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Tip-Enhanced Raman Spectromicroscopy of

Co(II)-Tetraphenylporphyrin on Au(111):
Toward the Chemists’ Microscope
Joonhee Lee,† Nicholas Tallarida,† Xing Chen,‡ Pengchong Liu,‡ Lasse Jensen,*,‡
and Vartkess Ara Apkarian*,†
†
Department of Chemistry, University of California, Irvine, Irvine, California 92697, United States
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

‡
Department of Chemistry, Pennsylvania State University, University Park, Pennsylvania 16802, United States
*
S Supporting Information

ABSTRACT: Atomically terminated and nanoscopically smooth silver tips effectively

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focus light on the angstrom scale, allowing tip-enhanced Raman spectromicroscopy

(TER-sm) with single molecule sensitivity and submolecular spatial resolution. Through
measurements carried out on cobalt-tetraphenylporphyrin (CoTPP) adsorbed on
Au(111), we highlight peculiarities of vibrational spectromicroscopy with light confined
on the angstrom scale. Field-gradient-driven spectra, orientational fingerprinting, and
sculpting of local fields by atomic morphology of the junction are elucidated through
measurements that range from 2D arrays at room temperature to single molecule
manipulations at 5 K. Notably, vibrational Stark tuning within molecules, reflecting
intramolecular charge distributions, becomes accessible when light is more localized
than the interrogated normal modes. The Stark images of CoTPP reveal that it is
saddled, and the distortion is accompanied by charge transfer to gold through the two
anchoring pyrroles.
KEYWORDS: tip-enhanced Raman spectroscopy, spectromicroscopy, confined light, Stark shift, field-gradient-driven Raman,
quadrupolar scattering, scanning tunneling microscopy

by a gap of ∼1 nm, is prototypical.2 By coupling light to surface

T o the extent that molecules can be regarded as

networks of balls (atoms) and springs (bonds), they
can be characterized by the frequencies of their internal
motions. This is the realm of vibrational spectroscopy, which
remains one of chemists’ sharpest tools for fingerprinting
molecules and characterizing their inner workings. As such, the
ability to record vibrational spectra of individual molecules, by
sounding off individual atoms within molecules, can be
regarded as the chemists’ ultimate microscopethe chemi-
scope for short. The task is challenging for several reasons. The
universally applicable method for recording vibrational spectra
is based on the Raman effect, which involves the excitation of
molecules with light and recording the spectrum of reradiation
by the vibrating molecule. The effect is feeble. To obtain a
useful signal at the level of 103 photons/s, it is necessary to
irradiate a molecule at intensities of terawatt/cm2. Moreover,
photons are much larger than atoms. The Abbe principle
recognizes that the wavelength of the photon limits the focus of
the optical microscope to a spot of ∼λ/2, with λ ∼ 500 nm in
the visible region. To reach the 0.1 nm size scale of the atom,
photons must be squeezed down to a thousandth of their size.
These challenges are met by resorting to plasmonic
nanoantennas.1 The nanoscale analogue of the antenna used
by Hertz, consisting of a pair of metallic nanospheres separated
charge oscillations (plasmons) of the dipolar nanoantenna,
electromagnetic fields are effectively focused at the nano-
junction. The large field enhancement due to confinement is
sufficient to record Raman spectra of individual molecules,3−5
through the surface-enhanced Raman scattering (SERS) effect,
which was discovered nearly four decades ago.6 Although there
has been an explosion of developments and applications of
SERS,7 the fundamentals of the effect remain the subject of
active research. It is recognized that the primary challenge
stems from the atomistic morphology of junction shaping the
local fields,8 which determines the SERS signal.9 This is
precisely the sensitivity required to image the internal motions
of individual molecules; at the same time, spectroscopy with
confined light is poorly understood, and characterization or
control of nanojunctions with atomistic precision is a challenge.
Resorting to the more controllable junction of a scanning
tunneling microscope (STM), under the rubric of tip-enhanced
Raman spectroscopy (TERS),10 has led to accelerated discovery
through TER spectromicroscopy (TER-sm).11,12 Noteworthy
Received: August 30, 2017
Accepted: October 4, 2017
Published: October 4, 2017

© 2017 American Chemical Society 11466 DOI: 10.1021/acsnano.7b06183

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among these was the realization of TERS with submolecular
spatial resolution13an effect that was not anticipated by then
standard classical models of tip plasmons.14 In the subnan-
ometer junction gaps necessary to reach single molecule
sensitivity, quantum effects cannot be dismissed.15−17 The
dynamics of optically driven electrons, which tunnel across
junctions, must be explicitly treated to describe the relevant
local fields.18,19 Atomistic electrodynamics simulations,20
coupled with quantum chemical treatments of the molecule
and the scattering process,21,22 are necessary for reliable
descriptions. Moreover, given the strong fields, field and matter
states can be entangled.23,24 The quantum electrodynamics of
plasmonic cavities, which confine photons, electrons, and the
molecule under study, provides a frontier in science that must
be mastered along the way to develop the chemiscope.
We use cobalt(II)-tetraphenylporphyrin (CoTPP) to carry
out a joint experimental and theoretical study of TERS at the
STM junction of a silver tip and an atomically flat Au(111)
substrate. CoTPP has been previously investigated through
STM,25 TERS,26 and theory.27 It saddles upon adsorption,
whereby the phenyl groups twist and tilt successive pyrroles up
and down (see Figure S1 in Supporting Information). The
saddled molecule contains the necessary geometric features to
scrutinize principles of vibrational spectromicroscopy with
confined light. As an important milestone, we show room
temperature TER-sm at the same resolution as STM, but now
with vibrational hyperspectral information. The spectra are
thermally activated. At 80 K, they degrade to field-gradient-
driven modes, which is Stark tuned. This allows TERS-relayed
vibrational Stark microscopy to image intramolecular charge
distributions, with prior examples of such information extracted
using atomically resolved Kelvin probe force microscopy
(KPFM).28,29 At 5 K, we manipulate individual molecules to
highlight the tensorial nature of single molecule spectroscopy
with confined light, and show that the spatial resolution of
TERS reaches the 1 Å limit. The range of observed effects can
be rationalized through simulations using the atomic electro-
dynamics model20,30 to describe confined fields and the dressed
tensor formalism31 to treat spectroscopy with confined light in
terms of local field/field gradient enhancement driven through
derivatives of electric dipole−dipole, electric dipole−quadru-
pole, and electric quadrupole−quadrupole polarizabilities.
Notwithstanding the necessary approximations, the combined
experiment and theory study yields deep insights on the salient
features and prospects of TER-sm.
RESULTS AND DISCUSSION
TER-sm. At room temperature, CoTPP forms an ordered
monolayer on Au(111), as seen in the simultaneously recorded
STM and hyperspectral TERS images in Figure 1a−c. The
latter consist of complete spectra recorded on each 1.4 Å × 1.4
Å pixel with an acquisition time of 1 s/pixel. The TERS
spectrum (Figure 1d) disappears upon 1 nm retraction of the
tip (Figure 1e). The gap dependence of the signal intensity can
be approximated as exponential, with a decay constant of 3.5 Å.
The scatter in the retraction data is due to motion of the
molecule, both thermal and lift-off by the van der Waals
attraction to the tip.32 The spectrum (Figure 1d) consists of
three distinct components: the exponentially decaying back-
ground of electronic Raman scattering on the metal at shifts
larger than 1700 cm−1 (better shown in Figure 6c), a flat
background with a cutoff near 1600 cm−1, and a set of thermally
broadened molecular vibrational lines within this window. The
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Figure 1. Vibrational spectromicroscopy at 300 K. (a) Topographic
image (57 × 57 Å2) recorded at 10 pA, +0.15 V. (b) Simultaneously
recorded Raman map integrated over the full window (300−1700
cm−1). (c) Mode-specific map of the highest frequency vibration
(integrated over the 1550−1600 cm−1 window colored by light pink
and blue bands). (d) Comparison between TERS of CoTPP on
Au(111) and simulated spectrum. Calculated normal modes nearest
to the color-coded windows are illustrated accordingly. (e)
Exponential decay of TERS intensity integrated over the 700−
1650 cm−1 window. The dashed line indicates the level for zero
intensity. Images are filtered due to the thermal noise at 300 K (raw
images are presented in Figure S4 in the Supporting Information).
presented spatial maps are the spectrally integrated TERS
intensity (Figure 1b) and the mode-specific map of the
vibration at 1576 cm−1 (Figure 1c). The mode-specific
vibrational images of all eight observed lines are provided in
Figure S3 in the Supporting Information. They show subtle
variations with respect to the STM topography. Inspection of
the images in Figure 1a−c is sufficient to infer that the spatial
resolution in the TER-sm is nearly the same as the STM.
A satisfactory reproduction of the spectrum is possible under
the assumption of electric field polarized along the tip axis and
molecules tilted out of plane. The best match is obtained upon
tilting the molecule out of the substrate plane by 32° relative to
the surface normal, followed by 42° rotation in the tilted
molecular plane. The field-active normal modes dominate the
spectrum, and at room temperature, the thermal population of
molecules that tilt out of the plane is observable.33,34 The
observed vibrations are normal modes that are principally
localized on the phenyl rings, as illustrated in Figure 1.
Nevertheless, there are subtle spatial variations in the mode-
specific images (see the Supporting Information). The maps of
the 1252 cm−1 (1220 cm−1 calculated) and 1576 cm−1 (1592
cm−1 calculated) mode are generally anticorrelated with the
location of the molecules, whereas the map of the mode at 1092
cm−1 (absent in the calculations) is closely correlated. The
1550 cm−1 is the only mode that does not involve phenyl
vibrations. It is mainly localized on the pyrroles, which pull out
of the porphyrin plane in the saddled molecule.
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Confined Field, Photon, and Signal. The enhanced
background without vibrational peaks tracks the STM top-
ography with high fidelity. This is clarified by the superimposed
contour maps of the STM topography and the background
(cyan band in Figure 1d) map in Figure 2a and associated line-
Figure 2. Raman signal of confined cavity mode. (a) Overlay of the
STM topography (black contours) and the cavity mode map (cyan
contours, integrated over the cyan band in Figure 1d, 320−500
cm−1). (b) Line profiles of topography (black) and cavity map
(cyan) taken along the two diagonal lines in (a), which are
displaced by 4 Å.
cuts shown in Figure 2b. The background is assigned to the
cavity mode, namely, the confined optical field in the junction.
Its intensity perfectly tracks the STM topography, but with a
diagonal displacement of ∼4 Å. The apparent displacement of
the optical signal from the terminal tip Ag atom by the
dimensions of one atom provides a direct measure of the lateral
confinement of the TERS signal to an area of ∼16 Å2. Together
with the decay length of the intensity with the vertical tip
retraction, a signal confinement volume of ∼100 Å3 can be
inferred. Although it is tempting to assign this volume to the
confinement of a photon, the local field that would arise from
one such photon, E = ℏω/2ε0V = 1.2 V/Å , is not sensible
because it would ionize any molecule. From the observed
scattered intensity and the Raman cross section of the
molecule, the local field can be estimated to be 100 times
Figure 3. Sculpted junction fields. Cross-sectional views of near-field and field gradient distributions are illustrated for a flat gold tip (a,b),
atomically terminated tip (c,d), and CO-terminated tip (e,f).
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smaller, ∼5 × 10−3 V/Å. Only a small fraction by volume, 10−4,
of one photon is ever present at the junction.
The observed localization of the signal is consistent with the
field confinement expected from the atomically terminated tip
presented in Figure 3. We use an icosahedral gold nanoparticle
consisting of 2057 atoms against a planar gold slab to calculate
the local fields. The dimensions and gap-independent
resonance of the structure, which matches the experiment,
2.32 eV (534 nm), is shown in Figure S5. The strongest and
most confined near-field is obtained at a slightly lower energy
than the plasmonic resonance.21 At the depicted gap distance of
5.5 Å, which corresponds to the experiment, the hot spot of the
Au-atom-terminated tip has a lateral width at half-maximum of
E21/2 ∼ 6 Å (Figure S5b), with associated field gradients that are
more tightly confined. When the quartic dependence of the
signal on the local field is taken into account, the predicted
lateral confinement of the field-induced signal is ∼3 Å, in
agreement with the experiment. The signal is localized down to
the size of an atom, nearly 4 orders of magnitude sharper than
allowed by the Abbe principle of optics and significantly smaller
than the spatial extent of vibrational normal modes that extend
over the molecule.
Silence and Activation of TERS with CO. Upon being
cooled to 80 K, the molecular TERS signal disappears. Due to
the improved thermal stability and planarity of the cold
molecules on the substrate, sharp STM images of the molecular
array can be recorded, as in Figure 4a. However, the
simultaneously collected TERS images are completely feature-
less. Indeed, if the scattering was electronically resonant via the
Q-band, then cancellation of the in-plane transition dipole via
its image in the gold mirror could explain the total silence.
However, the excitation wavelength at 634 nm is removed from
the Q ← X transition of CoTPP, which occurs at 530 nm
(Figure S2). Flattening the molecule from its room temperature
tilt into planarity reduces the signal by a factor of 5−10, but this
does not explain the complete silence of the spectra given the
dynamic range of detection. In the depicted junctions (Figure
3c,d), the hot spots of field and field gradient miss the aromatic
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Figure 4. CO as a cavity spoiler. (a) Topography of CoTPP
monolayer at 80 K with resolved phenyl groups. The set point is 16
pA and 0.2 V. (b) Degraded topography of CoTPP obtained at 80
pA, 4.9 mV, due to CO lattice gas on the surface. (c)
Simultaneously recorded Raman map with flashes as CO molecules
pass by. Each pixel is the Raman intensity integrated from 600 to
1650 cm−1. (d) Extracted spectra from the map (c), 1 and 2,
highlight the flashes. Acquisition time is 1 s. Spectra 4 and 5 are
recorded with a stationary tip engaged and retracted by 5 Å,
respectively (10 s integration). The 80 K spectra 1 and 4 agree with
the spectrum acquired at room temperature, 3. (e) TERS trajectory
while the tip is stationary. (f) Disappearance of Raman signal upon
initiating a scan. Scale bars in (a−c) are 1 nm long.
macrocycle, which remains in the electron spill-out region
where the electric field is screened. Not included in the model
is the Schockley surface state (SS) of gold,35 which provides a
nearly free 2D electron density, famously visualized by the
construction of quantum corrals.36 The coupling of the
slouched molecule with the SS is suspected as the origin of
the silence, which would also explain the prior TERS imaging of
planar porphyrins with bulky substituents that raise the
macrocycle plane.13 Consistent with this picture, the vibrational
spectra are activated upon introducing a 2D lattice gas of
mobile molecules, ostensibly by destroying the SS or by lifting
molecules out of the zone of silence.
Upon introducing CO molecules, which are mobile on gold
at 80 K but eventually desorb, complete vibrational spectra of
CoTPP emerge. This is illustrated in the simultaneously
recorded images of Figure 4b,c: the STM image is streaky, due
to the CO gas, and the simultaneously recorded TERS data
show no correlation with the STM image or any spatial
features. However, the bright streaks that appear sporadically
during the scan carry the sharp and rather complete vibrational
spectrum of the cold molecule (Figure 4d, trace 1). The
activated spectra are stable when probed with a stationary tip,
as illustrated by the TERS trajectory in Figure 4e. The lines are
instrument limited to FWHM = 6.7 cm−1, with fluctuations in
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the center frequency on the order of 1 cm−1. The large dynamic
range of the spectra identifies over 30 vibrational lines, with
direct lineage to the room temperature spectrum (see traces 3
and 4 in Figure 4d). Their single molecule TERS nature is
established by the retraction dependencethe spectrum
disappears upon 5 Å retraction of the tip (Figure 4d, trace
5). That the intercalated CO is only loosely attached to the
junction or to CoTPP is demonstrated by the trajectory in
Figure 4f: the activated spectrum is lost as soon as the scan
starts. Despite the high S/N ratio of the activated spectra, we
do not observe the characteristic CO vibrational line, which we
see when it binds to the apex at 5 K (see below). The possible
role of CO as a local field spoiler is considered by comparing
the field of an empty cavity and one in which a single CO
molecule or a single Au atom is introduced (Figure 3c−h). The
field lines and field gradients are sculpted quite differently in
each case. Their coexistence would generate significant
inhomogeneity on the molecular scale and destroy the extended
SS.
Alternatively, the spectra may be activated by chemical
binding of CO. As many as two CO molecules bind to the
central Co atom of CoTPP, with two possible binding
geometries: axial binding on opposite sides and bridge binding
with both carbonyls on the same face. The optimized structures
are shown in Figure 5, along with predicted spectra, generated
Figure 5. CO-activated spectrum at 80 K and simulations assuming
(a) bare CoTPP and its dicarbonyl with (b) axial and (c) bridge
binding. The spectra are dominated by field contributions.
by dressing molecular polarizabilities with field and field
gradient and adjusting their orientation (details in Table S1 of
the Supporting Information). The comparison between experi-
ment and simulation is informative. Although the direct lineage
between the 80 K and room temperature bare molecule is
established, the best agreement in Figure 5 is with the axial
dicarbonyl. The contradiction illustrates that, in the single
molecule limit, intensity patterns in spectra can be more
strongly influenced by orientation than chemical structure.
Here, the axially bound CO leads to tilting the molecule and
raising its slouch. As a result, the in-plane normal modes are
enhanced (e.g., 1342 cm−1 mode) relative to bare CoTPP and
bridging dicarbonyl. The calculations clarify that the local field
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Figure 6. Field-gradient-driven TER-sm and intramoleculear Stark imaging at 80 K. (a) STM topography of CoTPP lattice at 0.1 nA, 9.8 mV.
(b) Raman image anticorrelated with topography produced by integrating 1270 cm−1 mode intensity (634 nm laser at 5 μW/μm2, 1 s
accumulation per pixel). (c) Degraded TERS spectrum. (d) Background-subtracted experimental spectrum and simulation. (e) Zoomed-in
topography. (f−h) Super-resolution TER-sm. The 1270 cm−1 mode is fitted to a Gaussian (h), and the extracted intensity and frequency shift
are mapped in (f) and (g), respectively. The high pyrroles of saddled CoTPPs are resolved in the frequency map. (h) Line profiles from two
pixels in (g). Scale bars are 1 nm long. Images are filtered due to invasive imaging conditions. Raw images are presented in Figure S7 in the
Supporting Information.

dominates the spectra (E/∇E = 14 Å). Either geometry could,
in principle, lift the macrocycle out of the zone of silence.
Vibrational Stark Microscopy: Polarization of the
Pyrroles. TERS microscopy, albeit with a degraded vibrational
spectrum, becomes possible once the CO gas subsides. The
simultaneously recorded STM and TERS images are shown in
Figure 6a,b along with the observed spectrum in Figure 6c. An
adequate reproduction of the spectrum is obtained assuming
quadrupole−quadrupole scattering in extremely confined light,
E/∇E = 1.4 Å. Note that the contrast in the TERS images of
Figure 6 is inverted. The TERS intensity is largest when the tip
traces the metal intervening the molecules. This is, in part, due
to the conductivity of the junction, which controls field
confinement, and it is consistent with field-gradient-driven
scattering, which has previously been demonstrated to be more
efficient when the tip is placed outside the molecule.21 Despite
the weak signal, spatially well-resolved images can be obtained
by mapping out the Gaussian fit to the vibrational line at 1270
cm−1, with advantage analogous to that of super-resolution in
fluorescence microscopy.37 A given line now generates two
maps, one of intensity and one of frequency shift, as shown for
the magnified area scan in Figure 4f,g. The spatial detail in the
frequency shift image is significantly higher than that in the
STM. The intensity map shows that the signal is peaked in the
intermolecular pockets where phenyl groups converge. The
vibrational frequency shift arises from the Stark effect, due to
the local electrostatic field, F, sampled by the vibration. The
effect is first-order in dipolar transitions of odd (u) symmetry,
Δν = ΔμF/h, second-order in strictly Raman-active modes of
even (g) symmetry, Δν = ΔαF2/2h.38 The large vibrational
shift of 10 cm−1 observed across the image identifies an odd
transition that scatters into the far-field through the local field
gradient. We show in Figure S8 in the Supporting Information
that the 1270 cm−1 mode becomes the main spectral line when
|∇E/E| ∼ 2. The large field gradients alter the traditional
Raman selection rule so that quadupolar scattering dominates.
Because the measurement is carried out at a small bias, Vb =
10 mV, the source of the electrostatic field is dominated by the
11470
local contact potential. Due to the difference in work functions,
a contact potential of 0.57 V can develop between Au(111) and
Ag tip if we assume [111] termination.39 Stark tuning of a
mode within the molecule implies variation of charge density,
therefore potential, inside the molecule. The largest frequency
shift, 10 cm−1 relative to gold, occurs on the raised pyrroles of
the saddled molecule. The lower pyrroles appear inequivalent
due to the extent of their contacts to gold, whereas the cobalt
center appears at an intermediate potential. Clearly, the
molecule is charged, evidently by electron transfer to gold
through the anchoring pyrroles. These findings agree with the
recent theoretical analysis of CoTPP on gold, which predicts
nearly 1 electron transferred to gold, almost entirely from the
anchoring pyrroles.27 In effect, through vibrational Stark tuning,
super-resolved TER-sm maps out polarization and submolec-
ular charge distributions. An example of such a map was
produced through KPFM using CO-terminated tips.28 There,
the force neutrality point as a function of applied potential is
used to map the intramolecular charge distribution. Here, a
normal mode of the targeted molecule is probed with the bare
tip, with spatial resolution more localized than the mode itself
(see Figure 2g).
Isolated Molecules on Terraces at 5 K. The governing
principles of TER-sm are tested through measurements on
isolated single molecules immobilized at 5 K on the Au(111)
substrate. The manipulation sequence on the flat terrace is
summarized in Figure 7a−c. In the scanned area, we see three
molecules, but TERS is silent. When the tip is placed on one of
the phenyl groups, we only see the electronic Raman
continuum of the tip, void of molecular lines (orange trace in
first panel). Upon pressing on the phenyl ring (Vb = −2 mV, I
= 4 nA), a rather complete vibrational spectrum emerges (blue
trace). The spectrum remains stationary as we translate the tip,
indicating a molecule snagged by the tip. After measuring the
retraction-dependent sequence of spectra (middle panel), we
repeat the same area scan (Figure 7b). The distorted image of
the remaining molecules confirms that the missing CoTPP
molecule is firmly attached to the tip apex. Upon applying a
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Figure 7. TER spectra upon transferring a CoTPP molecule to the
tip at 5 K. The common set point for topographic images (104 ×
104 Å2) is 0.1 nA and +0.485 V. (a) First image of the transfer
sequence. The Ag tip is placed on the phenyl ring denoted by the
asterisk (*). The TER spectrum appears upon approaching the
molecule by changing the set point from 1 nA, +0.485 V to 4 nA,
−2 mV, as demonstrated at the beginning of the spectral sequence
denoted by *, as well. (b) Image scanned after picking up a CoTPP
molecule. The disappearance of a molecule is marked by a dashed
circle. With molecule held at the tip apex, TER spectra are recorded
as the tip is incrementally retracted and brought back to the
tunneling position. (c) Image taken after dropping the CoTPP by
applying a −3 V pulse. In the process, the porphyrin is accidentally
exchanged with a CO molecule as identified by the TERS of C−O
stretch and enhanced resolution of the image. The landing position
is displaced from the position where the pulse was applied
(denoted by x), which shows the CoTPP was adsorbed slightly off
the apex and possibly tilted. (d) Gap dependences of two
vibrational peaks at 807 and 1517 cm−1, respectively. The peak
intensities are obtained by integrating over shaded windows in the
spectral sequence. The exponential fit to the decay of 808 cm−1
peak intensity yields 2.2 Å in decay length. (e) Simulated spectra
compared with the experimental retraction dependence.
voltage pulse, the molecule is dropped and verified to be the
intact CoTPP (Figure 7c). In this manipulation, the CoTPP
spectrum is replaced with the single vibrational line of CO at
2065 cm−1. Now the tip is terminated with a CO molecule,
which also explains the sharper contrast in topography than in
the case of the bare tip (compare Figure 7a and 7c). Several
observations are noteworthy about the gap dependence of the
spectra of the molecule attached to the tip apex. The entire
spectrum disappears upon 2.4 Å retraction (Figure 7d), even
though the molecule remains on the apex. While the vibration
localized on the phenyl rings at 807 cm−1 decays, the pyrrolic
mode at 1517 cm−1 increases in intensity during the first 1 Å
retraction, and both decay exponentially over the next ∼1 Å
retraction (Figure 7d). The mode-selective variation in
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intensity arises from the relative orientation of molecule to
the local field. In the simulated spectra (Figure 7e), we employ
a vertically oriented free CoTPP, and |E/∇E|< 0.2 Å. The field
gradients play the key role in this case, which again indicates
that the field gradients break the traditional Raman selection
rules. However, when the molecule is lifted away by a few
angstrom, TERS dramatically changes. A larger ratio of field
and field gradient reproduces the spectrum at 2.13 Å, indicating
that the field contribution becomes increasingly dominant
during the tip retraction.
Tensorial TER-sm on the Angstrom Scale. As illustrated
in Figure 7, molecules isolated on terraces cannot be imaged at
gap distances required to see the TERS signal. They are
displaced or picked up by the tip even at 5 K. In contrast,
CoTPP molecules at step edges are strongly bound and remain
stationary under harsh tunneling conditions (4 nA, −10 mV).
The stationary molecules allow the direct demonstration of the
spatial resolution in TER-sm governed by field gradients.
Measurements on molecules decorating a step edge are
presented in Figure 8. We zoom in on three phenyl groups
from two different molecules that straddle the edge (Figure
8a−c) and record hyperspectral images in constant height
mode, enabled by the stability of the junction at 5 K. The
spectra observed on the three phenyls are displayed in Figure
8e. The mode-specific map of the shaded spectral window in
Figure 8d shows all three phenyls (P1-3). The TERS signal on
P2 arises from a 1 Å × 1 Å area, localized on the right side of
the topographic image of P2 (see contour lines). The image of
P3, which is closer to the tip, is larger; accordingly, the TERS
signal arises from a somewhat larger area, ∼2 Å × 2 Å, now
localized on the left side of P3. The spatial resolution is atomic
in scale, and the excitation is tensorial; it depends on the
orientation of the molecule and confined field. Had we mapped
the modes at 1500 cm−1, only P3 would have been imaged.
This captures the excitement and challenge of vibrational
spectromicroscopy with atomistically confined light.
CONCLUSIONS
The reported measurements were selected to underscore the
promise of TER-sm as the chemist’s ultimate microscope. We
directly demonstrate that the method can yield vibrational
spectroscopy with angstrom-scale spatial resolution, signifi-
cantly sharper than the extent of molecular normal modes,
therefore at the ultimate limit of relevance to molecular matter.
We have shown that cavity spectra alone lead to imaging of
molecular structure with resolution comparable to that of STM.
Beyond structure, the inner workings of molecules are
accessible through vibrational Stark microscopy. Befitting a
chemist’s microscope, TER-sm provides structure, bond
strengths, and charge distributions with submolecular reso-
lution. In the specific example of CoTPP considered here, we
show that the saddling of the molecule on Au(111) is
accompanied by charge transfer through the pyrroles in contact
with the metal; the central cobalt atom does not participate in
the transfer, and the molecule and the surrounding gold atoms
are polarized.27
The exposition also highlights the challenges that must be
overcome to develop a quantitative tool with analytical utility.
Spectroscopy with confined light does not obey standard
selection rules. A propensity rule previously noted is the silence
of cold molecules that lie flat on metallic surfaces.40 Here, we
suggest that this arises from coupling to the SS. They can be
activated by lifting or tilting with the tip using large tunneling
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Figure 8. Hyperspectral imaging on the angstrom scale of CoTPP
molecules adsorbed at a step edge. (a) Topography of molecules
decorating a step edge (66 × 66 Å2). (b) Close-up of the area
marked by the yellow box in (a). White dashed lines trace two
CoTPP molecules that straddle the edge, with a pair of phenyls
each on upper and lower terraces (highlighted by black dashed
lines). (c) Close-up of the area indicated by the yellow oval in (b);
note the scale bar. The common imaging condition for (a−c) is 0.1
nA and +0.48 V. (d) Raman map of the same area as in (c)
recorded in constant height mode (4 nA, −10 mV). (e) Spectra
recorded on the three phenyl groups (P1, P2, and P3) of two
different molecules. The shaded band is the spectral window used
in the TERS map in (d).
currents near zero-bias, and more interestingly, the spectra can
be activated by the introduction of a TERS-invisible mobile 2D
gas. In the present case, rather complete and sharp vibrational
spectra of individual CoTPP molecules have been obtained,
with high S/N ratio. Nevertheless, spectral interpretations are
nontrivial as multipolar scattering driven by field gradients
dominates spectroscopy with confined light. In the absence of
orientational averaging, the tensorial nature of scattering makes
it sensitive to 3D orientation of the targeted sample and the
cavity-confined fields.41 These are ultimately advantages, given
atomistically characterized and controlled junctions. It may be
11472
Article
recognized that with simple molecular reporters attached to a
substrate, TERS may be used to characterize tip morphology.
Alternatively, with a simple reporter molecule attached to the
tip, TERS of the tip terminus can be used to probe molecular
matter. The CO-terminated tip, which we encountered here, is
particularly valuable in this regard because it can act as a
transducer of electrostatic forces with atomic resolution, as
already demonstrated in our validation of TERS-bright silver
tips.42 Quite clearly, image quality and resolution will be
directly related to the signal strength and acquisition speed, and
significant improvement over the present can be expected
through tip-enhanced stimulated Raman spectroscopy, as
already demonstrated in related work.43
METHODS
The instrumentation used in the current studies has been described
previously.40 We use a cryogenic, ultrahigh vacuum STM equipped
with a parabolic collector mounted on a piezoelectric stack. The focus
of the parabola can be precisely centered on the tip apex by imaging
electroluminescence (EL) and modeling the image obtained through
the train of optical elements.40 The laser excitation is focused through
an aspheric lens (focal length = 79 mm) at 45° incidence angle with an
estimated spot size of ∼10 μm. The Raman spectra are recorded using
continuous wave diode lasers, at 532 or 634 nm, with a typical
intensity of 5 μW/μm2 delivered at the sample. The principle advance
that has allowed us to obtain reproducible TERS results is the
fabrication of sharp silver tips with nanoscopically smooth surfaces, as
recently described.42 After electrochemically etching and polishing tips
with an automated setup,44 we use field-directed sputter sharpening as
the final process. A detailed description of the procedure has been
reported.42 A good indicator of the formation of junction cavities is the
observation of gap-dependent shift in the EL spectra,45 and this
criterion is used to establish the TERS utility of a tip when reshaped
through field emission. The fine-tuning of the cavity is accomplished in
operando, while monitoring the electronic Raman scattering
continuum of the junction. TERS requires alignment of the cavity
window with the Stokes scattering range. Either the broad resonance
of the cavity window is moved toward the Stokes window or the color
of the laser is chosen to match it. In the present case, the excitation
wavelength was shifted from 532 nm, where no signal could be seen
despite the Q-band electronic resonance of CoTPP (see Figure S2 in
the Supporting Information), to 634 nm to match with the cavity
window.
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acsnano.7b06183.
Optimized geometry of CoTPP on Au(111); absorption
spectrum of CoTPP; mode-specific maps of all nine
vibrations seen at room temperature; raw images
recorded at room temperature; theoretical model of the
TERS junction; simulation of TERS spectra in the
dressed tensor formalism, junction resonance, field
profile, and gap dependence of field strengths (Figure
S5); raw images acquired at 80 K; field gradient driven
spectra (Figure S7); multipolar decomposition of Raman
scattering spectra (Figure S8); CO binding energies to
CoTPP and predicted orientations of CoTPP and
bicarbonyl CoTPP molecules at 80 K (PDF)
AUTHOR INFORMATION
Corresponding Authors
*E-mail: jensen@chem.psu.edu.
*E-mail: aapkaria@uci.edu.
DOI: 10.1021/acsnano.7b06183
ACS Nano 2017, 11, 11466−11474
ACS Nano
ORCID
Joonhee Lee: 0000-0003-4685-3511
Lasse Jensen: 0000-0003-1237-5021
Vartkess Ara Apkarian: 0000-0002-7648-5230
Author Contributions
J.L. and N.T. equally contributed to the experimental effort.
X.C. and P.L. carried out the modeling of the junctions and the
TERS calculations. V.A.A. and L.J. conceived and coordinated
the work and authored the paper with input from all co-authors.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
This research was supported by the grant of NSF Center for
Chemical Innovation dedicated to Chemistry at the Space-
Time Limit (CHE-1414466). We gratefully acknowledge Dr.
Laura Rios for her measurements of the porphyrin absorption
spectrum, and Prof. Everly Fleischer for many stimulating
discussions and for donating his collection of metalloporphyr-
ins. The cryo-UHV STM was constructed under Prof. W. Ho’s
supervision. Portions of this work were conducted with
Advanced CyberInfrastructure computational resources pro-
vided by The Institute for CyberScience at The Pennsylvania
State University (http://ics.psu.edu).
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11474 DOI: 10.1021/acsnano.7b06183

ACS Nano 2017, 11, 11466−11474