PHYSICAL REVIEW MATERIALS 3, 060401(R) (2019)

Rapid Communications

Jahn-Teller reconstructed surface of the doped manganites shown by means

of surface-enhanced Raman spectroscopy

S. Merten,* V. Bruchmann-Bamberg, B. Damaschke, K. Samwer, and V. Moshnyaga

I. Physikalisches Institut, Georg-August-Universität Göttingen, Friedrich-Hund-Platz 1, D-37077 Göttingen, Germany

(Received 20 November 2018; revised manuscript received 30 April 2019; published 28 June 2019)

We report direct evidence of the theoretically predicted electron-rich surface of doped perovskite manganites
La0.7 A0.3 MnO3 (A = Ca, Sr) by means of surface-enhanced Raman spectroscopy. The required Au nanoparticles
were grown on top of thin manganite films by the metalorganic aerosol deposition technique, which provides
a stable oxygen atmosphere and prevents deoxygenation effects. The acquired surface-enhanced Raman
spectra of rhombohedral La0.7 Sr 0.3 MnO3 thin films reveal the symmetry-forbidden Jahn-Teller stretching modes
demonstrating the predicted symmetry breaking at the surface and fallback into the orthorhombic (Pnma)
structure. This results in a unique Jahn-Teller reconstructed surface structure, which limits the capabilities of
mixed-valence manganites in spintronic applications, but will be highly favorable for catalytic reactions.

DOI: 10.1103/PhysRevMaterials.3.060401

I. INTRODUCTION surface was observed by conducting atomic force microscopy

[18,19] in La0.7 Ca0.3 MnO3 and by x-ray magnetic circular
Mixed-valence perovskite manganites, such as
dichroism (XMCD) [20] as well as by x-ray resonant mag-
La1−x Ax MnO3 (A = Sr, Ca), possess strong electron-spin-
netic scattering (XRMS) [21,22] on La0.7 Sr 0.3 MnO3 and the
lattice correlations [1,2], which result in many fundamentally
layered compound La2−2x Sr 1+2x Mn2 O7 . Segregation effects,
interesting and useful electronic properties. Some of them,
which are well known in manganite thin films [23,24], lower
such as a high degree of spin polarization [3] and a
the effective doping at the surface and can result in the recon-
high catalytic activity [4], make manganites promising
struction of the surface layer, forming a Ruddleson-Popper-
materials for many future applications, such as tunneling
like phase [25] or in a change of the manganese valence, as
magnetoresistance (TMR) devices [5] or solid oxide fuel cells
shown in La1−x Pbx MnO3 [26]. In the latter case, the valence
[6]. Therefore, a detailed knowledge of the surface structure
change was attributed to the possible higher oxidation states
is of crucial importance, as the electronic surface structure
of Pb, compared to Sr or Ca. These extrinsic segregation
determines the catalytic and fuel cell performance as well as
effects are related to oxygen deficiencies and thus depend on
the spin polarization at the TMR interface.
the growth conditions, i.e., temperature and oxygen partial
Numerous theoretical studies have aimed at the under-
pressure [27,28]. They provide a serious obstacle for the study
standing of the differently oriented LaMnO3 surfaces [7,8],
of manganite surfaces, since they alter the surface chemistry
the (001) surface of CaMnO3 [9,10], and the surface of the
significantly and, sometimes, in an irreversible way. As a re-
hole-doped La1−x Ax MnO3 (A = Ca, Sr) [11–14]. The alter-
sult, despite an enormous experimental effort, the theoretical
ations at the surface compared to the bulk structure range
predictions have yet to be proven and a mature picture of the
from large surface rumpling [7,8,13–15], over a spin flip in
surface nature is missing.
the surface layer [8,12] to a charge transfer from the bulk to
Over the last 20 years, Raman spectroscopy was estab-
the surface [11,13,14]. The latter results in the formation of
lished as a powerful tool to study correlated materials [29],
a nonmagnetic, most likely canted antiferromagnetic, insulat-
including mixed-valence manganites [30–32]. Numerous Ra-
ing Mn3+ -rich layer at the surface. Coaxial impact-collision
man studies engaged in the correlation of the observed Ra-
ion scattering spectroscopy on La0.7 Sr 0.3 MnO3 revealed a
man modes to the presence of Jahn-Teller (JT) distortions
MnO2 -terminated (001) surface [16]. Photoemission studies
in the manganite system [33,34] as well as in their rela-
of La0.7 Ca0.3 MnO3 and La0.9 Ca0.1 MnO3 showed further that
tion to the metal-insulator and ferromagnetic-paramagnetic
the surface termination depends also on the doping, changing
phase transition [31,33]. In the Raman spectra, these JT
from a MnO2 to a (La,Ca)O termination with decreasing x
distortions, which are inherent for the orthorhombic (Pnma)
[17]. A nonmagnetic and insulating layer at the manganite
structure of the lightly doped manganites (x < 0.5), are rep-
resented by two high-frequency stretching modes at 490
and 611 cm−1 [31,33]. In rhombohedral La0.7 Sr 0.3 MnO3 , in
*
Corresponding author: smerten@gwdg.de turn, these modes are forbidden [32,35,36], and instead the
Raman spectra are dominated by a sharp bending mode at
Published by the American Physical Society under the terms of the 442 cm−1 . Therefore, the appearance of the JT modes can
Creative Commons Attribution 4.0 International license. Further be used as a fingerprint of the lattice structure of the man-
distribution of this work must maintain attribution to the author(s) ganite film. Unique Raman techniques to probe the surface
and the published article’s title, journal citation, and DOI. structure of manganites or other correlated oxides could be

2475-9953/2019/3(6)/060401(8) 060401-1 Published by the American Physical Society

S. MERTEN et al. PHYSICAL REVIEW MATERIALS 3, 060401(R) (2019)

tip-enhanced (TERS) and/or surface-enhanced Raman spec- III. RESULTS AND DISCUSSION
troscopy (SERS), which both exploit the excitation of surface
Structural, electrical, and magnetic characterization of thin
plasmons in metallic nanostructures to enhance the Raman
LCMO and LSMO films are shown in Figs. S1.1– S1.4
signal from nearby adsorbates [37]. The strongly localized
in the Supplemental Material (SM) SM I [45] demonstrat-
character of the surface plasmon, i.e., its electric field E (r)SP
ing the high quality of our thin manganite films. The esti-
scales with 1/r 3 , limits the probing area down to a few
nanometers (dSP ≈ 4–5 nm) [38,39], making the study of mated pseudocubic lattice constants, aLCMO = 3.867 Å and
the manganite surface by means of Raman spectroscopy in aLSMO = 3.882 Å, are very close to the corresponding bulk
principle possible. However, up to now only a few studies values [46,47] indicating a strain-free state of the man-
were performed on oxides, mostly focused on nanoparticles ganite films on MgO(100). Electrical and magnetic mea-
rather than thin films [40–42]. Moreover, to the best of our surements reveal a coupled ferromagnetic-paramagnetic and
knowledge, only one TERS study on a strongly correlated metal-insulator transition, TMI = TC = 267 K, for LCMO and
material, the double perovskite La2 CoMnO6 [43], was pub- a ferromagnetic-paramagnetic transition, TC = 364 K, and
lished, but no surface-oriented studies of the mixed-valence metal-metal transition, TMM = 343 K, for LSMO. After the
manganites, La1−x Ax MnO3 , were reported up to now. deposition of the Au layer, the structural, electrical, and
In this Rapid Communication, we present a SERS study on magnetic properties of our manganite films did not change.
thin La0.7 Ca0.3 MnO3 (LCMO) and La0.7 Sr 0.3 MnO3 (LSMO) This is in line with density functional theory calculations
films. While the surface Raman spectra of LCMO are en- [48] and x-ray photoemission spectroscopy measurements
hanced but congruent, the surface of LSMO reveals the [49] showing no chemical interaction between an Au layer
dominance of two Jahn-Teller-like Raman modes. This gives and the manganite surface. However, Brivio et al. observed a
evidence for the presence of the cooperative JT effect due drastic decrease of the Curie temperature for ultrathin films
to the symmetry-breaking-induced electron enrichment at the with a thickness less than 8 nm [50]. They attributed the
LSMO surface. observed decrease of TC by ≈150 K for a 4-nm-thick LSMO
film to deoxygenation effects during the deposition of the Au
layer. Oxygen vacancies, strongly affecting the properties of
the manganites [51], are a well-known problem in common
II. EXPERIMENTAL TECHNIQUES thin-film deposition techniques using ultrahigh vacuum, e.g.,
LSMO and LCMO films have been grown by a metalor- pulsed laser deposition. However, the high partial oxygen
ganic aerosol deposition (MAD) technique [44] on MgO(100) pressure, p(O2 ) ≈ 0.2 bar, within the MAD prevents or at
substrates (Crystal GmbH). Acetylacetonates of La, Sr, Ca, least minimizes the formation of oxygen vacancies during
and Mn were used as precursors. The films were grown the deposition. This is supported by annealing experiments
at a substrate temperature Tsub = 950 ◦ C with a growth rate done on MAD-grown Ruddleson-Popper SrO(SrTiO3 )n het-
v = 10 nm/min and cooled down to room temperature in erostructures [52]. To verify the stability of our films with
15 min. The gold nanoparticles (Au-NPs) were subsequently respect to deoxygenation effects caused by the Au deposition,
deposited by MAD at Tsub = 550–570 ◦ C, using a gold(III) we prepared an ultrathin LSMO film, d = 12 u.c. (≈4.6 nm),
acetate precursor (Alfa Aesar, 99.9%) dissolved in dimethyl- on a TiO2 -terminated STO(100) substrate. Since the thick-
formamide to a concentration c = 0.02 M. The solution with ness is much smaller than 8 nm, one could expect a strong
a volume V = 1 ml was sprayed onto the manganite film reduction of the TC and TMM , because of deoxygenation. As
with a deposition rate v = 0.011 ml/s. Finally, the prepared one can see in Fig. 1, only minimal changes of the transition
Au-NP/LS(C)MO/MgO(100) samples were cooled down to temperatures, TC = 3 K and TMM = 7 K, occur, compared
room temperature in 10 min. X-ray diffraction in -2 to the huge decrease in previous works [50,53]. Therefore, de-
Bragg-Brentano geometry with Cu Kα radiation and small- oxygenation effects are negligible in our films. SEM images
angle x-ray reflectivity measurements were performed to char- of the manganite surface show a homogeneous formation of
acterize the structure and thickness of the films. Magnetic Au-NPs without any indication of clustering. Nevertheless,
(Magnetic Property Measurement System, Quantum Design) the particle size is distributed over a rather broad range with
and electrical four-probe characterizations (Physical Property a mean particle size dNP = 15–16 nm [see Fig. 1(d)], as
Measurement System, Quantum Design) were carried out for it is common for a self-aggregated growth of nanoparticles
temperatures T = 5–400 K. The morphology and size of the [54]. The reflectance of the studied Au-NP/manganite films
Au-NPs were characterized via scanning electron microscopy shows a surface plasmon resonance (SPR) around λSPR =
(SEM, Leo Supra 35). A four-lens optical reflection setup 592–606 nm, indicated by the broad reflectance peak [45,55]
under normal incidence, combined with a UV-VIS spec- seen in Fig. 1(c).
trometer (Maya 2000Pro USB, Ocean Optics), was used to In Fig. 2(a), the Raman spectra of thin LCMO films at room
determine the wavelength of the surface plasmon resonance temperature are shown. A detailed explanation of the process-
λSPR . The Raman spectra were acquired in a backscattering ing of the raw Raman spectra is given in SM II [45]. The
geometry with a confocal Raman microscope (LabRAM HR spectra are dominated by a rotational mode at 228 cm−1 (A1g )
Evolution, Horiba Jobin Yvon) equipped with a thermoelec- and by the two broad JT stretching modes: antistretching at
trically cooled charge-coupled device of 1024 × 256 pixels. 499 cm−1 (as-JT, A1g ) and stretching at 609 cm−1 (s-JT, B2g ),
A continuous-wave HeNe laser, λ = 632.8 nm, with a spot respectively [30,33,34]. One can also see a small contribution
size of d < 1 μm, was used and the laser power at the surface of the bending mode at 438 cm−1 (B2g ). The remaining modes
was kept at P0 = 0.65 mW during the measurement. at 343 cm−1 (B2g ) and 438 cm−1 (A1g ) can be also assigned to

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FIG. 1. (a) Electrical and (b) magnetic characterization of the ultrathin LSMO film (d = 12 u.c.). Slight changes of the magnetic
and electric transition temperatures infer negligible deoxygenation effects (black: LSMO; red: Au/LSMO). Reflectance measurements
(c) provide a SPR wavelength λSPR = 606 nm for LCMO (black) and λSPR = 592 nm for LSMO (red), respectively. SEM pictures of an
exemplary Au/manganite structure show the formation of Au-NPs with a mean particle size, dNP ≈ 15–16 nm, obtained from the particle size
distribution (d).

the orthorhombic structure [33]. However, since the bending (Eg ), whose positions are consistent with previous observa-
mode and the JT modes play an important role in the metal- tions [32,58] and lattice dynamical calculations [35]. Addi-
insulator transition [30,56] and the rotational mode is sensitive tionally, weak contributions of the “orthorhombic” modes at
to structural changes, e.g., octahedral tilting due to doping 331 and 396 cm−1 and the JT modes at 470 and 630 cm−1 can
[57], the focus in the following discussion will be on these be seen. Since these modes are forbidden in the rhombohedral
four modes. A direct comparison of the “bulk” Raman spectra structure of LSMO [35,36], we assign their appearance in
and the surface-enhanced Raman (SER) spectra of LCMO the bulk spectra to a small orthorhombic distortion at the
reveals only slight differences, i.e., an enhancement of the film/substrate interface, which is in agreement with previ-
spectra and a peak shift of the rotational mode as well as of the ous results [45,59,60]. The huge strain induced by the large
JT stretching modes. Furthermore, an additional mode around mismatch between the MgO(100) substrate (aMgO = 4.209 Å
568 cm−1 is observable [see Fig. 2(c)]. A simple approach to [47]) and LSMO (abulk = 3.889 Å [46]) is released by the
quantify the enhancement is to calculate the intensity contrast, formation of misfit dislocations, located within the first ≈2 nm
C = ISERS /IRS , with ISERS as SER and IRS as normal Raman from the interface [47,61]. After this defect- and strain-rich
intensity. The obtained intensity contrasts are summarized in region, the film grows unstrained and almost defect free [61]
Table I. Remarkably, both stretching modes have a different with a pseudocubic lattice constant, afilm = 3.882 Å, which is
sign of peak shift ω = ωSERS − ωRS : a blueshift for the almost identical to the bulk value. These misfit dislocations
as-JT mode and a redshift for the s-JT mode. are responsible for the observed orthorhombic distortions.
In contrast to LCMO, the most prominent features in the Additionally, a broad hump centered around 515 cm−1 is
“bulk” Raman spectra of LSMO [Fig. 2(b)] are the rotational clearly seen in the bulk spectra of LSMO and corresponds
mode at 178 cm−1 (A1g ) and the bending mode at 422 cm−1 to an collective plasmalike excitation [62]. The SER spectra

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S. MERTEN et al. PHYSICAL REVIEW MATERIALS 3, 060401(R) (2019)

FIG. 2. Comparison between the “bulk” Raman spectra of (a) LCMO and (b) LSMO and (c), (d) their corresponding SER spectra. For
LCMO (c), the Au-NP deposition results in an enhancement of the Raman spectra and an additional mode around 568 cm−1 . The SER spectra
of LSMO (d) show an moderate enhancement of the rotational and bending mode as well as the strong enhancement of the JT modes at 477
and 616 cm−1 , indicating a Jahn-Teller distorted surface structure.

of LSMO, shown in Fig. 2(d), reveal an additional mode in doped manganites with a hole concentration x = 0.3.
at 551 cm−1 and a strong enhancement of the JT modes at As a consequence, the crystal structure changes from the
477and 616 cm−1 , compared to the relatively weak enhance- rhombohedral (R3c) in the bulk to the orthorhombic (Pnma)
ment of the rotational and bending mode (see Table I). How- structure at the surface [14]. Since the JT modes are allowed
ever, this strong intensity enhancement cannot be attributed in this structure, the enrichment of the JT-active Mn3+ ion and
to an enhancement of the film/substrate interface, since the the lowering of the symmetry should lead to the appearance
electric field of the surface plasmon decays strongly within the of the JT modes within the insulating surface layer. Such
film. Considering the thickness of the film, dfilm = 89 nm, and a symmetry lowering cannot occur in an orthorhombic
the distance dependence of the plasmonic enhancement [38], system, since it already resides in the low-symmetric stable
I ∝ 1/r −10 , the intensity enhancement at the interface would structure, predicted by the tolerance factor for perovskite
be of the order of 10−8 compared to that of the surface. Hence, oxides [64]. This is supported by theoretical calculations
the observed enhancement of the JT modes in the SER spectra on orthorhombic LaMnO3 [8] and CaMnO3 [9,10] and in
of LSMO is certainly a surface phenomenon. This is further good agreement with the observed enhancement in our SER
supported by the observed peak shift of the JT modes. The spectra of LCMO. Chemical effects such as segregation of
absence of bonding partners at the surface causes a deviation the dopant [23–25,28] are well known for doped manganites.
of the Mn-O bond length dMn-O [14], which will be reflected However, since segregation is favored by a low oxygen partial
in the vibrational frequency. However, the redshift of the s-JT pressure [28], these effects should be suppressed due to the
mode in LCMO indicates a smaller dMn-O , but the blueshift high p(O2 ) provided by the MAD. An enrichment of Sr/Ca
of the as-JT mode a larger dMn-O [63]. Similar considerations at the surface would further result in a higher effective doping
apply to LSMO, but here the JT modes are related to the at the surface, leading thus to a reduction of the JT modes
film/substrate interface and not the bulk structure. The dif- [65] and not an enhancement. Another possible explanation
ferent sign of the peak shift suggests an asymmetric change for the appearance of the JT-like modes at the LSMO surface
of dMn-O favoring the asymmetric stretching of the in-plane is the Au-NP deposition itself. X-ray absorption spectroscopy
oxygen in LCMO, but the symmetric stretching in LSMO. on LSMO (d = 40 nm) with an Au-capping layer (d = 2 nm)
The appearance of the JT-like modes at the LSMO revealed the presence of Mn2+ at the interface between the
surface could be caused by different processes: A charge film and capping layer [66]. Additionally, the deposition of
transfer from the bulk to the surface [11] would lead to the Au-NPs onto the surface creates an interface between the gold
formation of an insulating Mn3+ -rich layer at the surface and the manganite surface, which could cause the observed
symmetry breaking. However, the formation of Mn2+ as well
TABLE I. Intensity contrasts obtained for the different modes of as the artificially created symmetry breaking would impact
LCMO and LSMO. the Mn3+ /Mn4+ ratio and thus result in a decrease of the
transition temperature. As mentioned before, even an ultrathin
Rotational Bending as-JT s-JT film does not show any significant changes of its properties
LCMO 3.75 1.5 3.15 4.34 after the Au-NP deposition. Therefore, the formation of Mn2+
LSMO 7.35 7 34.64 30.52 or an artificially induced symmetry breaking caused by the
Au-NP deposition is unlikely. Hence, the JT-like modes have

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FIG. 3. (a) Bulk and (b) SER spectra of CaMnO3 reveal no Jahn-Teller-related Raman modes, supporting the authenticity of our LSMO
spectra and the appearance of the Jahn-Teller stretching mode.

to be an intrinsic electronic surface phenomenon or they are Table I). By keeping in mind the strong distance dependence
related to the Au-NPs themselves. of the plasmonic enhancement [38], the significantly higher
To verify the authenticity of the appearing JT-like modes contrast of the JT modes in comparison to the bending mode
at the LSMO surface and to exclude effects caused by the can be directly linked to a stronger surface contribution of
Au-NPs themselves, we have grown orthorhombic CaMnO3 them. Hence, the bending mode can be considered as a bulk
thin films on the lattice-matched LaAlO3 (100) substrates mode and can be taken to estimate the thickness of the Jahn-
(see Fig. 1.5 in SM I [45] for plasmonic characterization). Teller distorted surface layer. The treatment as a bulk mode is
CaMnO3 shows a 60 times smaller JT distortion than the further supported by its negligible peak shift, which would be
orthorhombic LaMnO3 and does not feature any Jahn-Teller- expected from an undisturbed structure. Using the simplified
related Raman modes [Fig. 3(a)] [67]. Slab calculations of sphere model and the |E |4 approximation, the SER intensity
the CaMnO3 surface predict only a possible change of the scales with [38]
magnetic order [9,10], but no electronic or structural recon-
ISERS ∼ [(1 + r/a)]−10 , (1)
struction, which could cause a stronger JT distortion. As one
can see in Fig. 3(b), there are no additional JT-like modes with ISERS the SER intensity of the Raman mode, a the radius
present in the SER spectra of CaMnO3 . This verifies the of curvature of the field enhancing feature of the metallic
authenticity of the observed JT-like modes in the SER spectra surface, and r the distance from the metallic surface to the ad-
of LSMO and excludes their appearance caused by the Au- sorbate. Assuming the radius of curvature is given by the mean
NPs themselves [68]. However, as in LCMO and LSMO, an particle size dNP ≈ 16 nm, Eq. (1) yields the distance depen-
additional mode at 545 cm−1 is clearly visible in the SER dence shown in Fig. 4. Since we consider the bending mode as
spectra of CaMnO3 and likely will be of similar origin as the a bulk mode, the ratio η = Cbend /CJT represents the weakening
additional surface mode in LCMO and LSMO. of the plasmonic enhancement within the whole distorted sur-
Hence, we can conclude that the strong enhancement of the face layer. To estimate the thickness of the surface layer, one
JT-like modes has to be an intrinsic surface phenomenon of compares the determined ratio with the distance dependence
the LSMO surface and that they can indeed be assigned to the in Fig. 4. For LSMO, the determined ratio η ≈ 7/31 yields a
JT stretching vibrations, which are inherent to the orthorhom- thickness of the surface layer, dJT ≈ 7 u.c. ≈ 2.8 nm. Similar
bic (Pnma) structure of the lightly doped manganites. Note considerations for the modes of LCMO yield a significantly
that we assume a MnO2 -terminated surface of our manganite smaller thickness dJT ≈ 4–5 u.c. ≈ 1.7–2.0 nm. Both values
films as observed in previous works [16,17]. But, since the correspond well to the thicknesses of the insulating antiferro-
surface termination of the studied films is unknown, one has magnetic surface layer obtained from XMCD [20] and XRMS
to keep in mind that a different termination of the manganite [22]. The inset in Fig. 4 summarizes the proposed model of
surface could lead to an alternative surface reconstruction the manganite surface. Note that the intensity contrast of the
and thus to the suppression of the JT modes. Nonetheless, rotational mode in LSMO is only slightly higher than the
we can experimentally confirm herewith the theoretically contrast of the bending mode, indicating a rather bulk-related
predicted symmetry lowering at the manganite surface and than surface-related nature. In LCMO, however, the intensity
the formation of an electron-rich JT distorted surface layer contrast is similar to those of the JT modes and thus will be
in the ferromagnetic metallic LSMO as well as the electron associated with the surface structure. As mentioned before,
enrichment at the surface of the orthorhombic LCMO. this mode is sensitive to the tilting of the MnO6 octahedron,
To model the surface structure of LSMO and LCMO, we so that its blueshift suggests a change of the octahedral tilting
compared the intensity contrast of the different modes (see near the surface. However, both manganite systems show

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FIG. 4. The modeled (a) LSMO and (b) LCMO surface structure, determined from the distance dependence of the electromagnetic
enhancement due to the plasmonic excitation in the Au-NPs.

a comparable peak shift and therefore a similar octahedral IV. CONCLUSION

tilting. Considering that a structural transition occurs at the
We have studied the surface structure of the mixed-valence
LSMO surface, this is quite remarkable and, in combination
perovskite manganites by means of SERS. The SER spectra
with the slightly higher contrast of the rotational mode, hints
reveal an electron-rich surface structure, which is manifested
at the presence of an intermediate layer, which accommodates
by the dominance of the JT stretching modes. The strong
the structural transition at the surface.
enhancement of the JT modes in LSMO was attributed to
Finally, we want to discuss the assignment of the additional
a structural transition to the orthorhombic (Pnma) structure
mode around 550–570 cm−1 . Compared to theoretical calcu-
at the surface, which results in a unique surface structure.
lations [33,67], the closest mode would be the out-of-phase
This is a direct experimental confirmation of the theoretically
stretching mode at 536 cm−1 in CaMnO3 and 575 cm−1
predicted surface of the doped manganite with x = 0.3. The
in LaMnO3 of B1g symmetry, respectively. Although, our
authenticity of our SERS results obtained for the rhombohe-
backscattering geometry only allows the detection of the
dral LSMO is supported by the SER spectra of orthorhombic
A1g and B2g modes, one can imagine that the symmetry
LCMO and CMO.
breaking at the surface and the rearrangement of the MnO6
octahedron could result in a structural distortion at the surface
ACKNOWLEDGMENT
allowing the observation of B1g modes. Further studies, espe-
cially from the theoretical point of view, could give insight The authors acknowledge financial support from the
into the origin of the additional mode and our proposed Deutsche Forschungsgemeinschaft (DFG) via SFB 1073 (TP
assignment. B04, B01 and A02).

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