Scanning Near-Field Optical Microscopy (SNOM)

Gerd Kaupp
University of Oldenburg, Oldenburg, Germany

1 Introduction
2 Results and Discussion
3 Conclusions
Note
References

1
2
17
17
17

INTRODUCTION

The acronyms SNOM (scanning near-field optical microscopy) and NSOM (near-field scanning optical microscopy)
are used for the near-field microscopy. SNOM started with
the idea of a very small aperture (smaller than half the
wavelength of light) for the light source. The confined
light passing through a small aperture may break the Abbe
diffraction limit of microscopic resolution, giving optical
resolution below /2 of the light. The light is then collected in the far field using diverse techniques. Its history
started about five years after the development of atomic
force microscopy (AFM) in 1990s with illuminated metalcoated waveguide tips with apertures of about 100 nm.
Numerous instruments of that type have been sold, and the
history of aperture SNOM techniques has been reviewed.1
However, the necessary (expensive) blunt fiber tips exhibit
flat ends with total widths of about 500 nm at the end,
which prevents sufficiently close approach to rough surfaces
and also to molecularly flat surfaces because of their high

temperature due to the light confinement; also, the optical resolution was not better than the aperture. Aperture
SNOM techniques could not therefore develop as widely
used standard tools, although the heat of metal-coated tips
has been used for producing lithographic pits on surfaces.2
A detailed discussion on the difficulties encountered under
various circumstances is given in Ref. 3. Furthermore, apertureless photon scanning tunneling microscopy (PSTM),
which collects forbidden light with a transparent or opaque
contacting AFM tip from parallel backside illumination
above the angle of total reflection, could not find application to real-world surfaces, because topography and
local changes of the refractive index add to the optical
signal.
It was only a new and apparently unexpected or even
denied4 near-field enhancement effect in shear-force distance that allowed SNOM on rough surfaces with a constant
distance (more precisely in constant vibration damping gap)
of <10 or 5 nm to the surface with sharp uncoated tapered
waveguide tips by reflection back to the fiber (internal
reflection mode). This near-field collection of light occurs
under shear-force AFM control and thus provides a simultaneous topographic image independent of the optical surface
mapping with short scanning times (typically 2 min per
frame). This technique allows SNOM on real-world, rough
surfaces without topographic artifacts up to high slopes for
all types of transparent and opaque samples3, 510 where
hot and blunt metal-coated tips cannot follow the topography. After the successful establishment of the unprecedented near-field enhancement, the much more elaborate
apertureless SNOM techniques, that is, scanning interferometric apertureless microscopy (SIAM) and near-fieldscattering SNOM, were developed. SIAM focuses laser
light on vibrating AFM tips tapping on a vibrating surface.
The phase shift is detected in the far field, requiring double modulation for decreasing the background signal.11, 12

Supramolecular Chemistry: From Molecules to Nanomaterials, Online 2012 John Wiley & Sons, Ltd.
This article is 2012 John Wiley & Sons, Ltd.
This article was published in the Supramolecular Chemistry: From Molecules to Nanomaterials in 2012 by John Wiley & Sons, Ltd.
DOI: 10.1002/9780470661345.smc045

Techniques

The near-field-scattering SNOM focuses a laser beam to the

apex of a metal tip as scattering device that is in tapping
mode to the surface, in order to obtain field enhancement
under the metal tip. The dither provides the demodulation
of the signal at higher harmonics for reducing the background of scattering from both the illuminated probe shaft
and the sample. The optical near-field interaction signal
is extracted by the demodulation procedure.13, 14 Clearly,
these elaborate techniques are restricted to very flat surfaces, and are not applicable to mappings of rough and
delicate surfaces. At very low roughness, the structural
details in the optical response remain unclear. Another
apertureless near-field imaging technique using a siliconbased electrically pumped nano-light-emitting diode (LED)
probe in shear-force feedback and collection in transmission provided topographic resolution of 50 nm and optical
resolution of 500 nm.15 However, such resolution is easily
obtained by confocal microscopy.
We concentrate here on the simplest and most versatile
SNOM technique with illuminated, sharp, uncoated tips in
shear-force distance with reflection back to the uncoated
fiber, because only this technique is able to deal with
delicate surfaces that exhibit low or high corrugation in
supramolecular chemistry or for the characterization of
single and aggregated nanoparticles.

2
2.1

RESULTS AND DISCUSSION

The basics of SNOM

2.1.1 Foundation of apertureless SNOM with

near-field collection
Near-field light collection in shear-force mode requires
reflection back to an illuminated tip that is in shearforce contact16 with the surface in question. Therefore,

the well-established shear-force AFM with horizontal tip

dither at <10 nm (typically about 5 nm) distance is required.
The difference between aperture and apertureless tapered
tips is clearly demonstrated with an on-scale comparative
sketch and a photograph of a tapered tip in Figure 1.
Clearly, hot and blunt metal-coated tips (Figure 1a) cannot
reasonably follow topography. Also asperities or inclined
alignments do not help much. The improvement by placing
the typical 100 nm aperture at the apex of a hollow
four-sided aluminum pyramid (similar to the sketch of
Figure 1(a) but blunter with an opening angle of about
70 ) lowers the heat, but bluntness and high width/height
ratio of about 1.5 are unsuitable for narrow topographies
and resolution cannot be better than 100 nm when used
in tapping mode. Even the more recent use of a foursided hollow aluminum pyramid in beam deflection mode
for AFM control and collection of the scattered light
(alpha300 S scanning near-field optical microscope of Witec
Instruments Corp., Maryville, TN, USA)17 suffers from
rather low optical resolution in the range of 50100 nm.
However, ambient sharp tips (Figure 1b and c) easily follow
rough topography in shear-force mode (better than contact
mode with AFM using Si3 N4 cantilever tips3 ) with slope
angles up to the tip gradient under shear-force distance
control even on delicate samples.
The illuminated sharp dielectric tip without metal coating (Figure 1b and c) under shear-force control with a
horizontal dither at 100400 kHz (close to the mechanical resonance) illuminates a large spot with roughly 1 m
diameter. Nevertheless, it is possible to obtain nanometric
resolution due to an unexpected, very strong enhancement
of internal reflectivity into the sharp dielectric tip in the
shear-force gap.3, 510 Therefore, our new physical effect for
the local light collection in the very close near-field is used
here. The low constant background of far-field collection by
the transparent tip is not part of the optical contrast. The

Al

500

0
(a)

500

200 100 200

1000 nm

2000

0
(b)

1000 nm

2000
(c)

Figure 1 Sketch of (a) a typical metal-coated tip and (b) a sharp uncoated tip. (c) Photograph of an uncoated tapered tip indicating
the high aspect ratio (without resolution of the <20 nm end radius).
Supramolecular Chemistry: From Molecules to Nanomaterials, Online 2012 John Wiley & Sons, Ltd.
This article is 2012 John Wiley & Sons, Ltd.
This article was published in the Supramolecular Chemistry: From Molecules to Nanomaterials in 2012 by John Wiley & Sons, Ltd.
DOI: 10.1002/9780470661345.smc045

Scanning near-field optical microscopy (SNOM)

100
Scan
Optical signal (a.u.)

Surface
point

50

Coarse

Close

0.1 mm

1 m

10

20

Approach
5 nm

30

40

50

60

Time (s)

Figure 2 Approach of a sharp, uncoated, multimode (core

diameter 5.7 1 m) tapered quartz glass tip to a chemically
uniform surface while monitoring the signal level, showing highly
enhanced light intensity level only when the tip is at the shearforce distance.3

optical mapping of a surface reflects a chemical (or material) contrast due to differences in the near-field reflection
of different components at different sites. There is no topographical artifact by the corrugation, notwithstanding the
extreme conditions of steepness, overhangs, and so on.
The sharp uncoated tip is used both as an emitter and
a detector in this technique. The considerable increase
in collected reflected light intensity is easily seen with
a power meter or a plotter when the tip enters the
shear-force region at a preset vibration damping upon
approach. This is demonstrated by the approach curve in
Figure 2. It clearly shows that the coupled-in far-field light
intensity at low level is independent of the tip-to-surface
distance from 0.1 mm to a shear-force distance below 10
or 5 nm. The spike at the surface point occurs when
the shear-force vibration damping starts upon fast, coarse
approach and triggers immediate lift and hold of the tip
to 1 m distance. From there, a cautious close approach
is initiated and scanning is started at the high level of
near-field reflected light intensity, which strongly depends
on the material. Importantly, the reflection enhancement
is already seen for the short period before the lifting,
as required for tip protection from penetration into the
surface.
The sharp onset of the very close near-field enhancement only at the shear-force distance indicates an abrupt
start at a very close distance, and that is the reason why,
despite the 1 m wide illuminated area, a very good lateral
optical resolution (<10 nm) can be achieved with carefully pulled tips exhibiting around 10 nm end radius. The
enhanced reflection requires sharp tip radii of smaller than
20 nm. Blunt tips (e.g., etched ones with radii of 60 nm) or

broken tips do not give the enhancement and lead therefore

to topographic artifacts.3 As the enhancement is absolutely
necessary (the SNOM signal level should be more than
at least twice the far-field level and may reach factors
of up to >50, depending on alignment, radius, and material), every single measurement must exhibit the signal level
(energy meter). Shear-force AFM controls the distance and
is very well established for mapping surface topographies.
Therefore, only this apertureless SNOM can be used for
real-world samples (Figure 1). The scan in constant shearforce distance monitors only variations in the near-field
enhanced signal, and the constant far-field part does not
contribute to the contrast. A rough but chemically uniform
surface does not provide an optical contrast (notwithstanding edge contrasts at extreme topography such as verticals, overhangs, and slopes larger than the tip taper) and
thus proves the uniformity. The SNOM image maps differences of the chemical components at their surface sites,
due to differences in the reflectance enhancement, which
is also called chemical (or material) contrast. Comparison with the simultaneous AFM topography is an important bargain. Owing to the unexpected enhancement effect
in the shear-force gap, we get near-field resolution and
avoid crosstalk with the AFM detection of the topography. Hence, our near-field effect in the shear-force gap
ensures that topography does not influence the optical contrast (Figure 2). It also means that even high topography
(up to 1 or 2 m height) on a chemically uniform surface
does not give an optical contrast in artifact-free apertureless SNOM. This has been amply verified (see the several
examples in Ref. 3).
This SNOM technique does not rely on the phase
shift upon reflection,18, 19 and it has nothing in common
with depolarization SNOM using uncoated tips at constant
height (instead of constant distance) and a polarization
manipulator.20 Edge contrast but not chemical (or material)
contrast is reported in depolarization SNOM. Importantly,
aperture SNOM, even when hollow aluminum pyramids
are used, does not record enhanced chemical contrast but
reproduces topography (e.g., polystyrene beads), except
upon local staining with fluorescent dyes and collecting the
fluorescence light though at poor resolution. But this is a
task for confocal fluorescence microscopy.
The unprecedented reflection enhancement in the shearforce gap was unexpected before our investigations.7, 8
Even the manufacturer of the commercial instruments and
the supplier (DME, Danish Micro Engineering, Copenhagen) were apparently unaware of the enhancement necessity.21 Even worse, this near-field enhancement was denied4
clearly after unsuccessful experimentation with blunt etched
tips. As previous theoretical modeling efforts did not predict the experimentally found internal reflection enhancement,3, 510 we do not refer to all these papers here. It

Supramolecular Chemistry: From Molecules to Nanomaterials, Online 2012 John Wiley & Sons, Ltd.
This article is 2012 John Wiley & Sons, Ltd.
This article was published in the Supramolecular Chemistry: From Molecules to Nanomaterials in 2012 by John Wiley & Sons, Ltd.
DOI: 10.1002/9780470661345.smc045

Techniques

does not help that simulation of the intensity based on the

vector Helmholtz equation in the strict regime of linear
optics claimed the possibility for near-field resolution for
the reflected intensity orthogonal to the incident polarization for an uncoated tip with a diameter of 60 nm at the
apex and a distance of 30 nm.22 The latter parameters are
absolutely unsuitable for the experimental conditions of
reflection enhancement, which works only with end radii
of <20 nm and distances on the order of 5 nm. We need
the large difference in far-field and near-field coupling of
the reflected light intensity back to the tip (Figure 2) for
the artifact-free near-field resolution.

2.1.2 Equipment and realization

As aperture SNOM is amply described in Ref. 1 and, as
the scattered SNOM techniques with modulation1114 are
also not very useful for the present topics, their elaborate
equipment are not repeated here. However, the versatile
reflection-back-to-the-fiber SNOM is simply a shear-force
AFM with an optical addition. Figure 3 depicts a block
diagram.3
The light source is a high-quality laser (e.g., an Ar+ laser
emitting at 488 nm) focused to a coupler through a beam
splitter for the deflection of the reversibly reflected light
and a crossed polarizer, which is only needed for the effective elimination of stray light that would add to the back
reflected light (Figure 3, part 1). The coaxial optical waveguide does not retain polarization. The light passes through
the tapered uncoated multimode waveguide and produces a
concentric light spot of about 1 m diameter on the sample
at an XYZ piezo table (Figure 3, part 3) at typical energies of 6080 W, from where enhanced reflection into the
sharp vibrating tip (free lateral oscillation amplitude from a

Ar-laser
Fiber

Coupler

Generator

Photodetector

Ditherpiezo
2
Laser

Photodiode

AFM

3
XYZpiezo

Computer
Optical and
topografical

XY scan; Z feedback

Figure 3 Block diagram of an apertureless reflection-back-tothe-fiber SNOM setup with shear-force distance control and crosspolarization to minimize stray light: (1) beam splitter and crossed
polarizers; (2) shear-force arrangement; (3) sample mounted on a
piezo stage.

clamped dither piezo: 5 or 10 nm; frequency: 100400 kHz;

Q-factor 100) (Figure 3, part 2) occurs while it is at preset damping at the shear-force distance. The damping level
is typically chosen between 30 and 60%. A He/Ne laser
beam that is shadowed by the edge of the vibrating fiber,
and thus provides the feedback signal for maintaining the
preset amplitude, achieves shear-force distance AFM control. Half of the decoupled reflected light at part 1 enters
the photodetector with photomultiplier and is processed into
an optical image by a computer, which also processes the
AFM information in an independent channel. The fast light
control allows high scan speeds of up to 200 m s1 following high and varied surface topography also in large
scans with shear-force feedback. This is much superior to
the (also possible) slow tuning fork control requiring very
slow scanning. Fast scanning may be required for minimizing loss of contrast by heating of strongly light absorbing
surfaces or by photochemical conversions.6 All variations
in the enhanced near-field light are chemical (or material)
contrast due to all the effects that determine its internal
reflection efficiency. For local spectral analyses, optical filters can be used in front of the photodetector to eliminate
the primary light and pass only fluorescence or Raman scattered light, or the reflected light may be coupled to an
optoacoustic spectrometer with waveguide optics.
Sharp fused-quartz tips can be routinely pulled (as sharp
as possible; 10 or 20 of them within half an hour) with a
well-adjusted laser puller such as the P-2000 micropipette
puller (Sutter Instruments, Navato, CA, USA) at the proper
settings. End radii between 20 and <10 nm are detected
by SEM (scanning electron microscopy) of the counterpart.
Tips are more stable against breakages if their radius is
small. Etched tips2 are blunt (end radii of about 60 nm)
and do not attain the required sharpness. As the tapered
tips might break upon handling, or might slowly abrade
after repeated scans on a (very) rough material, or might
break at too high damping (very close distance) or on
sticky material, a power meter or oscilloscope must control
the enhancement level for every single measurement. The
minimum length of the commercial fused-quartz waveguide is about 80 cm (Figure 4). Numerous tips can be
economically pulled when starting with about 120 cm length
of the waveguide. We do not review here reports with
blunt, etched, uncoated tips (these do not exhibit reflectance
enhancement) that are glued to piezos or piezoelectric
bimorph cantilevers for the shear-force or tapping mode,
but all with far-field collection modes. These are expensive
and not easy to operate. Furthermore, they provide poor
subwavelength resolution of about 100 nm. Such resolution
can also be achieved with confocal microscopy in the 4
configuration.
The particular ease of the robust and versatile complete
setup of a RASTERSCOPE SNOM 4000 of DME A/S,

Supramolecular Chemistry: From Molecules to Nanomaterials, Online 2012 John Wiley & Sons, Ltd.
This article is 2012 John Wiley & Sons, Ltd.
This article was published in the Supramolecular Chemistry: From Molecules to Nanomaterials in 2012 by John Wiley & Sons, Ltd.
DOI: 10.1002/9780470661345.smc045

Scanning near-field optical microscopy (SNOM)

(b)

Figure 4 (a) Photograph of a fully installed apertureless shearforce SNOM with Ar+ laser, coupler, vibration-protected SNOM
head, receiver box, and hygrometer. The control unit with energy
meter, computer, screens, oscilloscope, and other auxiliary units
that are all on the table to the right are not shown. The very thin
transparent fiber between the coupling unit and SNOM table is
not resolved in the photograph. (b) Detail of the coupling and
receiving unit.

Copenhagen, for apertureless SNOM of real-world, rough

samples is depicted in Figure 4.3 Ventilation of the laser
is via the flexible tubing. It is even possible to support
the laser with a book. Parts 2 and 3 in Figure 3 and the
AFM are hanging on the three elastic ropes for vibration
protection.

2.1.3 Reflectance enhancement and shear force

Signal (mV)

The basic requirement for apertureless SNOM is the

reflectance enhancement in the shear-force gap. The studied
material strongly influences the efficiency of the shear-force
damping (100 d/d0 where d is the set amplitude and d0
the free amplitude of vibration). Thus, for example, 50%
damping will be obtained at different distances on different
materials, and the reflectance enhancement factor F (F =
I /I0 where I is the total intensity and I0 the far-field
background intensity) depends on the distance. Fortunately,
there are numerous material properties, such as refraction
index, gloss, crystal packing, water layer, and distance, that
influence the value of F . The far-field intensity I0 should

be kept as low as possible to increase the sensitivity, and

the useful range of F is from 2 to 50. It is important to
adjust the amount of shear-force damping to the material
in question. Too low damping decreases sensitivity and
will not properly engage the tip, while too high damping
abrades the tip. The increase of the enhancement factor
as a function of increasing damping with the same tip was
carefully detected for various materials.3, 23 It is exemplified
in Figure 5 for a gold surface that had been treated with H2 S
gas producing a self-assembled hydrophilic SH monolayer
(improvement of the shear-force mechanism).
It shows a linear dependence (within the shear-force
range) of signal intensity (as expressed by the voltage
reading at a stray light value of 100 mV) or enhancement
factor F from the damping settings. The latter reflects the
tip-to-surface distance. Such linearity within the shear-force
range was found for all studied materials. It has not yet been
theoretically analyzed. At preset damping values above
55% for the material of Figure 5, the tip started to abrade:
the tip radius increased and the enhancement decreased.
This again emphasizes that sharper tips give better results.
But abrasion must be avoided. So about 40% damping is
preferable for this material. Another point is the slope of the
approach curve F / (% damping), which characterizes
the sensitivity of the near-field enhancement of reflectivity
in the shear-force gap for the particular material. These
slopes can be used for rating different materials. The
differences are the reason for the chemical (or material)
contrast of SNOM. It is only qualitative, because the
thickness of the water layers is most important for the shearforce mechanism and this varies with ambient humidity
(differences in summer and winter if the relative humidity
is not kept constant). The thicker the water layer, the more
sensitive is the distance effect. The water layer of the fusedquartz tip certainly merges with the local water layer of the
sample for the coupling of the light in the shear-force gap.
In the absence of the water layer, the shear-force control

600

6.0

550

5.5

500

5.0

450

4.5

400

4.0

350

3.5

300

Factor F

(a)

3.0
20

30

50
40
Damping (%)

60

70

Figure 5 Approach curve to a gold surface with a hydrophilic SH monolayer, showing linearity in the appropriate damping region
with a slope F / (% damping) of 0.099.
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This article is 2012 John Wiley & Sons, Ltd.
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DOI: 10.1002/9780470661345.smc045

Techniques

is less efficient. Values for the slopes for various materials

have been measured between 0.0064 (anthracene) and 0.373
(ambient silicon).3, 23 This wide range also accounts for the
exceptionally good optical contrast that is achieved with this
type of apertureless SNOM even at very small structural
variations on chemically nonuniform surfaces.510, 23
The SNOM image depicts chemical (or material) contrast
between different materials. It depends on various factors
including Rayleigh, Raman, and fluorescence emissions,
absorption, polarization, and also on specific shear-force
influences. Even different polymorphs are differentiated by
the material contrast.3

(a)

(b)
Horizontal distance (L) 8.598 nm

2.1.4 Optical resolution

Resolutions down to 1 nm have been claimed for SIAM.11, 12
However, the origin of the high-resolution features remained unexplored (the object was a microscope cover slip).11
Furthermore, the optical contrast is recognizably artificial:
dark/bright edge contrast of the mica and droplets is seen
(Figures 2 and 3 in Ref. 12).
The reflection-back-to-the-fiber SNOM in the shear-force
gap, which works on the basis of the unexpected reflectance
enhancement, is able to achieve optical resolution on
rough and very rough surfaces equal to or even better
than the concomitant shear-force AFM resolution, due to
the light collection in the shear-force gap. That means,
the typical lateral resolution of shear-force AFM with tip
radius of 10 nm was repeatedly obtained for the optical
contrast at 10 nm. We considerably exceeded the common
8020% criterion by reporting top-to-bottom resolution
at natural test samples,3, 23 as exemplified in Figure 6.
Thus, our lateral resolution is considerably better (3.7 nm
instead of 8.6 nm in Figure 6c) when applying the less
stringent 8020% criterion that was used for all other
published SNOM techniques. This again underlines the
superiority of the easiest and most versatile apertureless
SNOM technique, which has profited from the unexpected
enhancement effect since 1997.7, 8, 24
Clearly, the topographic and optical resolution with
20 nm tip radius is 20 nm and for 10 nm tip radius 10
or 5 nm depending on definition. The superior resolution
has been equally shown with peak-to-peak distances on an
autoxidized anthracene surface and for gold projections on
a polycarbonate substrate test sample, all with resolutions
below 20 nm. Furthermore, top-to-bottom resolution of a
typical steepness artifact was 17.6 nm (when using 8020%
criterion: 8.4 nm resolution) at vertically oriented faces of
a 1 m high NaCl crystal.3, 23 Another indication of the
excellent resolution of the present technique was obtained
from fluorescing nanoparticles that reached the surface of a
resin (Figure 10, below). The AFM width was consistently
found to be 10 nm larger than the fluorescence SNOM

0
(c)

0.10

0.20

0.30

(M)

Figure 6 (a) Apertureless shear-force AFM on a polished marble surface (z-range 50 nm) and (b) simultaneous apertureless
SNOM showing no optical contrast at the hill side but at a geode
with interface as dark contrast. (c) Section line contour with excellent 8.6 nm top-to-bottom resolution (3.7 nm according to the more
common 8020% criterion) at 1.33 pixels per nanometer.

contrast, so the depth of the resin cover was judged to

be 5 nm.25 It is thus only the radius of the pulled tips and
the 532 pixels per scan length that limit the resolution in
the often-desirable much larger scan widths. All published
aperture SNOM reports are far away from these resolution
capabilities.

2.1.5 Artifacts
Aperture SNOM formulated credibility requirements for
near-field optical images that claimed, no correlation
between topographic and near-field image and correlated
structures must be displaced by a constant amount between
topography and optical image,26 because the apertures
cannot suitably follow topography and would require an offaperture fortuitous protrusion (or coating edge at inclined
alignment) for the distance control. However, such provisions contradict the actual goal of SNOM, which is detection of chemical (or material) contrast either in the presence
or absence of topography. Fortunately, this dogma does not
apply to apertureless SNOM; exactly the opposite is valid
for credible apertureless shear-force SNOM: the optical
contrast must be precisely at the site of the reflecting material! This is required at flat regions, slopes, depressions, or
hills. If such correspondence is not observed, the measurement is artificial. Clearly, noninterpretable images are of

Supramolecular Chemistry: From Molecules to Nanomaterials, Online 2012 John Wiley & Sons, Ltd.
This article is 2012 John Wiley & Sons, Ltd.
This article was published in the Supramolecular Chemistry: From Molecules to Nanomaterials in 2012 by John Wiley & Sons, Ltd.
DOI: 10.1002/9780470661345.smc045

Scanning near-field optical microscopy (SNOM)

(b)

nm

200

(a)

200

little practical value, and only artifact-free SNOM with the

precise local correspondence is the basis for all local spectroscopy. Any objections against constant distance SNOM
in terms of topographic artifacts26 do not apply for the
favorable conditions of the enhanced reflection back to the
sharp fiber in the shear-force gap (Figure 1). Fortunately,
undue measurements with blunt or broken tips are immediately recognized by absence of the enhanced intensity level
(Figure 2). It was therefore possible to study the various
appearances of SNOM artifacts with blunt or broken tips
and collect them in Ref. 10. Interestingly, the entire aperture SNOM images with their topographic artifacts exhibit
the same appearance and can thus be easily judged by comparison with the collection of the eight major types that are
multiply exemplified in Ref. 10.
These artifacts are as follows: (i) displaced optical
contrast with noncoincidence of topographic and optical
image (this artifact appears to be a necessity for aperture SNOM26 ); (ii) contrast change by tip breakage during scanning; (iii) interference fringes; (iv) stripes contrast at moderate slopes (bright/dark/bright/dark/. . . , or
dark/bright/dark/bright/. . .); (v) inverted derivative of the
topography in the optical response; (vi) inverted split contrast; (vii) local far-field light concentration at uniformly
structured topographies; and (viii) topographic artifacts with
no correlation to the tipsample convoluted AFM image.
The type of the artifact depends on the actual shape of the
blunt or broken tip. The same appearance of such artifacts
in aperture SNOM can have different reasons. Space limitations allow here for only one typical artificial image of
type (v) [1] from a nanoparticles sample with a broken tip
to be described. The larger features are at an unresolved
aggregation site. It must be stressed that a sharp tip on the
same sample as in Figure 7 gives the correct size of the
nanoparticles and the correct fluorescence SNOM contrast
(Figure 10; Figures 2.76 and 2.77 in Ref. 3; and Figures 7
and 8 in Ref. 25).
It appears necessary here to clearly demonstrate that
shear-force apertureless SNOM with sharp uncoated tips
does not produce topographic artifacts, for example, with
Figure 8. The high AFM topography of the freshly crystallized 4-nitroaniline crystal surface (Figure 8a) is not
caused by impurities, but it is chemically uniform. There
is no excessive steepness and no sharp edge. Therefore, the enhanced reflection in the shear-force gap cannot and does not exhibit a contrast in the SNOM image
(Figure 8b).8 That is valid for protrusions, slopes, and pits
on the same surface25 and amply documented with further
examples.69, 24, 27 Slight artificial contrast would only occur
at slopes that approach or exceed 80 , or in the presence of
sharp edges,7, 9, 28 or at local light concentration by strong
far-field reflections from slopes.6 However, the artifact-free

10

20 0

10

20 m

(c)

Figure 7 (a) Simultaneous strongly convoluted shear-force

AFM (z-range 400 nm) and (b) artificial apertureless SNOM of
fluorescent nanoparticles (100200 nm) embedded in polyvidone
with an axially symmetric broken tip, showing the optical image
like an inverted derivative of the diffuse AFM response also in five
small features. The section contours for (a) and (b) are horizontal
through the centers of the large features.3, 10

(a)

(b)

Figure 8 (a) Simultaneous shear-force AFM (10 m, z-range

500 nm) and (b) SNOM of the large features on a uniform 4nitroaniline crystal surface with a sharp reflectance enhancing tip
showing complete absence of optical contrast because of chemical
uniformity on the rough surface, thus excluding topographic
artifacts at proper SNOM measurements.

situation would, of course, be lost if the tip were blunt

(radius >20 nm) or broken.

2.2

Applications

2.2.1 Applications of SNOM for nanoparticles

The scanning of nanoparticles with shear-force AFM and
simultaneous apertureless SNOM is an easy task. The
nanoparticle suspension is spread and dried on a microscope
slide without further treatment and scanned as usual. Scanning in water is also possible, but the sensitivity under water

Supramolecular Chemistry: From Molecules to Nanomaterials, Online 2012 John Wiley & Sons, Ltd.
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DOI: 10.1002/9780470661345.smc045

Techniques

(a)

(b)

Figure 9 (a) Shear-force AFM (10 m, z-range 200 nm) and

(b) simultaneous apertureless SNOM of dried silver sol on a
microscope slide.3, 23, 29

is decreased considerably for a standard technique. Size,

chemical uniformity, and aggregation phenomena are reliably determined. For example, silver nanoparticles for use
in SERS (surface-enhanced Raman spectroscopy) are analyzed in Figure 9. The position correspondence of topography and optical response is strictly obeyed. There is dark,
bright, and very bright optical contrast all on the positive
objects. Only SNOM can distinguish their different properties. As silver reflects more strongly than the supporting
glass, it is clear that the dark contrast in Figure 9(b) indicates an impurity (probably Ag2 O; it could be secured by
local Raman SNOM, see below). But there are also differences in the small single and aggregated particles that
are of relevance for the SERS activity.3, 23 Similar measurements of a batch of SERS-inactive gold nanoparticles
revealed impurities and 400500 nm particles instead of

(b)

0.40 V

200 nm

(a)

nominal 50 nm particles.29 Clearly, proper SNOM is an easy

and rapid quality test and a time-saving indispensable technique for all SERS investigations. Numerous applications
of SNOM for all further applications of nanoparticles are
clearly envisioned.
Also, fluorescing dye-pigment nanoparticles that are
embedded in varnish and located at the surface can be
studied by apertureless internal-reflection-mode SNOM.3, 25
Some single (nominal size 100200 nm) and mostly aggregated particles at the surface produced the AFM topography. Figure 10 shows AFM and simultaneous fluorescence
SNOM (a cut-off filter transmitting from 506 nm onward
was used in front of the photodetector). The nanoparticles
mostly aggregated in an angular fashion, but some more
compact and even linear ones were also found in more
extended images (not shown here). The covering resin fills
the voids in the loops as shown by the AFM topographies
(Figure 10a), but only when also using the information from
the SNOM image (Figure 10b). Here and in more extended
scans (not shown here), the single particles have half-widths
in the AFM image that are consistently 10 nm larger than
in the SNOM image. It is thus clear that the polyvidone
cover on these surface particles is about 5 nm thick. Owing
to the resin cover, the SNOM features are indeed smaller
than the AFM features. The real aggregation geometry here
can be detected only by SNOM but not by AFM. This
has a bearing on the technical formulation of color shadings with nanoparticle dyes, for example, in automotive
varnish.

0
0.4
(a)

0.4
0.8

1.2 m

(b)

0.8

1.2 m

Figure 10 Simultaneous shear-force AFM (a, a ) and apertureless fluorescence SNOM (b, b ) of dye nanoparticles in polyvidone
resin showing angular aggregation by the difference in shape of topographic and optical image both in the top views (a, b) and in the
surface-views (a , b ).3, 25
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DOI: 10.1002/9780470661345.smc045

Scanning near-field optical microscopy (SNOM)

consuming purifying workup: pure products are formed

immediately with quantitative yield. The enormous sustainable profit from gassolid and solidsolid reactions
was thus strongly retarded by the adverse topochemistry
hype since 1964. The suppressed solid-state reactions had
therefore to be elucidated at the nanometric range by
AFM.5, 16 It was then required to analyze partially reacted
crystals with a suitable SNOM technique for rough surfaces to locate product sites and check for alleged defect
site reaction mechanisms via electronic excitation energy
transfer, which is a follow-up hypothesis that served as
an excuse for some of the failures of the topochemistry
hypothesis.

2.2.2 Applications of SNOM for supramolecular

chemistry and nanoscale composites
General aspects
The applications of SNOM in supramolecular chemistry
are manifold. At present, this refers mostly to reactions
of self-assembled molecular crystals or of composites
and to the detection of cell change upon cancer formation, whereas the identification of highly resolved cellular
organelles is an equally significant topic. Importantly, the
chemical contrast of SNOM in combination with simultaneous AFM is an invaluable tool for the evaluation
of the basic mechanistic questions in solid-state chemistry. For example, gassolid and solidsolid reactions
not involving liquid phases5, 28, 30, 31 were not appreciated, because they could not be understood on the basis
of Schmidts topochemistry hypothesis.32 This highly
acclaimed hypothesis strangely enough claimed absence of
molecular migrations within crystals and a limiting dis But
tance between successful reaction centers of 4.2 A.
surprisingly, such topochemistry did not appreciate the
undisputable local pressure formed when molecular shape
changes upon reaction within crystals, or the existing positive and negative exceptions of the distance claim, or
other inconsistencies.5, 16, 33 These severe failures strongly
impeded the development of supramolecular gassolid
and solidsolid syntheses despite their excellent sustainable performance, as most of these continue to proceed
in a waste-free manner and do not require the solvent

50 nm

50 nm

Molecular mechanism of organic solid-state photoreactions

Single or double layers on crystal surfaces exhibit molecular
effects upon chemical reactions. For example, the molecules
of anthracene scales on the overwhelming (001) face stay
steeply on their short edge, separated by the cleavage plane
(the skew orientations of the molecular planes are not
indicated in schematic Figure 11c). This is the reason for
the molecular steps of 14 molecular layers in Figure 11(a).

Closest distance between the reactive centers is 6.038 A,

but photochemical [4+4]-dimerization occurs in the crystal
where the absorbed light depletes down to about 200
molecular layers. Clearly, the internal pressure that would
be created if the molecules were to stay fixed in the
crystal is avoided by molecular migrations along the parallel
cleavage planes. As it is more difficult here to penetrate the

0
1

1
2
3

(a)

(b)

hn

(c)

Figure 11 Contact AFM image along [010] with 001 on top of an anthracene crystal, showing (a) molecular steps and (b) exit of
molecules at the molecular steps after short irradiation ( > 300 nm), which avoids internal pressure due to the [4+4]-dimerization
reaction. (c) Schematic sketch of the molecular arrangement of molecules under the (001) face of anthracene, symbolizing formation
of a (4+4)-photodimer molecule and exit of molecules at the molecular step for pressure release.
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DOI: 10.1002/9780470661345.smc045

10

Techniques

upper molecular layer, the molecules are shifted within the

layer and they exit at the molecular steps as is shown by the
AFM (Figure 11b) by the wavy features. It is schematically
depicted in Figure 11(c).
While this AFM result and the different behavior on
{110}, where crystal-packing-guided random volcano-type
features occur,34 already exclude the topochemical claims
of energy transfer to defect sites and reaction only there
distance strongly exceeds the alleged 4.2 A

(the 6.038 A
limit),3335 additional verification by SNOM was required
and obtained: the surfaces in Figure 11(a) and (b) and
other surfaces at higher conversions did not give a SNOM
contrast but images like the one shown in Figure 8(b).34
This indicates that there is no accumulation of product
dimers at the preferred exit positions at the crystallographic
molecular layers (molecular steps are not defect sites). The
defect site mechanism with the proposed energy transfer
is thus excluded: the photochemistry occurs everywhere
at the sites of light absorption, forming a uniform mixed
surface out of anthracene and its photodimer at the scale
of Figure 11, due to the far-reaching molecular migrations
within the crystal.
Similarly, the crown witness of topochemistry, the photodimerization of layered -cinnamic acid crystals (with
two different cleavage planes) to give primarily -truxillic
acid, exhibited packing-correlated far-reaching anisotropic
molecular migrations according to the AFM investigation,
but not single-crystal to single-crystal transformation without molecular migrations.28, 35, 36 The SNOM investigation
proved again that the photoreaction occurred everywhere
in the crystal at the sites where the light is absorbed. No
chemical contrast could be obtained at very low (small features along cleavage planes), medium (larger features), and
high transformation (aligned feature heights up to 1.5 m).
The features did not differ in composition at rough sites
or at flat parts. Thus, any alleged possibility for a clusterby-cluster type photoreaction without continuous molecular
migrations is excluded. Clearly, the surface of the crystal
exhibited a uniform mixture of reacted and unreacted material at every stage of conversion, as proved by artifact-free
SNOM. All of that clearly excludes the alleged topochemical process, and has been amply documented.3, 28, 33, 3537
The controversy is thus settled by reliable SNOM experiments.
Molecular mechanism of organic gassolid reactions
The situation at supramolecular gassolid reactions is different from photoreactions because the gas has to approach
the crystal and enter it via easy paths. Thus, even molecular steps when presenting the reactive groups can be the
sites of chemical reaction at the expense of nonreactive
surface layers with the reactive groups hidden underneath.
Several examples have been described.3, 35, 37 Particularly

interesting is the protection of crystals by the outermost

molecular single mono- or bilayer toward chemical reaction. The autoxidation of crystalline anthracene in air has
been studied with AFM and SNOM. Surprisingly, very thin
scales (P 21 /a) are stable, whereas large crystals autoxidize
to give evaporating water, the strongly absorbing (488 nm)
brown charge transfer (ct) complex between anthracene and
anthraquinone (moderately stable in the solid state), and
anthraquinone. Thin scales of anthracene present the overwhelming {001} face, the monolayers of which have the
molecules in an orientation that hides the reactive 9,10positions (left and right side in Figure 12c) and protects
them from attack by oxygen. This remarkable molecular
monolayer protection is clearly determined on a molecular basis by unchanged AFM topography and complete
absence of a SNOM contrast after six months of exposure to ambient clean air. Also, the molecular {100} steps
or minor defects were without reaction. Here, one of the
9,10-positions is hidden under the neighboring molecule
according to the molecular packing (left side of Figure 11c,
where the molecules actually staple in skew orientation).
When a prismatic crystal (P 21 /a) of anthracene was
exposed to air, its prominent flat {110} faces were also
stable, apparently because only the 9-position of anthracene
is available there but the 10-position of the molecules is
shielded (Figure 12c). Fortunately, it was also possible to
find some deep (e.g., 400 nm; slopes 1020 ) micrometersized craters at some sites on {110} with minor dams
at the rims by AFM as in Figure 12(a). The SNOM at
a sloping part of 1015 was nano-rough, with measured
peak-to-peak distances down to 18 nm (Section 2.1.4).7, 23
Only more extended SNOM (Figure 12b) could find out
that autoxidation had occurred at the slopes including
rims. Clearly, at slopes down or up from {110}, both
reactive 9- and 10-positions of anthracene are accessible
for oxygen attack to produce anthraquinone, initially as the
ct complex with unreacted anthracene. The SNOM contrast
in (Figure 12b) with respect to the medium value at the
{110} planes (unchanged anthracene) is dark (strongly
absorbing ct complex) in the depths of the craters and
bright at the rims and upper slopes (better reflecting
anthraquinone). Compact prismatic anthracene crystals are
therefore much more susceptible to autoxidation than the
very thin scales. Clearly, only a single molecular layer
efficiently protects the latter crystals.
Stronger reagents such as bromine gas to form 9,10dibromoanthracene and HBr gas from anthracene may break
the single monolayer surface protection of the scales of
anthracene on (001) by chance or at a rare surface defect.
This would then produce islands around such initiating
events where the crystal packing has been opened. AFM
investigation found such rare islands as in Figure 13(a),
after application of bromine vapor, in the form of steep

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DOI: 10.1002/9780470661345.smc045

11

0.50 V

500 nm

Scanning near-field optical microscopy (SNOM)

0
4

4
8

(a)

(b)

(c)

Figure 12 (a) AFM (10 m, z-range 500 nm) and (b) simultaneous SNOM surfaces of a {110} face of anthracene with some craters,
which was pre-exposed to ambient clean air; the slopes rarely exceed 20 (but 30 is also observed); the SNOM image indicates
three types of contrast: medium at the flat sites, bright (positive) at the upper slopes and rims, and dark (negative) at the depths; (c) a
projection of the crystal packing along [110] with (110) on top and (001) the left side.

verified with thin plates by AFM (Figure 14a) and the dark
SNOM contrast (Figure 14b) at the chemically generated
islands probably around initial defect sites on an initially
flat surface after long exposure to clean air. Single crystals

(a)

(b)

Figure 13 Simultaneous (a) shear-force AFM (3 m, z-range

500 nm) and (b) SNOM image of 9,10-dibromoanthracene islands
on anthracene as measured with a sharp uncoated tip, showing the
negative chemical contrast at the correct positions.

and high (400 nm) hilly islands. However, it was for

SNOM to prove that the chemical reaction had occurred
there. A strong dark contrast was detected precisely at
the island sites as expected for 9,10-dibromoanthracene
in Figure 13(b).3, 9 Such reactions can, of course, be completed at the reactive faces of the crystal, for example, by
using powdered crystals, exhibiting all faces.
A similar self-protection of layered crystals is found
with highly reactive 2-mercaptobenzothiazole, because all
functional groups are hidden within bilayers on their
most prominent {001} surfaces (Figure 14c). Such single
molecular bilayer stabilization works again toward oxygen
and other gases. Only the island mechanism is expected on
(001) in ambient air to give water and the corresponding
disulfide. This prediction from the crystal packing is

(a)

(b)

(c)

Figure 14 Simultaneous (a) AFM (11 m, z-range 500 nm)

and (b) SNOM of a partially autoxidized (001) face of 2mercaptobenzothiazole showing islands and negative chemical
contrast precisely at the island sites. (c) Molecular packing with
(001) on top, including the hydrogen bonds.

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DOI: 10.1002/9780470661345.smc045

12

Techniques

of 2-mercaptobenzothiazole are thus remarkably stable

toward autoxidation in air.3, 38 They can be handled in
air because the other faces are very minor. The single
molecular bilayer protection is not available on powdered 2mercaptobenzothiazole exhibiting all possible crystal faces
that autoxidize readily and cannot be handled in air.
These results pointed out that quantitative gassolid
reactions with aliphatic amines (salt formation) must be
carried out with powdered 2-mercaptobenzothiazole for
obtaining reactive crystal faces. Also, solidsolid oxidation with 1-oxo-2,2,6,6-tetramethyl-piperidinium nitrate
required milling for breaking the self-protection.39
Another problem with air-exposed crystals of polar
molecules is the formation of surface hydrates and hydrolysis. Phthalimide crystals have these possibilities, but the
major (001) face protects the functional groups that are
efficiently hidden under the hydrophobic benzene rings in
bilayers. Only one of the two oxygen atoms is less efficiently shielded. So hydration appears possible, but hydrolysis to give phthalic acid monoamide should be impeded by
the outermost molecular bilayer. Thus, only rare hydrolysis
events around an initial successful penetration with island
formation are expected.
The AFM analysis in Figure 15 reveals a very flat
initial (001) surface with molecular steps (bilayers) and
some peaks with heights of 2.33.3 nm (Figure 15a) which
persist in moist air. The surface hydration in moist air
is the only process taking place within two days. A
uniform change at the 10 nm high ranges is obtained
(Figure 15b). Numerous bilayer steps and deeper ditches
align along the long crystal axis [010], where the less
shielded oxygen atoms arrange in line. Therefore, this is
most likely surface hydration. No SNOM contrast was
obtained at that stage. More extended exposure to moist
air (weeks), or exposure to nearly saturated water vapor for
16 h, produced isolated islands of considerable height (up
to 180 nm) (Figure 15c), while the direction of preference
was retained (as detected with smaller z-scale). SNOM
(Figure 15d) indicated via dark chemical contrast that the
large islands are the result of the hydrolysis reaction with
long-range molecular migrations only at the islands. The

(a)

z = 10 nm

(b)

z = 10 nm

reliability of the measurement is demonstrated by the

precise local correspondence with the topographic image.
Similar dark chemical contrast in a more advanced state of
hydrolysis has also been found with SNOM using 633 nm
light.9, 37, 40
The important waste-free quantitative gassolid diazotization of aromatic amines to the solid diazonium nitrates
has been mechanistically studied with depth dependent
grazing incidence diffraction (GID)41 and SNOM.7, 42 The
use and performance of apertureless SNOM might be
demonstrated with sulfanilic acid monohydrate to give the
corresponding diazonium salt by the action of gaseous
NO2 .7, 41, 42 The AFM investigation on its natural flat (010)
surface showed that the reaction comes to a stop. This is
clearly understood from the packing diagram (Figure 16a)
showing hydrogen-bridged strings of molecules. These are
not able to move out over the (010) face after all accessible amino groups (any other molecule of the topmost
layer) are diazotized. However, the crystal can be chemically attacked from the sides (Figure 16a). This expectation
has been verified at a nanometric slope site on (010), which
was initially uniform with no SNOM contrast. After application of a 1 : 4 mixture of NO2 with air from 1 cm distance
and left for 1 min, there was no significant change of the
AFM (Figure 16b), but the bright SNOM contrast only at
the slope sites (Figure 16c) indicated the formation of the
diazonium salt only there and, once formed, the hydrogen
bonds were broken so that the molecules could migrate.
This is confirmed by the quantitative yield upon complete
conversion without melting. Thus, the solid-state mechanism has been nicely revealed by SNOM.
The elucidation of the solid-state mechanism at the
molecular level with SNOM supports the AFM-based general mechanism with face specificity and anisotropic molecular migrations along cleavage planes, or channels, or to
voids for avoiding local pressure. It consists of initial
phase rebuilding, phase transformation, and crystal disintegration with the all-deciding crystal packing. No solidstate reaction can occur for self-assembled crystal packing
without the presence of cleavage planes, or channels, or
crystallographic voids.3, 35, 43 From there, more than 1000

(c)

z = 200 nm

(d)

SNOM

Figure 15 AFM topographies (5 m) on (001) of phthalimide at room temperature (a) fresh from acetone; (b) after two days in
air at relative humidity of 5060%; (c) after 16 h storage in an atmosphere of almost saturated water vapor at room temperature;
(d) simultaneous apertureless shear-force SNOM (488 nm) with dark optical contrast precisely at the island site.
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13

100 nm

Scanning near-field optical microscopy (SNOM)

0
2
4 m

(b)

0.30 V

(a)

0
2
(c)

4 m

Figure 16 (a) Projection of the crystal packing of sulfanilic acid monohydrate along [100] (but 10 off) with (010) on top.
(b) Simultaneous AFM and (c) SNOM on the (010) face with slope sites after short exposure to diluted NO2 gas, showing bright
chemical contrast precisely at the slope sites in the various directions.

waste-free gassolid and solidsolid syntheses with 100%

yield have been achieved by strict application of the mechanistic facts.3, 39 The molecular crystal packing decides
the reactivity and crystal surface selectivity.3, 33 These
supramolecular syntheses have finally matured by acknowledging the mechanistic facts from AFM and SNOM, and
industrial applications are already at work.44, 45
Industrial and medicinal applications of SNOM
There are already patents and industrial uses of gassolid
and solidsolid reactions, the mechanism of which required
SNOM investigations.45 Equally, SNOM opens new ways
for medicinal (including biological) applications with subcellular analyses of organelles,3, 37 which, however, are not
discussed here.
A unique application of SNOM is the analysis of
dental alloys that leach into the patients mouths at the
nanometric level. To prevent adverse health effects, the
alloys have been tested by standardized electrochemical
corrosion with chemical analysis of the leachate before
approval and admittance. However, this technique urgently
requires the addition of the SNOM analysis of rough
surfaces. The technical alloys are polished, and a typical
surface looks like as shown in Figure 17(a), with sharp
edges that give rise to stripe artifacts in the SNOM
image (Figure 17b). These edges are smoothened away

due to the leaching tests and good quality is assured

if no chemical SNOM contrast arises.3, 29, 37 Fortunately,
such positive results are found for most dental alloys.
However, the previously approved and admitted nickel
alloy of Figure 17 exhibited craters at certain sites in the
AFM (Figure 17c) and even worse material contrast in the
SNOM (Figure 17d). The material contrast in a metallic
alloy indicated submicroscopic electrochemical pitting. So
this alloy had to be and was immediately removed from the
dental materials market after these measurements.3, 29, 37
Further, supramolecular reactions occur with native blood
in blood bags. The change of their rough surface materials,
which initially lacked an SNOM contrast, developed typical
dark and bright SNOM contrast after various blood filling
times.29, 37 This is of enormous economic importance and
should be used for optimizing the allowable storage times
by suppression of the deposition reaction.
A new approach in cancer prediagnosis is SNOM monitoring of the chemical change of healthy into cancerous tissue at the subcellular level. Apertureless shear-force SNOM
provides a rapid prediagnostic tool for early cancer recognition with very rough dried cold-cuts (cut at 10 C)
of unstained human bladder tissue. A safe differentiation
with AFM is not possible (Figure 18a and b) in this case;
however, SNOM provides characteristic differences. While
the healthy tissue provides no distinct chemical contrast at

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DOI: 10.1002/9780470661345.smc045

14

Techniques

(a)

(b)

(c)

(d)

Figure 17 Simultaneous shear-force AFM (a) (10 m, z-range 300 nm) and (c) (z-range 1.6 m) and apertureless SNOM (b, d) of an
abraded dental nickel alloy; (a) and (b) before, (c) and (d) after the electrochemical standard leaching test.

the 25 m scan range (Figure 18a ), the cancerous tissue

provides bright plate-like and dark ribbon-like chemical
SNOM contrast with sharp borders (Figure 18b ). This is
also observed at topographically very different sites of the
cold-cut and is thus very characteristic. It is always found
at the 20 m range, sometimes even more extended.3, 29, 37
The strong optical contrast reflects the increased chemical
diversity in different cancerous cells. The bright contrast
may be due to the accumulation of metal ions and mitochondria in the rapidly replicating cells, and the dark contrast to
accumulation of metabolic products. Applications to breast
biopsy material for fast precancer diagnosis when the cells
start with microcalcification are highly promising primarily
for patients with a genetic risk.

2.3

Local near-field spectroscopy

2.3.1 Local absorption and Raman spectra

Recently available commercial nanoscale IR spectrometers
do not collect IR light but detect the local surface deformation by absorption of monochromatic IR light with concomitant heat formation using oscillating AFM tips. Very

thin samples are mounted on a ZnSe prism through which a

pulsed tunable IR laser is irradiated from underneath. This
interesting though rather indirect technique has, however,
nothing in common with SNOM techniques.
Direct UVvis and IR-SNOM absorption spectra require
white illumination, and IR-SNOM46 is experimentally complicated. Absorption effects are, of course, part of the
enhancement factor in monochromatic reflection SNOM.3
Emission SNOM requires suitable cutoff filters or interference and notch filters for eliminating the primary light, or
a diffracting spectrometer.
Fluorescence SNOM with the hot tips of aperture SNOM
(Figure 1a) appears to be the only possibility for interpretable aperture SNOM on slightly rough surfaces though
at low resolution; however, it is not sufficiently local, due
to the noncoincidence with the site of the emitter. Conversely, apertureless SNOM at constant shear-force distance
is an enhancing technique for strictly local fluorescence or
Raman emission. Both techniques help identify the different
local materials of a composite by scanning the particular site using spectroscopic analysis. For example, it is
possible to identify geodes, local impurities, or organelle
constituents in biological material by these techniques. An
example is given in Figure 19. The AFM of the polished

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DOI: 10.1002/9780470661345.smc045

Scanning near-field optical microscopy (SNOM)

(a)

(b)

(a)

(b)

15

Figure 18 Shear-force AFM topographies (25 and 20 m, z-range 1 m) of (a) healthy bladder tissue and (b) cancerous bladder tissue;
(a ) and (b ) are the corresponding apertureless shear-force SNOM images, where only (b ) shows characteristic bright plate-like and
dark ribbon-like contrast.

dolomite surface (Figure 19a) did not indicate the presence

of a different material, but apertureless SNOM revealed
the position of a strongly reflecting geode (Figure 19b),
whereas the minor residual roughness in Figure 19(a) from
the polishing does not provide an optical contrast. Now, the
identification of the geode material required local Raman
SNOM precisely at its site. The local SNOM spectrum
in Figure 19(c) revealed the characteristic Raman lines of
pyrite (FeS2 ) by resonant Raman excitation at 488 nm.
The spectrum (Figure 19c) required only a short Raman
collection, because shear-force controlled apertureless internal reflection Raman SNOM also creates the characteristic
enhancement of the Raman reflection back to the sharp
tapered fiber.3, 25 Further, resonant Raman SNOM spectra of
silicon (519.7 cm1 ) under an old (5 nm) or a freshly grown
silica layer, and nonresonant Raman SNOM of these layers (500 cm1 ) as well as of gallium nitride (nonresonant;
E1 (TO) and E2 Raman modes at 560.8 and 570.4 cm1 )
on alumina (subtraction of the Raman response of support
and fiber) with the shear-force apertureless technique (using
488 nm light) at total collection times of 10 min have been
reported in Ref. 25.

2.3.2 Local surface-enhanced Raman spectroscopy

Local SERS SNOM over gold or silver nanoparticles is
highly efficient with shear-force apertureless SNOM. An
example is shown in Figure 20, where a dried drop of a
very dilute solution of adenine with silver nanoparticles on
a microscope slide was scanned in a 100 100 nm2 area.
Here, the Raman background of the glass and fiber was not
subtracted to demonstrate the efficiency. The well-known
Raman line of adenine at 735 cm1 is indeed prominent.
The sample was prepared from 10 l of an aqueous solution
containing 1 pg of adenine that was added to a drop of
standard silver sol, which gave a plane circle of 2 cm
diameter upon evaporation in air. The 20 mW Ar-ion laser
light at 488 nm was coupled into the uncoated tip, and the
collection time was 10 min. The local scanning area can, of
course, be considerably decreased.
This local technique is highly versatile, because the
silver sol can also be spread and dried on rough biological
surfaces, for example, medicinal preparations.3, 29
The difficulties creating uncertainties of near-field SERS
Raman spectra with apertured tips (apex 300 nm, aperture
70 nm, claimed lateral optical resolution <100 nm) and light

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16

Techniques

(a)

AFM tips (diameter <50 nm; metalized with silver) on

transparent samples were illuminated by a focused laser
beam from below through the support and the sample to
reach a 30 times increase of the scattered Raman light.48
This apertureless scatter SERS SNOM succeeded also with
an etched gold wire in shear-force distance with 40-fold
increase of the Raman signal, but this shifted the Raman
lines with respect to those in the bulk Raman spectra.
Nanopipette probes for apertureless SERS SNOM with gold
or silver particles held in the aperture are also available.
However, none of these elaborate techniques approaches the
capabilities and versatility of the easiest apertureless SNOM
with sharp pulled tips and enhanced internal reflection
(Figure 1b).

(b)
Pyrite
145 scanlines

Intensity (a.u.)

1.5
1.0
0.5

2.3.3 Local fluorescence spectra

0.0
250
(c)

300
350
400
Wavenumber (cm1)

450

Figure 19 (a) Shear-force AFM (5 m, z-range 100 nm) at the

surface of polished dolomite; (b) simultaneous chemical SNOM
contrast exhibiting a geode; (c) Raman spectrum from scanning
only within the geode region. The baseline is subtracted.3, 29

0.1

735 cm1

SERS with adenine

0.0
503.4 504.0

505.0

506.0
507.0
Wavelength (nm)

508.0

508.7

Figure 20 Local SERS SNOM spectrum from a 100 100 nm2

area of adenine in the presence of Ag nanoparticles within a
dried drop on a microscope slide without flattening or baseline
subtraction.3, 29

collection through a lens from a side of the metalized tip in

shear-force mode have been described for rhodamine 6G on
micrometer-sized silver islands.47 For example, there was
no local correlation of the optical signal with the island
sites, less enhancement than in far-field measurements, and
sample drift (tip temperature not mentioned), apart from
usual problems with topography with this type of SNOM
(Figure 1a). Enhancement can be obtained with a silver
particle at the end of a sharp tip scanning on an illuminated
surface with far-field detection. Also, SERS-active contact

Strictly local fluorescence can be diffracted off in a fiber

spectrometer, or it is more often only separated from the
primary light by a cutoff filter and detected as the total
fluorescence. An example is given in Figure 10(a) and (b),
where internally reflected and thus enhanced fluorescence
enables SNOM detection of 100 nm nanoparticles with the
correct width, and, in combination with simultaneous AFM,
also measures the thickness of the covering transparent varnish to 5 nm.3, 25 Furthermore, numerous applications in
fluorescing dye technology (including measurement of diffusion coefficients and photobleaching) have been reported
in Ref. 25. This easy technique can be applied for the local
detection of fluorescence markers on biological objects with
enormous potential for medicinal questions3, 29, 36 because
there are no topographic artifacts with very sharp uncoated
tips in constant shear-force distance.

2.4

Related techniques: STED, super lenses with

NIM, and some other techniques

Apart from SNOM (or NSOM), two new, highly resolving

techniques are emerging that deserve brief mention here.
These are stimulated emission depletion (STED) using
focal and doughnut-focal beam shapes, and the microscopy
with super lenses out of negative index of refraction
materials (NIMs).
In the theoretically analyzed NIM technique, objects are
imaged with a resolution much smaller than the illuminating
wavelength, because NIMs, unlike conventional materials,
make light to refract inward rather than outward, due to the
negative index of refraction.49 Flat nanolenses of this kind
can be used as light couplers in nanooptics.50 This does,
however, not signify a behavior of the surface material,
but is rather a particular super lens effects. Practical
applications are to be expected.

Supramolecular Chemistry: From Molecules to Nanomaterials, Online 2012 John Wiley & Sons, Ltd.
This article is 2012 John Wiley & Sons, Ltd.
This article was published in the Supramolecular Chemistry: From Molecules to Nanomaterials in 2012 by John Wiley & Sons, Ltd.
DOI: 10.1002/9780470661345.smc045

Scanning near-field optical microscopy (SNOM)

STED uses confocal femto- and picosecond two-laser
scanning with a claimed axial resolution of 3346 nm
of fluorescence spots.51, 52 A recent publication describes
the difficulties with staining procedures and photobleaching at the STED light intensity of up to 2.1 GW cm2
which required the synthesis of more photostable fluorinated rhodamine dyes.53 The observed fluorescence of
protein fibers was 22.5 times sharper than in confocal
fluorescence microscopy, which is far from the 10 nm
spatial resolution capability of the comparatively very simple apertureless shear-force SNOM in internal reflection
mode that does not change the object by staining and
simultaneously provides the 3D information. Furthermore,
STED is limited by orientation requirements not allowing for considerable roughness, and it is restricted to
intensely fluorescing objects or materials stained with fluorescent dyes. The photobleaching of fluorescing materials
or staining dyes would detract it from general applications. Also, further super-resolution fluorescence techniques
like PALM (photoactivated localization microscopy) and
STORM (stochastic optical reconstruction microscopy)
are unable to detect nonluminescent materials and appear
restricted to microbiological samples. They require very
elaborate equipment, are experimentally difficult, and
do not reach the resolution of apertureless shear-force
SNOM.
Electron microscopy (TEM, transmission electron microscopy; SEM) also reaches super resolution. It is covered
in Scanning Electron Microscopy, Techniques.
Recent digital 3D microscopy should also be added here.
It enables useful surveys to be carried out on composite
materials for locating sites of interest, which can then be
studied with AFM and SNOM. A brief description is given
in Ref. 3. The available enlargement is up to 5000-fold
to the screen. For example, the nuclei of Fuligo varians
are observed with a diameter of 3 mm (0.6 m) to 10 mm
(2.0 m). Combined use of 3D microscopy with nanoscopic
techniques has appeared.54, 55

CONCLUSIONS

Apertureless shear-force controlled internal-reflection

SNOM using a light trigger for fast scanning on rough surfaces without topographic artifacts on rough surfaces and
with the same or better optical resolution as the simultaneous AFM uses very sharp, uncoated tips in the 10 nm
final radius range. It provides 10 or 5 nm optical resolutions and is superior to all other SNOM or STED,
PALM, STORM, or NIM techniques. It is by far the
simplest and most economic SNOM technique and provides interpretable results not only for standard test materials but also for real-world rough samples. It is enabled

17

by the well-established, strong enhancement of internal

reflection back to the illuminating tip in the shear-force
gap, both for strongly or weakly fluorescing and nonfluorescing transparent or opaque materials. The practical applications for nanoparticles, supramolecular chemistry, and
biology, medicine, and industry are manifold, whenever
nanometric structures are involved. The most important
basics of the unique though unexpected internal reflectance
enhancement have been elucidated. This favorable effect
depends on numerous influences that contribute to the
chemical contrast, which is the reflectance efficiency of
the material (e.g., absorbance, emission, refractive index,
molecular structure, polarity, and, in particular, the shearforce mechanism). As shear-force strongly depends on the
ambient humidity, it is most likely that a water meniscus forms between the water layers of the material and
the silica tip in the shear-force gap, or that the water
layer on the silica tip is connecting with dangling bonds
of the surface in the absence of a surface water layer.
These varied influences make simulations and predictions
of the optical contrast intensity difficult. But fortunately,
this fertile diversity of specific influences allows differentiating very minor chemical or physical differences with
surprisingly strong material contrast. Therefore, numerous important questions have been and will be reliably
answered in supramolecular chemistry, with nanoparticles,
cells, organelles, and all fields dealing with solid and waxy
composite materials.
Further, rather elaborate SNOM techniques do not profit
from the internal reflection enhancement that enables
artifact-free strictly local SNOM even at high topographies.
The present SNOM will be the technique of choice if ease
of operation, reliability, economics, and versatility for practical applications with real-world samples are the criteria.

NOTE
[1] A focusing paper (G. Kaupp, The enhancement effect
at local reflectance and emission back to apertureless
SNOM tips in the shear-force gap) has been accepted
to appear in The Open Surface Sci. J., 2011, 12 p.

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Supramolecular Chemistry: From Molecules to Nanomaterials, Online 2012 John Wiley & Sons, Ltd.
This article is 2012 John Wiley & Sons, Ltd.
This article was published in the Supramolecular Chemistry: From Molecules to Nanomaterials in 2012 by John Wiley & Sons, Ltd.
DOI: 10.1002/9780470661345.smc045

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DOI: 10.1002/9780470661345.smc045

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Supramolecular Chemistry: From Molecules to Nanomaterials, Online 2012 John Wiley & Sons, Ltd.
This article is 2012 John Wiley & Sons, Ltd.
This article was published in the Supramolecular Chemistry: From Molecules to Nanomaterials in 2012 by John Wiley & Sons, Ltd.
DOI: 10.1002/9780470661345.smc045