time
the cutoff time from decreasing to values shorter than the
results in a sharper tip. With a cutoff time as short as 600 ns,
delay time. The circuit used by Ibe et al.1 without a differ-
they succeeded in obtaining a tip radius as small as 20 nm.
entiator succeeded in reducing the cutoff time down to 600
However, they did not study further whether the shorter cut-
ns, but it would suffer from the ambiguity of the reference
off time yields a reproducible sharper tip by this scheme.
level if the cutoff time became much shorter.
The present report describes an improved circuit that
Figure 1 shows the electronic circuit we constructed to
shortens the cutoff time, thereby facilitating reproducible
realize much shorter cutoff times. The circuit is similar to
fabrication of atomically sharp tips that allow high-resolution
that used by Anwei et al.,9 but is different in several points.
STM observations. The dependence of tip sharpness on the
The change in the etching current monitored by a field-effect
cutoff time was investigated by directly measuring the tip
transistor FET buffer amplifier 2SK125 is detected by a
radius by field ion microscopy FIM. With the sharpest tips,
differentiator composed of a high speed operational amplifier
we achieved field emissions of electrons with current values
EL2075C ELANTEC, which has a fast slew rate of 800 V/
as large as 6 nA at the tip bias of 200 V. The experimental
s. The output of the differentiator is directly connected to a
dependence of emission currents on tip bias was found to be
flip-flop IC 74F74N, instead of a comparator, whose
well described by fitting the FowlerNordheim formula with
transistor-transistor logic TTL output is fed through a RC
a reasonable value for the emission area.
circuit to two sets of analog switches. One is a FET that
shunts the electrodes in the cell, and the other consists of a
II. EXPERIMENTAL PROCEDURE series of FETs that opens the bias supply circuit. The RC
A. Control circuit circuit behind the flip flop determines the feedback delay that
was intentionally elongated so as to examine the effect of
In most of the techniques developed so far, the etching
cutoff time on tip sharpness.
current is cut off upon detecting an abrupt drop of the moni-
tored electrolytic current below a particular reference level.
Generally, however, it is difficult to anticipate the appropri- B. Etching procedure
ate level to be set as the reference, because the critical cur- A polycrystalline tungsten wire of 99.95% purity with a
rent at which the lower part of the wire drops off is variable. diameter of 0.3 mm was immersed in a solution of 2 N
An improved method was proposed by Anwei et al.,9 who NaOH used as the electrolyte at a depth of 2 mm beneath the
introduced a differentiator to detect the differential signal of surface. The wire and a PtIr ring placed around the wire in
the electrolyte served as the anode and cathode, respectively.
a
Electronic mail: maeda@exp.t.u-tokyo.ac.jp An etching current of 10 mA was adjusted to flow between

0034-6748/99/70(8)/3373/4/$15.00 3373 1999 American Institute of Physics

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 3374 Rev. Sci. Instrum., Vol. 70, No. 8, August 1999
FIG. 1. The circuit controlling termination of etching. Delay circuit B is
added to elongate the cutoff time intentionally.
the two electrodes that were connected to terminals C and A
in Fig. 1. It took typically 10 min until the wire eventually
broke apart. The variation of the electrolytic current was
monitored by the voltage at C. The cutoff time was varied by
changing the resistance in the RC delay circuit. The current
profile on breakage of the wire was recorded by a digital
oscilloscope.
C. Measurements of tip radius
Scanning electron microscopy SEM formerly used3,79
to measure the radius of the curvature of STM tips has not
enough resolution to permit measurements of atomically
sharp tips. For more accurate measurements, we used a FIM
to directly image the atomic arrangement at the tip apex. A
tip fabricated by the above method was rinsed with distilled
water, quickly loaded into an ultrahigh vacuum chamber of
FIM and placed opposite to a counter electrode which was
biased at about 6 kV with respect to the tip. The image of
the tip apex was formed at room temperature with a He im-
aging gas of 104 103 Pa and a Chevron-type microchan-
nel plate.
The FIM images of tungsten tips thus prepared revealed
that we have in most cases a 011 face at the center of the
apex with satellites of 112 faces around it. The radius of
curvature was evaluated by
nd
1
1cos 30
with n, the number of the rings between the 011 face and
the 112 faces Fig. 2, and d, the monolayer step height.11
D. Measurements of field emission current from tips
In principle, the FIM assembly could be used to measure
field emission current simply by reversing the polarity of the
tip bias. However, when the base pressure is not sufficiently
low, the tip is easily sputtered by residual gas molecules that
are ionized by the impact of energetic electrons and acceler-
ated backward to the tip by the applied voltage. Owing to
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Nakamura, Mera, and Maeda
FIG. 2. Tip geometry illustrating how to evaluate the tip radius .
this effect, the emission current thus measured in the FIM
chamber was found to quickly decrease to a substantially low
level. Hence, we measured the emission current of a STM
configuration in an ultrahigh vacuum environment.
A tip fabricated by the present method was loaded into a
STM chamber whose base pressure was kept lower than 3
108 Pa. The tip mounted on the STM scanner was faced
to a cleaved surface of highly oriented pyrolytic graphite
HOPG at a distance of 2 mm. The current flowing into the
tip due to the emitted electrons was measured as a function
of the negative bias voltage applied to the tip with respect to
the sample. No difference in the emission current was found
between the tip prepared by the above cleaning process, and
the one subjected to sharpness measurements by FIM in the
chamber connected to the STM chamber by a gate valve.
III. RESULTS AND DISCUSSION
Figure 3 shows a SEM image of a tip fabricated with a
cutoff time of 50 ns, which demonstrates the high aspect
ratio of the tip cone. Figures 4a, 4b, and 4c show FIM
images of the tip apices fabricated with cutoff times of 50 ns,
750 ns, and 12 ms, respectively. The radii of curvature of
these tips evaluated from these images by Eq. 1 are plotted
in Fig. 5 with respect to the cutoff time. The sharpest tips,
8 nm on average, were obtained at the shortest cutoff
time of 50 ns. The data obtained by Ibe et al.1 are added to
the plot for comparison. The systematic discrepancy between
the two data sets is considered to be due to the difference in
the resolution of the microscopy. These results clearly indi-
cate that it is effective to shorten the cutoff time to obtain
tips much sharper than before. The error bars in Fig. 5 evalu-
FIG. 3. An SEM image of a tip fabricated with the cutoff time of 50 ns.
 Rev. Sci. Instrum., Vol. 70, No. 8, August 1999 Atomically sharp tip fabrication 3375

FIG. 6. A typical STM image obtained with the sharpest tip. The sample is
C60 films grown on a Si 111 77 surface. The sample bias and the current
were set at 2.0 V and 0.1 nA, respectively. Note that the internal structure
of the C60 clusters is resolved.

7 substrate. The internal structure of each C60 cluster was

routinely resolved as in Fig. 6 when we used the tips pre-
pared in the present scheme.
The field emission current from a tip fabricated with the
shortest cutoff time of 50 ns is shown in Fig. 7 as a function
of bias voltage V b applied to the tip. The maximum current
achieved at 200 V was 5.9 nA. The error bars indicate the
magnitudes of the current signal noise power. Theoretically
the field emission current per unit area is given by the
FowlerNordheim formula

FIG. 4. FIM images of apices of tips fabricated with the cutoff times of 50
ns a, 750 ns b, and 12 ms c.
J
1.6106 E 2

exp
6.9109 3/2
E
A/m2 2

with eV and E V/m denoting the work function of the

ated for 57 tips at respective cutoff times demonstrate the electron emitting material and the electric field at the surface,
reproducibility of this method. The results were insensitive respectively. If we neglect the variation of and E over the
to the variation of the wire depth in the range between 1 and
2 mm.
A typical STM image obtained with the use of the sharp-
est tip is shown in Fig. 6 for C60 films grown on a Si1117

FIG. 7. The tip bias dependence of the field emission current from the tip
FIG. 5. The dependence of tip radius on the cutoff time of etching. The data fabricated with the cutoff time of 50 ns. The HOPG sample placed 2 mm
obtained by Ibe et al. are shown with open circles for comparison. from the tip was used as the positive electrode.
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 3376 Rev. Sci. Instrum., Vol. 70, No. 8, August 1999 Nakamura, Mera, and Maeda

tip surface, we expect the total emission current to be JA,
where A is the effective area of the electron emitting surface.
For the present separation between the tip and the sample
that was chosen as much larger than the tip radius, the elec-
tric field E may be approximately given by
Vb
E ,
5 2
where m is the tip radius experimentally measured. The
solid line in Fig. 7 represents the best fit of Eq. 2, obtained
when one uses a relevant value of 4.6 eV for tungsten,
and the effective surface of the sharpest tip area, A, is ad-
justed to 50 nm2 . This value of A 50 nm2 ) is 18% of 2 2
280 nm2 ), the surface area of a hemisphere to which the
tip apex ( 6.7 nm in this specific measurement is approxi-
mated. It may be reasonable that electrons are emitted from a
fraction of the hemispherical tip facing the sample.
ACKNOWLEDGMENTS
The authors thank Dr. T. Hashizume for his valuable
advice on improvement of the FIM system. Part of this work
has been supported by a Grant-in-Aid for Scientific Research
B, C and that on Priority Areas.
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