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X-ray diffraction analysis and orientation contrast scanning electron microscopy imaging of La0.7Sr0.3MnO3
epitaxial layers grown on (001)-SrTiO3 substrates have been used to track the shear strain and twin domain
period as a function of the thickness of the films, t. To this end, the diffraction by a periodically modulated
twinned structure is analyzed in detail. In contrast with current equilibrium models, here we demonstrate
the occurrence of a critical thickness, tt y 2.0–2.5 nm, for twin formation in rhombohedral perovskite films.
The absence of twinning below tt is explained by the formation of a monoclinic interfacial phase
presumably driven by electronic interactions between film and substrate not taken into account in
theoretical models. Above tt, twin domains develop concomitantly with the build-up of misfit shear strains
associated with the formation of the rhombohedral structure. At a thickness y10 nm, the in-plane and
out-of-plane shear strain components exhibit similar values, as imposed by the rhombohedral symmetry.
However, upon increasing the film thickness, both strain components are found to follow divergent
Received 15th January 2013,
Accepted 8th March 2013
trajectories indicating a progressive perturbation of the octahedral framework which allows the in-plane
lattice parameters to remain fully strained within the explored thickness range (up to 475 nm). Despite
DOI: 10.1039/c3ce40085a
these structural perturbations, the twin size follows a t1/2 dependence as predicted for homogeneous films
www.rsc.org/crystengcomm by equilibrium models.
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formation in epitaxial films is the accommodation of the shear formation of the magnetically dead layer.18 Above tt, the fully
misfit strain. in-plane strained rhombohedral phase condenses at y10 nm.
It is well established that in free-standing thin films the Above this thickness up to 475 nm the in-plane and
domain period grows as the square root of the film perpendicular shear strain components evolve independently
thickness.10 This implies a rapid increase of the number indicating a progressive departure from the rhombohedral
density of domains at small film thicknesses, i.e. when the size symmetry. Despite this behavior, however, the thickness
of the device is within the nanoscale. The potential of domain dependence of the twin domain period follows a t1/2 law as
structures for elastic energy relaxation in epitaxial films was theoretically predicted for homogeneous epitaxial films.
first recognized in 1976 by Roitburd,11 and since then
numerous theoretical works have focused on the determina-
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elastically strained epitaxial films. At variance with lattice 475 nm were grown by RF magnetron sputtering from a LSMO
parameter misfit relaxation by interfacial dislocations, which stoichiometric ceramic target. Substrates were treated before
is associated with a critical thickness above which the stored deposition in order to obtain clean and smooth surfaces with a
elastic energy overwhelms the dislocation array formation single TiO2 atomic termination. The process includes a
energy,12 in rhombohedral films there is no critical thickness cleaning stage in an ultrasonic bath with milliQ water and
for domain formation.9,13 However, at the interface, coherence annealing at 1000 uC in air for 2 h. After annealing, the
with the cubic substrate prevents the development of eigen- substrate morphology exhibited the typical morphology of
strains (stress free self-strains) associated with the sponta- terraces and steps with a height corresponding to the STO unit
neous symmetry reduction of the film upon the ferroelastic cell (a y 0.4 nm). Deposition was performed at 900 uC in an
transition. As a result, an exponential decay of the domain oxygen pressure p = 0.19 mbar. The films were in situ annealed
period is predicted below a characteristic length Dt = EW/Gx2 at 900 uC at an oxygen pressure of 466 mbar for 1 h to improve
where EW is the domain wall energy, G is the shear modulus their magnetic and structural properties.20 The surface
and x is the shear mismatch strain between the rhombohedral morphology was characterized by Atomic Force Microscopy
domains and the cubic substrate. An estimation gives Dt y 3 (AFM) working in tapping mode (Molecular Imaging PicoSPM
nm for LSMO/STO.9 and Cervantes from Nanotec Electronica).
A critical point in modeling epitaxial domain configura- Film thicknesses were determined by X-ray reflectometry.
tions appears to be the definition of the actual interface The structure of the films was systematically investigated by
structure, i.e. the mechanisms governing the structural high resolution X-ray diffraction (XRD) using a diffractometer
coherence. In these models interfacial strains associated with equipped with a four angle goniometer and a conventional Cu
domain development are relaxed by the introduction of virtual tube, and primary optics consisting of a parabolic mirror and a
arrays of interfacial dislocations (so-called coherency defect 4 6 Ge(220) crystal asymmetric monochromator (X’Pert Pro
approach14), while the conventional lattice parameter misfit MRD-Panalytical, Almelo, the Netherlands). The lateral (in-
strain is allowed to relax by classical interfacial dislocation plane) correlation of the twin structure was determined either
mechanisms. Octahedral frameworks of correlated oxides like by reciprocal space mapping around of 00L reflections (taking
LSMO exhibit, however, inherent octahedral tilting15 and the z-axis as the direction perpendicular to the film), or by
electronic16,17 degrees of freedom that provide efficient strain performing Qx horizontal scans along a direction parallel to
relaxation at a lower energy cost than dislocation mechan- the [100] in-plane substrate axis, at Qz values corresponding to
isms.18 Electronic degrees of freedom become particularly the 00L (L = 1, 2, 3) LSMO reflections (as referred to the
relevant at the LSMO–STO interface owing to the need to pseudocubic perovskite cell). In-plane 2h/v 2 w area scans
cancel its polar discontinuity17 and the potential influence of were measured in the same XRD equipment around different
the Mn oxidation state and selective orbital occupancy19 on the HK0 reflections by using a non-monochromatic primary beam
in-plane dimensions of the unit cell.18 Altogether, such effects with an incidence angle of 0.5u, and a parallel plate collimator
draw a radically new misfit relaxation scenario that easily of 0.27u acceptance angle for the in-plane diffracted beam. The
bypasses energetically costly plastic deformation mechanisms. structure of the thinnest films was determined using a 6 circle
In this work we have grown LSMO films on STO substrates diffractometer at the BM25 (SpLine) at the European
and followed the evolution of the shear strain from the early Synchrotron Radiation Facility (ESRF), with an incident energy
stages of strain relaxation up to 475 nm. In contrast with E = 14.5 keV (l = 0.856 Å) and a fixed incidence angle of 0.5u
theoretical predictions, we determine a critical thickness, tt, slightly above the critical angle of 0.2u. High temperature
for twin formation at y2.5 nm. The critical thickness results diffraction experiments on 003 LSMO reflections were carried
from a charge enrichment driven monoclinic distortion which out on one of the thick samples (120 nm) up to 850 uC in air
cancels the shear component of the misfit strain.18 This atmosphere in order to investigate the temperature depen-
interfacial electronic and structural transformation suppresses dence of twin domain tilt by using a DHS1100 non-ambient
the ferromagnetic order and appears intimately related to the chamber (Anton Paar GmbH, Graz, Austria). Twin patterns
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Fig. 3 (a) Reciprocal space maps of different H03 reflections (H = 0, 1, 2, 3) for a 475 nm thick film with equal probability of biaxial twinning parallel to [100] and [010]
directions. Note that splitting along Qz is proportional to the H value, while along Qx is constant for all L = 3 reflections. (b) Corresponding reconstruction of the
reciprocal space. A/A9 twin domains (with common (100) twin plane) produces a splitting of their corresponding H0L reflections (only 003 and 303, for simplicity)
along Qx (independent of H value), while maintaining Qy and Qz values of the undistorted primitive cell, indicated by the small black spots. Their corresponding 0KL
reflections are also split in Qx (not in Qy) and shifted in Qz proportional to the K value and sign (showing a single common 033 reflection). All together the coexistence
of even amounts of the eight A/A9, B/B9 C/C9 and D/D9 twin domains define six different H0L reflections split in Qx, Qy and Qz, as shown in the scheme on the right
panel (five reflections for 303 because of the coincidence of 033A and 033A9). The inset illustrates the relation between Bragg splitting and the shear strain
components wi along the three main directions. Note that w3 = wI, and w1 and w2 correspond to w)components associated with (100) and (010) twin planes,
respectively.
being coincident at K = 23 (common 03̄3 reflection for A and temperature dependence of the twin angle up to 800 uC is
A9 domains). The combination of the four sets of twin domains depicted in Fig. 4(b). Extrapolation to the film deposition
(A, B, C, D), with even probability, defines six different H0L/0KL temperature, 900 uC, gives 0.01u which, in contrast with
reflections with splitting along Qx, Qy and Qz, like the one previous reports,24 indicates that, within experimental accu-
depicted in the right panel in Fig. 3(b), with their Qx splitting racy, the films grow with negligible shear distortion. Moreover,
dependent only on L, and their Qz dependent on the K value, a determination of lattice parameters indicated that at 800 uC
while the Qy splitting depends both on K and L values. Note the films still exhibit a clear tetragonal distortion: c = 3.908 Å
that the particular optics of the X-ray diffractometer used in and a = 3.937 Å, which comes from the epitaxial strain. The
these measurements does not provide sufficient resolution extrapolation to the growth temperature indicates still a large
along Qy (Cu tube long fine focus source with axial beam degree of tetragonal distortion. Therefore ferroelastic domains
divergence only controlled by Soller slits). Therefore, the develop during cooling within an elastically strained state
experimental maps contain a projection of the reflections split imposed by the cubic substrate. Hence, the selection of only
in Qy. This makes the projection of the H03 reflections to those twin planes perpendicular to the substrate does not
appear as four spots in the maps (only three in the 003 map). allow for the complete relaxation of the 3D shear strain state
Temperature dependence of the twined structure. In order associated with the development of rhombohedral phase.
to ascertain whether twin domains form during film growth or Consequently residual shear strains are expected to build up
during the cooling step, Fig. 4(a) shows examples of three within the films, as will be analysed in detail in the last section
reciprocal space maps corresponding to a 120 nm thick film of the paper.
obtained at 26 uC, 400 uC and 800 uC around the 003 reflection Dependence of diffraction features on film thickness. The
illustrating the progressive reduction of the splitting. The dependence of the relative weight of each contribution on film
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Fig. 4 (a) Reciprocal space maps of the 003 reflection for a LSMO film of 120 nm
measured at different temperatures. For this reflection the observed splitting in
Qx is only related to the twin domain tilt angle and decreases with temperature.
(b) Twin angles for the different temperatures.
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Fig. 6 Intensity maps obtained from simulation of Qx scans of an ideal schematically depicted in the schemes shown in Fig. 7(b).
rhombohedral LSMO film (STO substrate not included) as a function of twin Twin domains A/A9 sharing (100) planes present common a*
domain periodicity, L, for the three 001, 002 and 003 reflections. For large direction (same Qx and Qy) and both contribute to the central
domain periodicity (L . 100 nm) the Qx scans reveal mainly L-dependent Bragg
reflection along [100], whereas their corresponding b* splits
splitting associated with the imposed 0.5u twin angle. While for small domains
(L , 30 nm) the scans show a central peak along with satellites, equivalent for
along [010] because of the shear in-plane angle of the
all 00L, coming from the lateral modulation. Note that the region with rhombohedral distortion (same Qy, two different ¡Qx), see
coexisting contributions depends on the L value. Fig. 7(a). The coexistence of B/B9 twin domains with common
(010) twin plane gives rise to a double peak along [100].
Together, the even population of A/A9 and B/B9 domains
signal was observed for this type of measurement (Fig. 5e), generates a triple peak for all H00 and 0K0 reflections, and
therefore, neither twin tilt angle nor twin spacing could be four peaks for the HH0 reflections. Both 100 and 200
extracted. reflections were scanned at W = 0u, whereas 110 area scans
In order to contrast our experimental results with theory, a were centered at W = 45u. As expected, no significant
kinematical two-beam approximation was used to simulate differences were observed between area scans obtained along
equivalent W ¡ 90u azimuths. For the whole set of samples,
diffraction patterns as a function of the lateral period of the
average positions of all in-plane reflections appeared centered
twinned structure, L.25 The simulation was performed for an
on the substrate (HK0) positions, which is an indication of the
ideal 2D twinned crystal model in Qx Qz space with a constant
perfect in-plane registry of the film and substrate structures.
rhombohedral shear angle of 0.5u and a constant vertical
As in previously described out-of-plane measurements, the in-
component of the diffraction vector. A quasiperiodic sequence
plane XRD configuration revealed different regions depending
of symmetric triangular waves with constant angle and
on film thickness. In the thicker sample (140 nm) both 100
variable period was used to displace atom positions in the
and 200 reflections show clear splitting along the W1-axis,
z-direction (perpendicular to the film) from the perfect cubic
giving rise to a triple peak. No variation in the 2h positions is
configuration. Fig. 6 shows intensity maps obtained from
observed for the peaks. At the employed grazing incidence
simulated Qx scans for the different 00L (L = 1, 2 and 3)
(0.5u), no significant contribution is expected from the STO
reflections. As experimentally observed, when the twin
substrate since penetration depth at this grazing incidence is
modulation is smaller than a certain value (L , 30 nm) the
reduced to a few tenths of nanometers. Both 100 and 200
XRD patterns show a central peak along with nth order
reflections show the same DW splitting about ¡0.53u, which is
satellites dominated by the modulation contribution (same
more than twice the value measured for out-of-plane reflec-
splitting for any 00L), while the larger the domains (L . 100 tions (¡0.23u) in the same film. This indicates that epitaxial
nm) the more dominant the pattern exhibiting only two tilted LSMO structure deviates from that corresponding to the
Bragg domains (splitting increasing with 00L). The intermedi- rhombohedral bulk phase with equal shear angle distortion
ate region where both contributions may coexist is shifted along any ,100. direction. Similarly, for HH0 reflections, the
towards smaller lateral modulation upon increasing the L (100) twin plane causes splitting along Qx, whereas the (010)
value. Therefore, there might be a region of lateral modulation twin plane induces the same splitting along Qy. Altogether,
values where it is possible to obtain Qx scans with predomi- they split in four peaks, as it is observed in the (110) reflection
nant satellites for low L values, whereas they may show area scan. In this case the peaks show two different values of
dominant Bragg peaks for larger L scans, as experimentally 2h and W angles. On the other hand, the film with 9.4 nm
observed in the L scans in Fig. 5(b) for L = 146 nm. thickness shows clear 1st and 2nd order satellite peaks along
In-plane diffraction analysis. Experimentally, by using a Cu W axis. Note that in this case the DW splitting of the 100
tube X-ray source and standard four-angle goniometers it is reflection is twice that of the (200) one. This is consistent with
not possible to obtain any additional information of the a splitting due to twin periodicity with common DQy for any
twinned structure of very thin films for symmetrical 00L H00 reflection. Satellites up to 2nd order were also observed
reflections because of the weak signal from the very small associated to the 110 reflection giving rise to a symmetric
analyzed film volume and the small coherence length of the crossed ‘‘X’’ pattern. A twin periodicity of L = 38.9 nm was
beam in the projected in-plane direction (in relation to the extracted for this sample, while no traces of twin periodicity
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Fig. 7 (a) In-plane 2h–W area scans of 100, 200, and 110 reflections of LSMO epitaxial films of different thicknesses. All scans correspond to 3u span in both 2h and W
angles, and were centered in the ideal positions of cubic primitive cell with a = 3.905 Å. (b) Scheme of the expected reflections for the in-plane reciprocal space cut
and corresponding h00 and hk0 reflections for each of the four non-equivalent twin domains, in the case that there is no contribution of twin size periodicity (clear
Bragg peaks appear due to in-plane twin angle) and when twin modulation is dominant (satellites peaks up to 2nd order are depicted). The squared areas correspond
to the measured 2h–W area scans.
could be detected in corresponding out-of-plane measure- yields elastic energies per unit film thickness E(x)/t # 1.4 MPa
ments. The arrangement of satellite reflections coming from and E(e)/t # 10 MPa, i.e., despite the close similarity between
the twin size periodicity is also depicted in the scheme in the normal and shear strains, the energetic contribution of the
Fig. 7(b). Films with intermediate thickness between 140 and latter one is significantly larger. Current models assume that
9.4 nm show more complex patterns which combine both E(x) and E(e) are cancelled independently by twinning on (100)
contributions. Still for some samples it was possible to extract and (010) planes perpendicular to the substrate and a square
twin angles from the more intense 200 reflection. Thinner grid of misfit dislocations, respectively. On this basis, theory
films with 3.4 and 2.5 nm still show weak satellite peaks predicts that there is no theoretical critical thickness for twin
associated to the intense 200 and 110 reflections, and values formation, i.e., E(x) is expected to be relieved from the initial
for twin periodicity of 25.6 and 25.4 nm were extracted for both growth stages,9 while the e contribution should be totally
samples, respectively. The thinnest sample of 1.9 nm did not relaxed at a critical thickness of y10 nm,29 in strong contrast
show any evidence of twin periodicity, in agreement with OC- with this investigation and previous reports.30 Deviations from
SEM images (Fig. 2a). theory predictions arise from the fact that the deformation
Interfacial layer, evolution of the shear strain and twin domain behavior of a perovskite-type ABO3 octahedral framework does
period not necessarily follow linear elasticity, but may be strongly
affected by the interplay of electronic and octahedral-tilting
According to linear elasticity, the total elastic energy of the degrees of freedom18 governing the relative strength between
film can be written as the sum of the shear and lattice the B–O–B bond angles bridging adjacent octahedra and the
parameter misfit contributions: E = E(x) + E(e), where:27 E(x) = B–O bonds forming the octahedra.31
(1/2)Gx2t and E(x) = 2[(1 + n)/(1 2 n)]Gx2t, E being defined as
Thickness dependence of the shear strain. The thickness
the energy per unit interface area, n y 0.33 the Poisson’s ratio
evolution of the in-plane (wI) and out-of-plane (w)) shear
(see below) and G y 68.2 GPa is the shear modulus.28 This
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Fig. 9 Twin size (L/2) dependence on t1/2 as derived from direct inspection of
Fig. 8 Thickness dependence of the in-plane (wI) and out-of-plane (w)) shear
OC-SEM images and in-plane and out-of-plane XRD measurements.
angles as measured from the 200 and 002 reflections, respectively. Octahedral
models viewed along [001] (upper scheme) and [1̄10] (lower scheme)
illustrating the effect of octahedral tilting about the c-axis (c) and about the a
and b-axes (a and b), respectively. The epitaxial relation with the substrate Mn–O bonds, the MnO6 octahedra very likely evolve to a rigid
imposes that a = b, which results in a net in-plane tilt about the [110] direction.
unit behavior. Since on a pure rigid octahedra basis, the in-
According to ref. 32 c-tilts are correlated with wI, and (a,b)-tilts are correlated
plane lattice parameter is determined by octahedral tilts a and
with w), as discussed in the text.
c, as a = a0cosacosc,34 the trajectory followed by wI and w)
reflects a combined octahedral tilting mechanism whereby the
elastic strain of the equatorial octahedral Mn–O bonds is
angles is shown in Fig. 8. It can be seen that both values tend relaxed while simultaneously keeping the in-plane lattice
to converge at y10 nm. Above this thickness the divergence parameters fully matched with those of the substrate.
between the main components of the shear strain indicates Thickness dependence of the twin domain period. Fig. 9
that the average structure departs again from the rhombohe- presents the twin size (L/2) dependence on t1/2 as derived from
dral symmetry. This is a rather surprising result as it indicates direct inspection of OC-SEM images and from the twin
that strictly speaking the canonical rhombohedral phase is modulation satellites obtained from rsm’s. The plot shows
only stable in a narrow range of film thickness and in a fully that L/2 increases as the square root of the film thickness, t1/2.
strained state. According to the analysis of geometrical This behavior is consistent with predictions from thermo-
relations in rhombohedral perovskites by Megaw and dynamic modeling of ferroelastic domains in epitaxial
Darlington,32 to a first approximation the shear components systems:10 L/2 = (kDtt)1/2, where k is a numerical constant,
are related to the in-plane (a) and out-of-plane (c) octahedral and Dt = EW/Get2 is an elastic length-scale parameter,35 EW, G
tilt angles as wI y (1/3)c2 and w) y (1/3)a2, respectively.33 and et being the elastic energy density per unit area of the
Therefore, the observed divergence between the main shear domain wall, the shear modulus and the transformation misfit
strain components in fact reflects a perturbation of the strain associated to the cubic prototype A ferroelastic phase
octahedral tilt pattern as illustrated by octahedral models transition, respectively. Noticing that the elastic strain energy
included in Fig. 8, with an increase in the octahedral rotation density per unit area stored in a slab of material with thickness
angle c upon thickness increase while a, b octahedral rotation d under a strain et is EW = KGet2d, one finds d = 2Dt. The
angles are reduced. length-scale parameter Dt thus corresponds to the half-
It is interesting to note that according to a half-loop thickness of an elastically strained slab of material centered
nucleation mechanism12 the critical thickness for misfit strain on a plane strain source (cf. the twin wall), which those models
relaxation is calculated to be y10 nm,29 i.e., the thickness at associate with the domain wall half-thickness.35
which the elastically strained rhombohedral phase is stabi- For the film–substrate interface, an elastic length-scale
lized. Thus, the fact that the perturbation of the octahedral parameter with the same form as Dt has been derived, which
framework appears at a film thickness at which the stored determines the film thickness, tt, at which the effect of
elastic energy equals the energy associated with the formation coherency with the substrate on the development of the twin
of misfit dislocations, strongly suggests that the driving force structure vanishes.9 For t . tt Farag et al. find the expected L/2
for the modification of the octahedral tilt pattern is the need to y t1/2 dependence with k = 3.84{(1 2 n)/(2 2 n)}1/2, while for t
relax the elastic energy stored in the tensilely strained , tt, L/2 would exponentially increase as the thickness
rhombohedral phase. In this thickness regime, the films grow decreases up to ‘ at the interface.9 For a domain wall energy
far from the interface and therefore one can expect that these EW = 3 mJ m22 one obtains Dt y 3 nm,9 similar to our
distortions are not influenced by substrate–film electronic experimentally determined critical thickness for twin nuclea-
interactions. Hence, upon relieving the elastic energy stored in tion tt y 2–2.5 nm. However, despite the similarity between
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the values obtained for Dt and tt, their origin and physical 2.5 nm. This critical thickness has profound implications on
meaning is notably different: While the calculation of Dt the functional performance of the films as ferromagnetic order
assumes a pure plastic relaxation mechanism of the shear and metallic behavior are degraded within the monoclinic
strain through a coherency defect approach,14 which allows phase for t , tt.18 For t . tt the film progressively evolves
twin domains to nucleate just ahead from the film–substrate towards the canonical rhombohedral form of LSMO, which
interface with the twin size exponentially decaying down to a under the present growth conditions is stabilized at a
minimum equilibrium value at Dt, above which the L/2 y t1/2 thickness y10 nm. Further growth is accompanied by a
dependence is established, the observed tt indicates a
progressive departure from the rhombohedral symmetry as
thickness at which twins nucleate within an non-twinned
revealed by the divergent trajectories followed by the in-plane
matrix of reduced symmetry. Thus, twins nucleate as soon as
and out-of-plane components of the shear strain. This
shear strains start to build up as a result of the progressive
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