2015 - Deckert Et Al. - Spatial Resolution in Raman Spectroscopy - Faraday Discussions

Faraday Discussions
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Spatial resolution in Raman spectroscopy

Volker Deckert,*ab Tanja Deckert-Gaudig,a Marco Diegel,a Isabell Götz,a
Lucas Langelüddecke,b Henrik Schneidewind,a Gaurav Sharma,b
Prabha Singh,b Pushkar Singh,a Steffen Trautmann,a
Matthias Zeisbergera and Zhenglong Zhanga
Published on 31 March 2015. Downloaded on 9/29/2020 5:31:51 PM.
Received 6th March 2015, Accepted 24th March 2015

DOI: 10.1039/c5fd90014j
This article is intended to set the scope of the meeting, in particular, the high spatial
resolution section.
1 Introduction
A constant motivation to develop advanced technologies addressing temporal and
spatial resolution is the investigation of structural changes of a single molecule
while it is reacting. The dream is to follow a bond breakage or bond formation of a
single selected molecule with a method that provides structural sensitivity, time
resolution, and local specicity. Presently, such a combined technique is not yet
available, however, regarding each single requirement of the mentioned list,
tremendous progress has been made over the last few decades.
This overview will specically discuss the spatial resolution aspects that are
required to address, if not a single molecule, at least a sample volume that is
small enough to distinct the target structure from the background. The 2014
Chemistry Nobel prize awarded to Moerner, Hell, and Betzig, highlighted the
importance of high resolution techniques specically for biochemical applica-
tions. While the awarded uorescence approach is certainly extremely useful
whenever dye labelling is possible and no interference with the function of the
target system is expected, in particular for smaller molecular systems such
labelling is not practical or even possible. In such cases vibrational spectroscopy
techniques can be used, oen at the cost of lower sensitivity, however, as struc-
tural information is obtained directly no labelling is required and sample prep-
aration becomes easier. In this article we will solely present the high lateral
resolution aspects of Raman spectroscopy, many of those aspects can be easily
applied to infrared absorption spectroscopy if the specic factors of the particular
a
Leibniz Institute of Photonic Technology, Albert-Einstein-Str. 9, 07745 Jena, Germany. E-mail: Volker.
[email protected]; Fax: +49 3641 206 139; Tel: +49 3641 206 113
b
Institute of Physical Chemistry and Abbe Center of Photonics, University of Jena, Helmholtzweg 4, 07743 Jena,
Germany
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Faraday Discussions Paper
wavelength range are considered. As mentioned before, the sensitivity of uo-
rescence label techniques easily allows the investigation of single molecules. With
normal Raman scattering this is not possible as the scattering cross sections are
several orders of magnitude lower compared to uorescence. Since the mid 1970s
a method has existed to enhance the Raman signals considerably.1–3 By using
roughened noble metal surfaces or noble metal nanoparticles an enhancement of
several orders of magnitude can be achieved mainly due to plasmonic effects.
This bridges the gap between uorescence and Raman spectroscopy and allows
the investigation of single molecules with so called surface-enhanced Raman
scattering (SERS).4–6
At present the only possible way to overcome the diffraction limit7,8 with
Raman spectroscopy requires the use of optical near-elds. Consequently, we will
deal solely with the special properties of near-eld Raman scattering,9–11 which
luckily is in many ways directly associated with the aforementioned plasmonic
effects. Accordingly a combination of near-eld optics and SERS provides access
to a high lateral resolution, low detection limit, and high structural sensitivity.
Furthermore, many aspects regarding the investigation of small sample volumes,
and thus restricted number of sampled molecules, can be regarded as general
aspects whenever such small dimensions are probed.
2 Experimental
General setup
All investigations mentioned here were measured using a so-called tip-enhanced
Raman scattering (TERS) setup. Fig. 1 shows the schematic sketch of our system.
The main components are an atomic force microscope (AFM) and an inverted
optical microscope equipped with an x, y, z piezo stage for automated sample
scanning. The whole system is designed for a precise positioning of the near-eld
optical probe with respect to laser focus and sample. These parts are shown in
dark grey. Additionally, coarse sample and tip alignment standard xy stages with
2 mm precision are also available, but not shown in detail. Further details about
this particular setup can be found in the literature where a straightforward
adaptation to a reection setup giving access to opaque samples is also pre-
sented.12–14 The illumination through substrate and sample on to the plasmonic
tip seems to be demanding and prone to losses, however, this setup allows for the
best collection efficiency and implementing proper polarisation allows an
optimal excitation of the nanoparticles.
TERS tips
Theory. The TERS tips are the integral element of the entire system. Their
special properties are responsible for the combination of high lateral resolution
and signal enhancement. When irradiating silver or gold (other metals like Cu or
Al have also been tested for special purposes) nanoparticles with light of an
appropriate wavelength, electrons in the conducting band are collectively excited
and oscillate with the same frequency as the incoming electromagnetic eld. This
can be considered as an optical analogue of a receiving antenna15 and leads to an
enhancement and connement of the elds depending on the shape and size of
the actual nanoparticle. For details on the enhancement mechanism and a
10 | Faraday Discuss., 2015, 177, 9–20 This journal is © The Royal Society of Chemistry 2015
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Fig. 1 Schematic view of a TERS epi-illumination setup. Tip and sample can be scanned
independently using precision piezo stages. Illumination and collection for the Raman
system is carried out via a high N. A. objective. The detection of the Raman signal is done
after appropriate filtering using a standard multichromator/CCD detector arrangement.
thorough theoretical description see ref. 16–19. In essence, if the experimental

conditions are matched properly the eld is conned to a very small volume close
to the tip. Fig. 2 shows model calculations of “ideal” tips, either with a single
nanoparticle on an AFM tip apex or even with only a single metal sphere. In both
Fig. 2 Left panel: field distribution of an ideal TERS probe with one single nanoparticle
attached to the apex of an AFM tip. Right panel: detail of the field distribution E(x, z)
obtained by FEM simulation for a silver sphere (similar to the dipol–mirror dipole model) of
radius 10 nm and a distance from the surface of 5 nm, l ¼ 413 nm. Field distributions in
both cases are comparable.
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cases a total internal reection illumination from the lower le was simulated.
This results in an evanescent eld excitation of the tip, which has some experi-
mental advantages, but is not essential for such modelling. This geometry
nevertheless explains the slight asymmetry of the electric eld distribution. Most
importantly, these simulations reveal the extreme light connement in all three
dimensions. The main lateral enhancement is concentrated underneath the
sphere with a size of roughly the radius of the particle. In the focus direction the
eld decays even faster. As the Raman intensity scales approximately with the
fourth power of the incident eld a lateral resolution for realistic tip sizes (in our
case 15–30 nm diameter) can be expected to be well below 5 nm. This value takes
into account only the electromagnetic theory for the “macroscopic” appearance,
specic atomic scale protrusions like corners or edges, as well as specic chem-
ical interactions between the silver atoms and the sample, which could both
potentially increase the resolution, are not considered. Interestingly, at very small
scales below 3 Å quantum effects start to play a role, nally limiting the lateral
resolution.20 In any case one can expect a spatial resolution that renders many
samples as single crystals or at least oriented in a statistically unexpected direc-
tion, if special care is not taken in sample preparation.
Tip preparation. Fig. 3 shows typical SEM images of the tips mostly used in our
group. These tips are obtained by physical vapour deposition of silver onto
commercially available AFM tips21 and the resulting silver nanoparticles have
diameters of less than 30 nm. This approach aims to produce one more or less
isolated small silver nanoparticle at the apex of the AFM tip and was initially
developed for SERS substrates.21–23 The nanoparticle at the tip apex serves as the
active nano-antenna mentioned above. Inspecting more than a hundred tip
batches, three main geometries of the outermost silver nanoparticles were found.
Type (a) reveals a single silver nanoparticle at the top of the AFM tip in close
vicinity with other particles. Most of the time the nanoparticles are slightly off-
axis. A second type (b) shows two silver nanoparticles at the top. Usually, one of
the two nanoparticles is located a few nanometers in front of the other one. Thus,
we can expect that one acts as the plasmonically active device in the TERS
experiment. About two thirds of our prepared tips t these two classes. Last but
Fig. 3 SEM images of the main manifestations of the silver nanoparticles on top of the
TERS tips: a single nanoparticle at the outermost top (a), two nanoparticles at the top (b), or
a single nanoparticle at the edge of the AFM tip (c), respectively. The scale bar applies to all
images. The insets show the same tips using the material contrast.
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not least, a small number of tips showed one clearly isolated frontmost silver
nanoparticle, again usually slightly off axis (c). As the practical yield, e.g. the ratio
of tips in a batch that produce a considerable enhancement, of such tips is around
90% the actual geometry is inuencing merely the details of the enhancement
and, also quite importantly, the properties for the topographic sensing. Recently a
more directed approach was successfully investigated for the particle attachment
using dielectrophoresis.24–28 This method allows single preselected nanoparticles
to be placed onto an AFM cantilever, and hence, seems to be promising for
dedicated applications with preformed particles. Furthermore, many different
approaches to tip production have been presented and which type is most suited
certainly depends on the specic experimental requirements.23,24,26–28,29–31,32
Application examples
Self-assembled monolayers. In order to provide a reproducible method of
sample preparation, self-assembly is a well-established tool. This way only a single
layer of molecules can be investigated and the orientation is generally pre-
determined. Certainly this approach is not feasible for most realistic samples,
nevertheless, the study of self-assembled monolayers (SAMs) is ideal to rule out
specic concentration effects. In particular if working with an extremely distance
dependent method like TERS, a layer with such thickness and orientation control
is important to examine fundamental parameters. Several TERS studies have been
performed on molecules adsorbed onto gold single crystals.29,30 This provides
reliable conditions, as any surface roughness effects can be ruled out. In partic-
ular for STM based reection TERS systems this is an ideal arrangement. In order
to utilize the advantages of single crystalline surfaces for epi-illumination setups
like the one shown in Fig. 1, methods were developed to manufacture gold32–35 or
silver36,37 single crystals thin enough for the transmission of light. Those were
readily applied to study small molecules like thiophenols, amino acids and small
peptides.33,34,38,39 It became apparent that, in particular, the spectra of aromatic
amino acid monolayers lacked some usually strong bands, but could still be
identied by other marker signals. If the experimental results were compared
with theoretical models of amino acids on gold (111) surfaces it became evident
that, due to the most favoured at orientation of the molecules versus the surface,
the typical “ring breathing” modes were not efficiently excited in the TERS setup
where the electric eld vector is oriented orthogonally towards the surface and
consequently orthogonal to the ring stretching vibrations.36,40–43 Interestingly, the
eld components at the tip side (see Fig. 2) did not play a role, as these compo-
nents should have excited the suppressed modes. This indirectly hints towards a
high eld connement, i.e. a high lateral resolution, which is of course difficult to
determine on a SAM. To further study that effect an even simpler system was
chosen.38 Thiophenol was immobilized on at and rough gold and silver surfaces.
Here, the “ring breathing” mode was excited, as the perpendicular orientation of
the molecule with respect to the surface is favourable for TERS excitation. The
main target of the work was to study differences between the SER and TER spectra
of thiophenol monolayers. Oen TERS signals tend to uctuate slightly and the
idea here was to control the orientation and layer thickness as well as possible.
Fig. 4 shows the most intriguing features of the experiments. The two spectra (a)
and (b) on the le side show the two selected SERS bands of a self-assembled
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Fig. 4 Comparison between SERS (a and b) and TERS (c and d) spectra of thiophenol
monolayers. Due to the small number of molecules detected in the TERS case, averaging
effects like in the case of the SERS spectra are absent or not yet pronounced. This leads to
stronger fluctuations in the TERS case.
thiophenol monolayer on a gold island lm measured at arbitrary locations. The

band parameters, width, intensity, and spectral position, hardly vary as can be
expected if both the lm and the substrate are homogeneous. The term “SERS
substrate homogeneity” is a bit contradictory, as the substrates resemble more or
less the silver island lms on the AFM cantilevers shown in Fig. 3. On the other
hand the laser spot is comparably large, and from the data it can be concluded
that the inhomogeneities of the lms were averaged out. In this respect, the
corresponding TERS experiment should be even more reproducible: a 30 nm
thick gold ake, of diameter 2–3 mm, and a surface roughness of typically around
2 Å, is a much more regular sample support than any SERS substrate can
intrinsically ever be. On top of this gold plate the TERS tip was positioned, whose
enhancing properties hardly changed during the measurement. Still, the experi-
mental data show much stronger band position uctuations at different positions
on the gold crystal compared to SERS (see Fig. 4c and d). A similar time dependent
experiment over several minutes effectively showed the same behaviour for the
SERS and TERS experiment, respectively. We attributed this behaviour to the fact
that in the TERS experiment we probed such a small sample volume that aver-
aging of minute molecule orientations was not observed, whereas in the SERS
case many more molecules and also much more enhancing sites led to an
effective averaging of the Raman signals. To support this hypothesis the band
widths of the TERS and SERS experiments were also compared. Not surprisingly,
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the TERS data showed a broader distribution, however, the average width of the
TERS experiments was always lower compared to the SERS spectra. As for both
experiments the same physical constraints were applied, we hypothesise that the
SERS spectra are a combination of many local single particles or single hot spot
events, which would fundamentally resemble the TERS experiment. Moreover,
these results raise the question how many molecules are actually probed in a
TERS experiment? Again a direct estimation of the resolution is not possible from
a monolayer measurement, but it is certainly interesting to speculate on the
number of molecules required for averaging effects to dominate the spectra. For
comparison, a hundred closely packed thiophenol molecules approximately t on
a 4 4 mm area.
Protein structures and spatial resolution

As a kind of by-product of our TERS investigations of protein structure surfaces,
namely amyloid brils, the lateral resolution aspect emerged again.40–44 When
investigating brils with TERS using a step size of 5 Å between subsequent
positions, surprisingly pronounced spectral changes could be observed if a long
enough acquisition time was chosen to allow a detailed band analysis. It should
be mentioned here that Paulite et al. have presented TERS images of well-ordered
amyloid nanotapes that appear homogeneous.45 Unfortunately the signal-to-noise
ratio in those experiments was chosen such that apart from the phenylalanine
“ring breathing” mode no other signal was detected and a prediction regarding
structural changes was hardly possible. Hence, we consider the signal variations
detected in our experiments to be signicant and related to the actual sample
composition. If one considers furthermore the ndings of the previous experi-
mental and theoretical section concerning the lateral resolution, the choice of
step size to be 5 Å was set quite conservatively to avoid accidental undersampling
of the dataset. When investigating the data we typically nd results like those
shown in Fig. 5. Here we investigated an insulin amyloid protolament and
clearly saw structural changes occurring on a length scale of a few Ångströms. For
instance, in the rst four spectra one can observe an amide I band (at 1604 cm1)
representing a-helix/unordered secondary structures. This is also observed,
however slightly weaker, in the h spectrum, but then vanishes in the remaining
two spectra. Similar patterns can be observed for the disappearance of the
phenylalanine “ring breathing” mode and the appearance of a tyrosine marker
band. The marker bands of cystine also change, however, as many different
conformations around the disulde bridge affect the exact spectral position and
intensity ratios of the associated bands, a full assignment would be too complex
here. Similarly, as detected in the self-assembled thiophenol monolayer case, one
can observe similar spectral band position variations that are related to the
immediate local environment of the sample. This can of course also involve the
tip. These results can be simply understood as a way to investigate structural
changes with high lateral resolution. But, in fact, this resolution is rather unex-
pected as we do not observe average peptide spectra, but rather locally dependent
changes that reveal distinct amino acid contents.44 Looking at the data of Fig. 4
and considering previous data on brils41,42,44 and on DNA bases46,47 a lateral
resolution of about 1 nm can be estimated which is actually at the limit of
sampling in the case presented. Bearing in mind the TERS SAM experiments
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Fig. 5 TERS spectra detected on an insulin amyloid protofilament generated at pH 1.5,

laser excitation 532 nm, acquisition time 10 s/spectrum, distance between positions 0.5
nm. Two major patterns can be clearly distinguished: only in the first 5 spectra a-helix/
unordered structures can be clearly identified by amide I bands at 1640 cm1. A transition
is also apparent in the synchronous appearance and disappearance of phenylalanine,
tyrosine and cystine.
where a direct estimation of the resolution was not feasible, such a lateral reso-
lution would relate to less than 10 molecules in the active region under the tip.
For such a small number a “non-average” behavior becomes reasonable.
There is an important caveat to the generalization implied here. At the
moment we are not aware of a full theoretical description that explains the lateral
resolution of the experiments. It seems that either the size and shape parameters
of the plasmonic tips have to be modeled differently, or that direct interactions of
the tip and the sample provide an additional contrast that leads to the enhanced
resolution observed. The latter aspect is oen termed “chemical enhancement”.
While currently strong efforts are being made to unravel this issue, we think that
any high resolution beyond 3–5 nm can be utilized to sequence virtually any
material.
General method for sequencing a single strand

For such sequencing we will provide the outline of this method and an estimation
of the precision that is required for a successful application.48 One can consider a
tip as a simple point dipole, with the dipole in the z-direction, with a given eld
distribution that results in a TERS interaction volume as mentioned previously.
This means for the following ideas we assume the theoretically predicted lateral
resolution values and not even the values we experimentally determined. If, for
instance a DNA single strand is aligned along the x-axis with bases at the positions
xk (k ¼ 1, 2, ., K) and z ¼ 0, and the tip moves along x at height z, the signal at
position xn for one particular Raman peak will be
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X
K
Sðxn Þ ¼ bk Pðxn xk ; zÞ; n ¼ 1.N
k¼1
where bk equals either 1 or 0, depending on whether the monomer investigated

(here a nucleobase) is present at xk (or not). P(x,z) is related to the inuence of the
tip and is proportional to the 4th power of the eld. For N > K, the coefficients bk
can be calculated using a least square tting method that requires the inversion of
the matrix (M).
X
N
Mlk ¼ Pðxn xk ; zÞPðxn xl ; zÞ; k; l ¼ 1.K
n¼1
Such inverse problems are oen ill conditioned, i.e. a small error in the input
values (S(xn)) can result in huge errors in the reconstructed solution (bk). A useful
method to evaluate this problem is the singular value decomposition of the
matrix M which provides the condition number C. This number allows the esti-
mation of the error of the reconstructed b values for a given error DS/S of the
actually measured signal S.
Db DS
#C
b S
Fig. 6 shows the condition number of our problem as a function of the distance
between tip dipole and base size normalized with respect to the base-to-base
Fig. 6 Condition number C of the inverse sequencing problem using the theoretically
modeled enhancement profile of a TERS tip. The graph shows how quickly the method
becomes unreliable if the distance z between tip and sample increases. The x-axis values
represent normalized distances normalized to a single unit of interest Dxk (for instance a
base-to-base distance in DNA). Interestingly an AFM can achieve the small distances
required.
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distance. We assumed 5 samples per base, i.e. N ¼ 5K, in other words, the polymer
strand is scanned in such a way that each single base is sampled at ve different
subsequent TERS tip positions. The data show that a direct reconstruction of the
bk values is only possible for extremely small distances between the bases in the
DNA strand and the tip dipole which corresponds to the center of the Ag sphere in
the experiment. If, for example, the error in the Raman signal is 1% this esti-
mation results in a maximum distance z of two base-to-base distances corre-
sponding to roughly 1 nm. In addition to this general estimation we performed
simulations where we started with several arbitrary base arrangements and
calculated the corresponding TERS signal. Aer adding a certain noise to the
signal we recalculated the base positions. The simulations show that slightly
higher distances are allowed compared with the estimation given above, but the
general trend was conrmed. While this renders the sequencing a challenging
problem, it is also clear that the method's quality will improve dramatically with
improving lateral resolution. Taking into account the experimental resolution
value estimations and further improvements in the above mentioned method (for
details see ref. 48) a direct sequencing as proposed already in the rst TERS paper
on DNA strands49 is possible.
3 Conclusion
We presented the high resolution aspects of Raman spectroscopy using different
approaches. By studying homogeneous samples under controlled conditions, a
comparison of signal position uctuations indicates that TERS probes very small
sample volumes where individual orientation effects are not averaged. Comple-
mentary studies on proteins and protein brils reveal a surprising capability to
distinguish amino acid distributions locally on a length scale of at least 1 nm, also
conrming the high spatial resolution of TERS. Interestingly, no consistent theory
is at hand to explain this resolution with the usual approach using “macroscopic”
tip parameters. Last but not least we presented a general method that allows a
direct sequencing of single polymer stands with TERS that would already work
with the current theoretically predicted resolution.
The time resolution aspects of TERS have not been addressed here, but are
currently being successfully investigated by the van Duyne group.50 In this way the
goal to combine ultimate temporal, spatial and spectral resolution as a general
tool should be reached in the not too distant future.
Acknowledgements
We gratefully acknowledge support from the Deutsche Forschungsgemeinscha
(FR 1348/19-1) the Alexander von Humboldt foundation, the Carl-Zeiss Founda-
tion and the Thüringer Auaubank (FKZ: 2011 FE 9048; 2011 VF 0016) for their
nancial support.
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2015 - Deckert Et Al. - Spatial Resolution in Raman Spectroscopy - Faraday Discussions

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Spatial resolution in Raman spectroscopy

Received 6th March 2015, Accepted 24th March 2015

thorough theoretical description see ref. 16–19. In essence, if the experimental

thiophenol monolayer on a gold island lm measured at arbitrary locations. The

Protein structures and spatial resolution

Fig. 5 TERS spectra detected on an insulin amyloid protoﬁlament generated at pH 1.5,

General method for sequencing a single strand

where bk equals either 1 or 0, depending on whether the monomer investigated

39 E. M. van Schrojenstein Lantman, T. Deckert-Gaudig, A. J. G. Mank, V. Deckert

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