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The AFM As A Tool For Surface Imaging
The AFM As A Tool For Surface Imaging
The AFM As A Tool For Surface Imaging
The atomic force microscope was introduced in IYXh as a new instrument lor examining the \urtace (11 Insulating cl_~atal\. I‘hr~-c.
was a clear implication in the first paper that it was capable of resolving single atoms. Unambiguous evidence lor atomic rc\olut~on
with the AFM did not appear until 1993. In the intervening years the AFM evolved into a mature instrument that prcrvidcr u\ with
new insights in the fields of surface science, electrochemistry, hiology and the technology. In thih paper WC nilI discus\ the cwlution
of this new high resolution microscope and describe some of the events that led up to the present state-of-the-art In\trument
what they don’t know. Then, when they see other forces and produces hysteresis in the force
vaguely in their fog something they recognize, versus distance curve.
they think, “Ah, I know that.” And then it’s The group with Paul Hansma in Santa Barbara
just one more step to, “Ah, I know the whole reasoned that if imaging was possible with the tip
thing.” And their mind thrusts forward into penetrating the film, it would be equally possible
the unknown and they begin to recognize what for the system to operate with the entire can-
they didn’t know before and they increase their tilever immersed in fluid [7]. Their observation
powers of understanding [S].” was profound. It carried the force microscope
The lectures at Oberlech are hazy in my mind, into electrochemistry and biology.
but the walk led by Heini Rohrer is still vivid. It I was introduced to electrochemistry by the
was to begin at 9:30 on Saturday morning. Heini work of A. Gewirth at the University of Illinois.
told us that we should be well rested, it would be While he listened to Hansma describe his liquid
a strenuous walk over at least one mountain pass. microscope, Gewirth designed an experiment to
When I turned in Friday evening, Gerd and Heini observe the deposition of copper on gold. He
were deep in conversation. On my way to break- traveled to Santa Barbara, and in two weeks time
fast the next morning I encountered Heini and performed the copper on gold experiment IS]
Gerd in the same position discussing their philos- with the results shown in Fig. I. It was a dramatic
ophy of experimental science. When he saw me, event with manifest repercussions.
Heini jumped up saying, “I must get some rest”. We are optimistic about the prospects for
Two hours later he showed up at the meeting molecular biology because of the work with the
place ready to go. Indeed, it was a strenuous walk DNA molecule. The group with Bustamante, first
but Heini insisted on maintaining a good pace at in New Mexico and now in Oregon, collaborating
the head of the pack. Sunday I sat in front of the with Helen Hansma in Santa Barbara and Keller
TV watching Boris Becker winning the Wimble- in New Mexico have recorded meaningful and
don. It was 2 o’clock in the afternoon when Heini definitive images of biological molecules [9]. In a
emerged from his room muttering, “Sleep is such different setting Eric Henderson at Iowa State
a wonderful thing”. found that the liquid instrument could produce
The atomic force microscope emerged from its images of whole cells and delineate the internal
cocoon more slowly than the STM. When the fibril structure in the living cells [lo].
Zurich group released the image of a silicon (111)
7 x 7 pattern, the world of surface science knew
that a new tool for surface exploration was at
hand. With the force microscope it was a series of
incremental steps. I realized the strength of the
force microscope when Albrecht measured the
atomic structure of boron nitride. I began to
believe when the results started to emerge from
Paul Hansma’s laboratory in Santa Barbara. Mc-
Clelland [6] with the group at IBM/Almaden
studied the force on the cantilever as the tip was
brought into close contact with the sample sur-
face. The force versus distance curve for the
withdrawal cycle was distinctly different from that
of the approach cycle. They concluded that there
must be a thin liquid film covering the surface,
and when the tip penetrated this liquid film a
capillary was formed around the tip. The capil- Fig. 1. The AFM image illustrating deposition of copper on
lary force on the tip is large. It dominates the gold (courtesy of A. Gewirth).
In another sector of the world of science and
technology, Professor T. Ohmi [I I] was con-
cerned with the roughness of silicon wafers. In
modern devices the width of the lines and the
thickness of the oxide beneath the gate electrodes
continue to shrink. The E-field that an oxide film
can sustain before breakdown is a measure of the
dielectric strength of the film. If thin oxides are
grown on rough silicon substrates, the gate oxide
Spacmg between Particles a.”
integrity is comprised by a reduction in the di-
Fig. 2. Interatomic force between two small particle\
electric strength. It is, therefore, imperative to
measure the roughness of silicon wafers and Pro-
fessor Ohmi selected the force microscope for The geometry of the force microscope does
this task. It was a wise selection. He has deter- not correspond to two closely spaced atoms.
mined that the RMS value of roughness must be rather it resembles a small sphere above a plane.
reduced to 1-2 A to maintain the integrity of the The force versus distance curve for this configu-
gate oxide. ration comes from the calculation in Ref. [12].
Seven years have passed, and the atomic force Section 10.2. The general features depicted in
microscope has emerged as a commercial instru- Fig. 2 remain intact with a repulsive force for
ment. The microcantilevers have been perfected. small spacings and an attractive force for large
The instrument has been embraced by scientists spacings. The majority of the force microscopes
and technologists. Electrochemists use the device operate in the contact mode where the tip moves
to study electrolytic deposition processes, bio- against the “hard core” potential of the sub-
physicists use it to observe biological molecules in strate. Even though the forces are small (10 7-
aqueous solutions. Surface scientists use it to 1OY” N), surface damage is still encountered with
study structures on non-conducting surfaces. some samples. For those applications the attrac-
Technologists use it to study fabricated structures tive mode is preferred since there is no contact
on silicon substrates. Others believe it can be between tip and sample.
used for new high density storage devices. All of The attractive force, known as the van der
these are interesting areas but we will only exam- Waals force [ 131, originates from the polarization
ine a partial list in this paper. of the electron cloud surrounding the atomic
core. The van der Waals force for the sphcrc
above the plane varies as the inverse square of
2. Section of forces the distance between tip and sample.
There is no known example where the van de1
The forces measured with the force micro- Waals force has been measured with the force
scope are discussed in the book by Israelachvili microscope. The reason is quite simple. This force
[12]. Force, as the negative gradient of the inter- diminishes as the physical volume decreases. In
action potential, is easily measured with physical the force microscope with a tip of nanometer
apparatus. For two closely spaced atoms, or small dimensions the attractive forces due to the in-
molecules, the interaction energy is described by duced polarization are small and stronger forces
the Lennard-Jones potential. The force between control the motion of the tip. The force micro-
the particles as a function of their separation is scope normally operates in ambient air where
illustrated in Fig. 2. There are two regions, one to electrostatic charges can accumulate. Furthcr-
the left of the potential minimum where the more the humidity of the air leads to the forma-
particles are repelled from each other and one to tion of a thin layer of liquid over the surface oL
the right where the particles are attracted to each the sample and a capillary forms when the tip
other. dips into the film. The capillary [14] and electro-
C.F. Quate / The AFM as a tool for surface imaging 983
static [15] forces dominate the polarization forces over the surface with a spacing of 50-200 .&. This
of van der Waals. spacing is controlled by monitoring the I‘esonant
In the attractive mode [16] the tip is scanned frequency of the cantilever. This feature iis impor-
Fig. 3. (a) The heart of the AFM - the cantilever with integrated tip. (b) Enlarged view of integrated tip and cantilever (courtesy of
S. Akamine).
tam, and we divert the discussion to describe the force field. In turn, resonant frequency changes
primary feature of the method. to
The cantilever spring constant, k, relates the
w, = V-(k - 3F/h)/i-. (4)
displacement, AZ, of the end of the cantilever to
the force, F, applied to the end of the cantilever This change provides a method for controlling
by the relation [17], the spacing between tip and sample. The can-
tilever, as mounted on a piezoelectric motion
F=Az. (1)
device, can be moved in z in such a manner as to
The resonant frequency, wr, of a cantilever with a keep the resonant frequency constant. This means
mass, m, is given by the relation, that the tip moves in a region where the force
gradient is constant. This implies that the tip
w,. = (k/m (2) spacing is constant since the gradient is a single-
This situation prevails if the force at the end of valued function of the z-spacing.
the cantilever does not vary with the z-position of
the cantilever. In general, this is not the case.
The force does vary with the distance between tip 3. Cantilevers and tips
and sample. We can express it thus,
The cantilevers and tips used in the FM arc
F=F,,+(i)F/az)Az=k AZ, fabricated with anisotropic etching of silicon. This
art is part of the emerging field of micromachin-
F,, = (k - aF/az)Az. (3)
ing [IS]. When silicon is etched in a solution of
We see from this that the effective spring con- KOH, the (111) face etches slowly in comparison
stant changes in the presence of a gradient in the with the other faces. This characteristic makes it
Fig. 4. Classical systems for detecting the motion of cantilevers in the AFM
C. F. Quate / The AFM as a tool for surface imaging 985
easy to etch pyramidal shapes into the (100) face Beyond that a more refined technique has
of silicon. The pits are in the form of inverted evolved to the point where pillar-like tips can be
pyramids. A thin film of silicon nitride deposited grown on top of the pyramidal tip. The new tips
on this surface will conform precisely to the to- are formed when the surface is bombarded with
pography and fill in the inverted pyramid. Subse- the electron beam for an SEM. Presumably this
quent to the nitride deposition, the underlying comes from the polymerization of the residual
silicon can be completely removed leaving only hydrocarbons in the atmosphere of the SEM.
the deposited film of nitride. This forms the Recently David Keller [21] in New Mexico has
cantilever where the tip extends outward toward demonstrated the utility of this type of tip in
the sample. connection with his work with biological mol-
Conversely the anisotropic etching characteris- ecules.
tic can be used to form a tip of silicon extending
outward from the surface as shown in Fig. 3. This
configuration is intriguing since the tip can be 4. Detection of cantilever motion
sharpened with further etching. This procedure
follows from the work of Marcus and Sheng [19] The FM does not measure force; it measures
where they observed that the oxidation rate of the deflection of the microcantilever. The linear
silicon was dependent on the curvature of the relation expressed in Eq. (1) between force and
silicon substrate. They found that a planar sur- displacement permits us to use the displacement
face will oxidize at a faster rate than a surface data to measure the force. The detecting systems
with curvature. The flat sloping face of a pyramid for monitoring the deflection fall into several
tip oxidizes faster than the other regions. When categories illustrated in Fig. 4. The first device
the oxide was removed by etching, the induced introduced by Binnig was a tunneling tip placed
curvature on the pyramidal faces results in a above the metallized surface of the cantilever.
sharpened tip. Akamine and Quate [20] used this This is a seasitive system where a change in
principle to sharpen the apexof a silicon pyramid spacing of 1 A between tip and cantilever changes
to form a tip for the force microscope. the tunneling current by an order of magnitude.
Fig. 6. ‘I’he molecular structure of didodecylbenzene (DDB) molecules on graphite imaged with the AFM in the contact mc~ic
(courtesy of H. Fuchs).
C.F. Quate / The AFM as a tool for surface imaging 981
Fig. 7. The surface of an unpatterned silicon wafer in the AFM. The rms roughness is 1.5 A (courtesy of B. Doris).
adhesive force for Mg-Mg is 5 X 10” N/m’, or force of a single atom tip ttr IO--“I N to avoid
about 5 x lO_“’ N/atom. This force applied to a def(wmation of the surface through plastic flow.
single atom in the Mg crystai would resuft in The imaging force used to recwd atoms with the
brittle fracture. At most temperatures Mg fails in AFM is greater than IO ” N. With 2 lilnitjn~
plastic flow, and we must thcreforc reduce the pressure of 5 x 10” N/m’ WC conclude that the
Fig. 9. The profile of a surface feature of a 16 MB DRAM. The trenches <ire 0.5 pm in width and 1 pm in depth (courtry of
K. Wickramasinghe).
CJ. @ma ,I’ The AFM as a tooi for suijkc~ imaging 989
contact area must extend over several atomic to the studies of surface roughness (see Fig. ‘7)*
sites. ISow then do we rationahze the images that Roughness of silicon wafers can increase during
report atomic resolutions Heretofore, the pub- the fabrication of microchips, and it is necessary
lished images have dispIayed perfect periodic&y to monitor this parameter as the wafer moves
without defects, and the lack of defects is the key through the FAIL The example from Uhmi’s work
to the dilemma. We know that multiple images of [llf, shown in Fig, 8, illustrates that surface
periodic structure are also periodic. It is not roughness can increase when excess ammonia is
possible to distinguish between a single image used in one of the standard wafer cleaning steps.
and superimposed multiple images that arise from Surface roughness is one facet, surface profil-
broadened tips or from multiple tips. To resolve ing is another, The ilhrstration in Fig. 9 is typicai.
the ~mbi~ui~ and demonstrate true atomic reso- With the advancing state of art in microchips the
lution it is necessary to reduce the imaging force line widths will shrink to 0.25 iurn while the
to 10-i* N and image atomic detaif on surfaces thickness of the photoresist Layers will remain at
with fat&e im~rf~t~ons~ such as step edges, or f pm, Via’s with this aspect ratio are diffi~~It to
lattice vacancies. This has n5w been accom- profife with avaiiabje tools. We know that the
phshed [30] in a way that we discuss in a later force microscope will play a role because of the
section. work carried out by groups such as those with
We will bypass the marvelous work done by Wickramasi~~h~ at IBM and Griffith at AT&T,
the electrochemists and the biophysicists and turn The IBM group has used the non-contact mode
70
35
b
O- \ 0.2
0
Fig. 10 (continued).
.o.*
6. The non-contact mode
ously in Section 2. The essence of this idea is detail on the rounded hillocks is only visible with
contained in the work of Israelachvili and Tabor the non-contact mode.
[33]. It was introduced to the force microscope in The shift in resonant frequency of mechani-
the work of Martin, Williams and Wickramas- cally vibrating elements is a powerful method for
inghe [16] and Albrecht et al. [34]. controlling narrow spacings. It is used routinely
The non-contact mode is essential for examin- in the magnetic force microscope where a mag-
ing soft samples where tip contact could change netic tip is used to image magnetic field patterns.
the topography. A striking example is shown in We will return with more details in the next
Fig. 10. This soft sample is a layer of photoresist section. The principle is also used in the near
that has not been hardened with baking. A sec- field optical microscope when it is combined with
ond example of the utility of the non-contact the force microscope for the purpose of control-
mode is illustrated in Fig. 11. It is a polysilicon ling the spacing between the optical aperture and
surface with the structure of the grains as the the sample [35].
prominent feature. Grain structure of polysilicon The non-contact mode is now available in
is easily recorded in other modes but the fine “large sample” instruments. There the probe can
80
60
urn
60 70 6@ 50 40 30 20 10 @
urn
Fig. 12. Image of the magnetic field pattern on a hard disk (courtesy of I. Smith).
be positioned over any segment of an 8 inch in Fig. 12 is typical of the work that can bc done
silicon wafer. Imagine the response when this with the instrument.
mode is introduced to the semiconductor indus- The magnetic resonance force microscope [4O]
try, “The scanning probe, with nanometer resolu- is the offspring of the magnetic force microscope.
tion, allows the operator to examine the full area In this instrument a small particle of paramag-
of an 8 inch wafer without touching the silicon nctic material is mounted on a cantilever. The
surface.” This indeed must be the threshold of unit is then immersed in a magnetic field which
the 21~ century. polarizes the spinning electrons. The electric field
from a small RF coil is used to drive electron spin
resonance (ESR). The magnetic field fixes the
7. Other modes resonant frequency, and when this field is modu-
lated. the force on the cantilever is modulated in
Just as the STM spawned the AFM so it is that a corresponding manner. If the modulation frc-
the AFM spawned other forms of scanning quency of the magnetic field is adjusted to excite
probes. The friction force microscope [36] which the mechanical resonance of the cantilever. the
measures the lateral force on the scanning tip has amplitude of motion in the cantilever builds to a
been used to great effect by workers such as detectable level. The modulating frequency is
Mate at IBM and Kaneko at NTT to study the equal to one-half the resonant frequency since
coefficient of friction for various surfaces. The the driving force on the cantilever is proportional
capacitance microscope [37] is used to measure to the square of the gradient of the field. In the
the variation in capacitance between the tip and system studied by Rugar et al.. the noise floor of
sample. It has been used to profile the doping the vibrating cantilever was 10 ” N. This was in
levels in silicon. The interfacial microscope [38] vacuum at room temperature. They predict that
uses a double ended cantilever to measure the the sensitivity can be improved by several orders
curve of force versus distance at various points in of magnitude if the cantilever is redesigned and
the image. cooled to liquid helium temperatures.
Among the members of this family the mag- The magnetic resonance force microscope has
netic force microscope [39] (MFM) has special some remarkable features. Electron spin rcso-
significance since it has spawned an offspring of nance at 1000 MHz can be detected with a me-
its own, one that responds to signals from mag- chanical device resonant near 10 kHz. The spatial
netic resonance. The magnetic force microscope,
operating in air, images magnetic patterns with-
out special preparation of the sample. The MFM
is used to image the gradient of the magnetic
field with a lateral resolution that is better than
0.1 pm. A spacing of 100-200 A between tip and
sample is maintained throughout the scan. In the
magnetic force microscope a magnetic tip with
the magnetization aligned with the axis of the tip
is mounted on a flexible cantilever. The magnetic
dipole of the tip interacts with the stray magnetic
fields from the sample. The stray magnetic fields
exert a force on the magnetized tip, and this is
the information displayed in the image. In reality
the gradient of stray fields alters the resonant
frequency of the cantilever as described in Sec-
tion 2, and it is the change in resonant frequency
that is used for the information signal. The image
CF. Quate / The AFM as a tool for surface imaging 993
position of spins in the lateral plane can be magnetic resonance with a sensitivity sufficient
imaged when a gradient is introduced into the for the imaging of a single spin may be within
magnetic biasing field. A microscope based on their grasp!
4.5 nm
distance (MI)
Fig. 14. True atomic structure with the AFM in the contact mode. This is the surface of calcite immersed in purified water showing
the oxygen atoms as the bright spots (courtesy of F. Ohnesorge).
A second example where microwave frequen- nig [30] of the IBM Laboratory in Munich ap-
cies arc used to deflect a mechanical cantilever peared in June 199.3. They used the AFM im-
comes from the group with D. Bloom at Stanford mersed in water to study the cleaved (lOi4) fact
[4I]. They worked with a conventional tip of calcite. With this arrangement they reduced
mounted on a metal coated cantilever and the force exerted on the sample to IO I” N which
scanned over the surface of an integrated circuit. is a factor of IO less than that LISCCI in convcn-
The stray electric fields from the IC exerts a force tional microscopes. Their images not only show
on the cantilever. The mechanical cantilever can- the atomic arrangement of the uppermost oxygen
not respond to microwave frequencies, neverthe- atoms but they also show atomic scale dcfccta.
less the group with Bloom devised a system to Atomic structure and atomic steps between tcr-
monitor the spatial variation of electric fields at races are common in the images from the tunnel-
microwave frequencies. They applied two RF sig- ing microscope but they did not appear in the
nals, ,f, and fi, to the circuit beneath the can- images from the AFM until Ohnesorgc and Bin-
tilever. The force on the cantilever is propor- nig published their results. Their images of cal-
tional to the square of the E-field. It is a cite are shown in Fig. 14.
“square-law” detector for force, and this is used It has been a grand time for those associated
to generate a force at ,f, -fr. When the differ- with this era. The era is not over, there is more to
encc frequency is adjusted to the mechanical come as this form of instrumentation is moved
resonance, the amplitude of cantilever motion beyond imaging and employed in the fabrication
reaches a level that is detectable. The tip is of nanostructures.
scanned over the active circuit to record the
spatial variations in the E-field.
8. Summary
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