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Real-space visualization of atomic- and molecular-scale structures
has always attracted researchers, and they welcomed the invention
of scanning tunneling microscopy (STM) in 1981. STM images of many
crystalline compounds revealed their atomic and molecular arrangements
as well as various single-atom defects. STM applications, however,
were limited due to requirement of sample conductivity.
Therefore, atomic force microscopy (AFM), which can be applied
to any kinds of samples, became the leading scanning probe method.
For the past 20 years AFM has been developed into a powerful characterization
technique but the question of atomic-resolution in AFM is still
opened. The initial AFM measurements were performed in the contact
mode and the atomic-scale lattices were revealed first in the images
of graphite, MoS2, BN and mica [1]. Similar observations were later
reported for a large number of organic and inorganic crystals and
layers [2]. These images were usually obtained using Si3N4 probes
(an averaged tip size ~ 20 nm) and soft Si probes (tip size in the
10-20 nm range).
The main drawback of these images was an absence of atomic-scale
defects that implies only lattice but not true atomic resolution
[3]. The latter suggests a presence of single-molecular defects
that, indeed, were observed in AFM images obtained in oscillatory
frequency modulation (FM) and amplitude modulation (AM) modes. The
images of surface lattices of Si (7x7) and InP crystals were obtained
in FM studies in UHV [4-5]. Latter, true atomic-scale FM visualization
of mica and polydiacetylene (PDA) crystals was achieved in air and
under water [6-8].
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| (a) Scan size 15 nm. Height image. A single defect in molecular
lattice of PDA crystal is visible. |
(b) Scan size 23 nm. Height image. Molecular lattice
of PDA is observed only. |
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These results were obtained by researchers which used custom instruments
with optical deflection and interferometric detection systems. It
also became clear that FM is not unique oscillatory mode for observation
of surface lattices with defects and similar results were achieved
in AM studies in air [9-10]. The related images of polydiacetylene
crystal obtained with Dimension 5000 (Veeco Instruments) and Agilent
5500 (Agilent Technologies) microscopes, Figures 1a-b. In these
studies different MikroMasch probes (Hi-Res-C and DP-14) were applied.
The molecular-scale observations in AM, whose feedback mechanism
is slower than in FM, require a low thermal drift environment. Also
it is easy to achieve the molecular-scale resolution using most
sharp probes if they are not damage in the engagement procedure
and preserved from breaking in the low-force imaging.
For users of MultiMode and Dimension 3100 and 5000 SPM microscopes
(Veeco Instruments) there are more specific recommendations for
preventing sharp probes from damage:
1. Excessive tip-sample forces can be generally avoided by using
softer cantilevers though there are limitations caused by a need
of the probe retraction from a surface in every oscillation cycle.
This circumstance limits a use of probes with stiffness below
0.3-0.5 N/m for imaging in oscillatory modes.
2. Engagement should be done most gently. In Nanoscope software
under "Microscope" there is a window "Tapping Engage",
the following choice of parameters looks most promising.
Engage delta set-point 0.01
Engage final delta set-point 0.00
Engage test threshold 100
Engage min set-point 50
TM engage gain 0.4
Sew tip Yes
Parameters below "sew tip" are not relevant after "sew
tip" is "Yes".
While using soft cantilevers and the above engagement parameters
one might experience a 'false" engagement especially when
initial amplitude is rather small, say 0.5V. If this happens than
further moving a probe down with a stepper motor in step-by-step
approach might help to accomplish the engagement routine.
3. Light tapping conditions are preferable for scanning with
sharp probes. In other words, free amplitude (or target amplitude)
should be chosen rather small. Practically, 0.5V amplitude seems
to be fine for imaging relatively smooth surfaces. After the engagement,
set-point amplitude should be chosen as close as possible to the
free amplitude. In other words, one should adjust set-point, scanning
rate (slower - better) and gains (increase of Integral and Proportional
gains can be done up to the point at which periodical oscillations
appear). set-point amplitude is lowered from amplitude of free-oscillating
probe One can achieve low-force imaging (light tapping conditions)
by lowering set-point amplitude (from initial amplitude of a non-interacting
probe) to the point that "trace" and "retrace"
height profiles (in Scope mode) become close to each other and
the phase of interacting probe is still not far from that of the
free-oscillating probe.
Despite the fact that so-called true atomic resolution was achieved
in the FM and AM imaging modes the value of these results is still
questionable. The computer simulation of AM imaging of polydiacetylene
crystal showed that real atomic-scale resolution could be achieved
only when the AFM probe has an apex of the atomic size and imaging
is performed in the low-force regime [11]. Otherwise, even the observation
of the isolated atomic- or molecular-size defect does not mean that
the molecular arrangement surrounding such defect is reproduced
correctly.
Consequently, there is still a lot of room for further improvement
of high-resolution imaging that requires the use of sharp probes
and better quality instrumentation allowing low-force imaging using
such probes.
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References:
1. Albrecht T., Quate C., J. Appl. Phys. 1987, 62,
26.
2. Magonov SN, Whangbo M-H, Surface Analysis with STM and AFM. Wenheim:
VCH, 1996.
3. Landman U., Luedke W. D., Nitzan A., Surf. Sci. Lett. 1989, 10,
L177.
4. Giessibl F. J. Science 1995, 267, 68.
5. Sugawara Y., Ohta M., Ueyama H., Morita S., Science 1995, 270,
1646.
6. Fukuma T., Ichii T, Kobayashi K, Yamada H, Matsushige K., Appl.
Phys. Lett. 2005, 86, 034103.
7. Fukuma T., Kobayashi K., Matsushige K., Yamada H. Appl. Phys.
Lett. 2005, 86, 193108.
8. Hoogenboom B. W., Hug H. J., Pellmont Y., Martin S., Freederix
P.L.T.M. Fotiadis D., Engel A., Appl. Phys. Lett. 2006, 88, 193109.
9. Klinov D., Magonov, S. Appl. Phys. Lett. 2004, 84, 2697.
10. Magonov S., Amer. Lab. 2008, 40, XXX.
11. Belikov S., Magonov S., Jap. Journ. Appl. Phys. 2006, 45, 2158.
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