Thin Solid Films 609 (2016) 1–5

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Thin Solid Films

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Growth and characterization of textured YBaCo2O5 + δ thin films grown

on (001)-SrTiO3 via DC magnetron sputtering
V. Galeano a, O. Arnache b, I. Supelano c, C.A. Parra Vargas c, O. Morán a,⁎
a
Universidad Nacional de Colombia, Campus Medellín, Facultad de Ciencias, Departamento de Física, Laboratorio de Cerámicos y Vítreos, A.A. 568, Medellín, Colombia
b
Grupo de Estado Sólido, Departamento de Física, Universidad de Antioquia, A.A. 1226, Medellín, Colombia
c
Universidad Pedagógica y Tecnológica de Colombia, Departamento de Física, Avenida Central del Norte 39-115, Tunja, Colombia

a r t i c l e i n f o a b s t r a c t

Article history: Thin films of the layered cobaltite YBaCo2O5+δ were successfully grown on (001)-oriented SrTiO3 single-crystal
Received 23 June 2015 substrates by means of DC magnetron sputtering. The 112 phase of the compound was stabilized by choosing an
Received in revised form 4 April 2016 adequate Co reactant and through careful thermal treatment of the target. The results demonstrate the strong in-
Accepted 12 April 2016
fluence of these variables on the final phase of the compound. A substrate temperature of 1053 K and an oxygen
Available online 13 April 2016
pressure of 300 Pa seemed to be appropriate growing conditions for depositing (00ℓ)-textured YBaCo2O5+δ thin
Keywords:
films onto the chosen substrate. In like fashion to the polycrystalline YBaCo2O5+δ, the films showed a clear se-
Thin films quence of antiferromagnetic–ferromagnetic–paramagnetic transitions within a narrow temperature range.
Sputtering Well-defined hysteresis loops were observed at temperatures as high as 270 K, which supports the existence
Cobaltites of a FM order in the films. In turn, the dependence of the resistivity on the temperature shows a
Magnetism semiconductor-like behavior, without any distinguishable structure, within the temperature range measured
(50–350 K). The analysis of the experimental data showed that the transport mechanism in the films is well de-
scribed by using the Mott variable range hopping (VRH) conduction model.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction variations in the physical properties, the various possible spin states of
cobalt ions also dramatically influence the magnetic behavior of the
Recently, Co-based compounds have been intensively investigated 112 cobaltites. These compounds feature successive paramagnetic–fer-
due to the existence of fascinating magnetic, electrical, and romagnetic–antiferromagnetic (PM–FM–AFM) transitions within a
magnetotransport properties, such as an exceptionally high magnetore- range 200–300 K and an insulator–metal transition between 300 and
sistance in the ordered oxygen-deficient 112 phase double perovskites 400 K [1]. The understanding of such magnetic and electrical phases is
LnBaCo2O5+δ (Ln = Eu, Gd) [1]. The rich phase diagram exhibited by a matter that is undergoing serious debate. Among the cobalt oxides
these oxides is linked to the variations of the oxygen content δ. Indeed, synthesized over the last few years, the compound with Y3+, which is
the electronic states of the Co and the surrounding oxygen are markedly a non-magnetic ion, is a good candidate for isolating the intrinsic prop-
changed by varying this parameter [2,3]. Currently, the crystal structure erties of Co in the layered perovskites. Moreover, Y3 + is among the
of these oxides is described as an ordered sequence of [CoO2]-[BaO]- smallest cations that can form this compound. Besides the basic physical
[CoO2]-[LnOδ] layers along the c-axis, where oxygen vacancies exist in aspects, the technical potentialities of LnBaCo2O5+δ cobaltites should
the lanthanide layer. Thus the structure of the LnBaCo2O5+δ cobaltites not be overlooked. Indeed, the high ionic and electronic conductivities
turns out to be very flexible and sensitive both to tiny variations of the and the catalytic and electrocatalytic properties of cobalt-containing
oxygen content and to the size of the Ln3+ cation. This, in turn, leads compounds make them promising materials for the development of
to strong variations of the magnetic properties [4,5]. The oxygen content electrochemical devices such as cathodes in solid-state fuel cells, mem-
δ controls the mixed valence state and coordination (pyramidal or octa- branes for oxygen separation, and a variety of sensors [6]. To improve
hedral) of the cobalt ions. The valence of Co ions varies from + 2.5 at the performance of those devices, the mixed ionic electronic conducting
δ = 0 (pyramidal environment of Co ions) to +3.5 at δ = 1 (octahedral materials should meet the requirements of both high oxygen diffusivity
environment of Co ions). At δ = 0.5 (O5.5), one might expect that only and great enhancement of the surface exchange rate [7]. These two de-
Co3+ ions will be present (alternating pyramidal and octahedral envi- sirable attributes are typically found in the oxygen-deficient doped pe-
ronments). Although the oxygen content δ and the Ln size lead to strong rovskite cobaltites LnBaCo2O5+δ [8]. It should be mentioned that the
average valence of the alkaline earth element cation (Ba in the present
⁎ Corresponding author. case) favors a compensating population of oxygen vacancies at low ox-
E-mail address: [email protected] (O. Morán). ygen partial pressures and therefore leads to the observed high ionic

http://dx.doi.org/10.1016/j.tsf.2016.04.020
0040-6090/© 2016 Elsevier B.V. All rights reserved.
2 V. Galeano et al. / Thin Solid Films 609 (2016) 1–5

conductivity. Moreover, the size and distribution, ordered or disordered, atoms between regions of different stoichiometry but also increases
of the alkaline earth element cations may drastically influence the the influence of re-sputtering and re-evaporation, especially at higher
mixed conductivity [9]. temperatures [14]. Intense scattering of the sputtered particles, which
To fully understand the physical phenomena in complex systems, occurs due to the high oxygen pressure, results in isotropic spreading
single crystalline materials are becoming critical for tackling these prob- of the elements, which provides a uniform composition of the thin
lems. Nevertheless, in the case of YBaCo2O5+δ cobaltites, their complex film. The ~ 3 cm diameter of the target is large as compared to the
crystal structures hamper the achievement of high-quality single crys- 0.5 × 0.5 cm dimensions of the substrates used. The target-substrate dis-
tals for systematically studying their interesting anomalous physical tance was kept at ~4 cm in order to prevent the plasma from touching
properties. Therefore, highly epitaxial thin films grown on crystalline the substrate surface. This geometry provided uniform thickness of
substrates offer an alternative route for exploring the nature of these the thin films that were produced. Target particles traveling longer dis-
physical phenomena [8]. In addition, for many applications, such as tances and thermalized by multiple scattering are also less likely to
gas sensing, high-quality YBaCo2O5 +δ thin films are highly desirable. cause re-sputtering from the substrate surface. YBaCo2O5 + δ films
Various deposition techniques, including DC magnetron sputtering (~ 230 nm) were deposited in oxygen atmosphere at a pressure of
and pulsed laser deposition (PLD), have been widely used to grow 300 Pa (measured using a Pirani gauge and a MKS 937 A gauge control-
high-quality oxide thin films. The deposition techniques should allow ler), a power of 30 W, and a substrate temperature of 1053 K, achieved
one to fabricate stoichiometric, high-quality thin films by pulverizing by a resistive element. The indicated substrate temperature is the tem-
or ablating multi-component targets. In this regard, the physical proper- perature of a thermocouple located within the substrate heater. Before
ties of cobaltite films are strongly dependent on crystalline quality and adding oxygen (purity 99.999%) for sputtering, the system was evacuat-
texture, which, in turn, very much depend on the process parameters ed up to a base pressure of 0.01 Pa using a two-stage, rotary vane, vac-
and the substrate materials. For the deposition of YBaCo2O5 + δ films, uum pump. After deposition, the substrate temperature was lowered
commercially available cubic perovskite, (001)-oriented SrTiO3 sub- to 723 K, and the chamber was then flooded with oxygen at a pressure
strates, with lattice parameter 3.90 Å, may be suitable due to the ther- of ~8 × 104 Pa. The films were annealed under these conditions for 1 h.
mal and lattice matching. In the present paper, results of the growth The deposition temperature was chosen based on previous results
of YBaCo2O5+δ films on (001)-oriented SrTiO3 substrates via DC magne- achieved for YBaCo4O7 films [15]. X-ray diffraction patterns of the
tron sputtering, as well as their magnetic properties, are reported. YBaCo2O5+δ target and the thin films were recorded with a Panalytical
X'Pert Pro MPD diffractometer using CuKα radiation (λ = 0.15418 nm).
2. Experimental details The composition of the films was determined via energy dispersive X-
ray spectroscopy (EDS). The microstructure of the films was tested
Polycrystalline YBaCo2O5+δ samples were obtained through stan- using a JEOL JSM-6500F field-emission scanning electron microscope
dard solid-state reaction [10]. Stoichiometric quantities of Y2O3, (FESEM) equipped with EDS probe. The magnetic properties of the
BaCO3, and Co3O4 reactants were weighed and thoroughly mixed with thin films were systematically studied by using a vibrating sample mag-
a mortar and pestle, adding ethanol for homogeneous mixing. All the re- netometer (PPMS VersaLab system from Quantum Design). The electri-
actants were used as received, i.e. no preheating process was performed cal transport measurements were carried out with the standard four-
prior to their use. The mixture was first heated in air at 1173 K for 15 h probe method using a He closed cycle cryostat within a temperature
to achieve decarbonization. An alumina tube furnace (~5 cm in diame- range of 50–320 K.
ter) was used for this purpose. Sequentially, the powder was ground for
1 h using mortar and pestle and reacted in air at 1273 K for 36 h, follow-
ed by slow cooling to room temperature (~5 K/min). The latter treat- 3. Results and discussion
ment was repeated in order to remove trace amounts of phase
impurities (Y2O3 and/or BaCoO2.9). In particular, the cubic Y2O3 impuri- As stated above, the YBaCo2O5+δ powders were prepared through
ty probably stems from a small volume of non-reacted yttrium. The standard solid-state reaction. Although several authors report initial
black, single-phase YBaCo2O5+δ powder was ground and pressed into thermal treatments (decarbonization) at temperatures as high as
the form of targets (~3 cm in diameter and thickness ~ 0.5 cm), using 1273 K [16], it was established in the present study that the achieve-
pressure as high as 3.1 × 107 Pa. The targets were maintained at this ment of high-quality samples, i.e. samples with reduced presence of for-
pressure for five minute and then carefully extracted from the die. The eign phases, requires an initial thermal treatment at 1173 K followed by
pressed targets were set on an alumina-disk and introduced into the very slow cooling to room temperature (278 K/min). For a second ther-
oven for sintering. Finally, the targets were sintered in air at 1323 K mal treatment, the sample should be reacted at 1273 K for at least 36 h
for 36 h and slowly cooled to room temperature. The YBaCo2O5+δ target followed by slow cooling to room temperature. A third treatment was
was coupled to a non-commercial magnetron source that allows for carried out at 1273 K for 30 h, followed by very slow cooling to room
much higher pressure operation than is typical for sputtering [11–13] temperature. Thermal treatments at slightly higher temperatures (say
and pre-sputtered before film deposition in order to remove possible 1323 K) led to the formation of the YBaCo4O7 + δ (114) secondary
contaminated surface layers from the target. The sputtering system phase. Fortunately, the targets treated at 1323 K for 36 h resulted in
used to grow YBaCo2O5+δ films is not equipped with secondary sources being correctly sintered without being greatly affected by secondary
of ionization radiation such as ultraviolet or microwave radiation. phases. In addition, it was observed that the formation of the 112
Hence, the sputter source used in the present work is fundamentally dif- phase is very sensitive to the chosen Co reactant. In the present paper,
ferent from that described in Ref. [11]. The films were grown on as- the stabilization of the 112 phase was practically impossible using
received, (001)-oriented SrTiO3 substrates (0.5 × 0.5 × 0.05 cm) sup- Co2O3 instead of Co3O4. Although a detailed study of the influence of
plied by the MTI Corporation (United States). SrTiO3 possesses a cubic the valence on the physicochemical behavior of YBaCo2O5+δ is neces-
perovskite structure and the lattice constant is 3.905 Å.YBaCo2O5 +δ sary, it seems that the mixed-valence character of the Co3O4 reactant
thin films were deposited using high pressure oxygen sputtering [11]. plays a central role in the formation of the 112 phase of the cobaltite
This is one of the physical vapor deposition methods in which a material under study. The XRD pattern of the target is shown in Fig. 1(a) along
of desired composition (target) is vaporized using an ionic beam and with the simulated spectrum for a compound with an oxygen content
subsequently condensed in the form of a film coating on a suitable sur- of δ ≈ 0.5. The XRD pattern indicates that the compound is single-
face (substrate). Here, the deposition rate is slow compared to other phase with no effect of secondary phases. Although the oxygen content
methods such as pulsed laser deposition (PLD). A slow rate extends in the target was not explicitly determined, a comparison of the struc-
the time of formation of the upper layers and allows diffusion of tural and magnetic results with the detailed characterization by
 V. Galeano et al. / Thin Solid Films 609 (2016) 1–5 3

Fig. 1. (a) XRD pattern of the YBaCo2O5+δ sputtering target. The simulated spectrum corresponding to the compound with δ ≈ 0.5 is also plotted. (b) XRD pattern of an as-grown
YBaCo2O5+δ thin film on an (001)-oriented SrTiO3 substrate.

Akahoshi and Ueda [16] of samples with varying oxygen content strong- Fig. 2(b). A crystallite size of ~ 10 nm is estimated for the analyzed
ly suggests that the oxygen content in the target is δ ≈ 0.5. film. Note that the FESEM images show a non-directional growth of
For the deposition of YBaCo2O5 + δ films, commercially available the film, which apparently differs from the preferential orientation
(001)-oriented SrTiO3 substrates with lattice parameters a = 3.90 Å shown by the XRD pattern. Here, it is probable that the FESEM image
may offer reasonable conditions for a textured growth because of the is screened by the effect of the breaking or cutting of the substrate,
cubic structure closely related to the orthorhombic YBaCo2O5.5 with lat- since the FESEM images were taken without polishing the cross section.
tice parameters a = 0.392 nm, b = 0.382 nm, and c = 0.751 nm [16]. A Nevertheless, it is also likely that the films are textured polycrystalline,
typical XRD θ-2θ scan of an YBaCo2O5+δ thin film grown on a (001)-ori- i.e. the films consist of grains with a preferred orientation along one out-
ented SrTiO3 substrate is shown in Fig. 1(b). The strong (00ℓ) reflec- of-plane axis. Without doubt, additional experimental work should be
tions appearing in the diffraction pattern, superimposed onto the carried out in order to obtain deeper insight into the crystalline struc-
substrate peaks, suggest that the films are c-axis oriented. From the nor- ture of the YBaCo2O5 + δ films grown by DC magnetron sputtering.
mal θ-2θ scan, a c-axis lattice parameter of 0.778 nm was calculated, Fig. 2(c) shows the EDS analysis of the film, which exhibits sharp
suggesting that the film grows under tensile strain in this direction. peaks corresponding to the expected elements (Y, Ba, and Co). Apart
Apart from the (00ℓ) reflections, a small peak stemming from a from the Sr and Ti peaks, stemming from the SrTiO3 substrate, no
minor impurity (probably Y2O3 or BaCoO) can also be seen in the XRD other contributions were detected.
pattern. The small amount of material (thin film) makes unambiguous Fig. 3(a) shows the low-field magnetization versus the temperature
identification of these peaks difficult. These impurities can be eliminat- (M–T) for the YBaCo2O5 +δ target recorded in a 0.1 T magnetic field
ed by means of further annealing of the films, as has been verified for under the zero-field cooling (ZFC) procedure. As shown in Fig. 3(a),
the polycrystalline samples. Thus although the present results are en- the magnetization of the target rapidly increases below TC ∼ 290 K and
couraging, additional work is necessary in order to optimize the process then rapidly decreases below T⁎ ∼ 270 K. It is apparent that TC and T*
of growing YBaCo2O5 +δ film films by means of the magnetron are temperatures associated with magnetic transitions. Without
sputtering technique. It would be interesting to study the possible influ- doubt, at T = TC a paramagnetic (PM) to ferromagnetic (FM) transition
ence of parameters such as substrate temperature, oxygen pressure, occurs, whereas at T = T⁎, the magnetization abruptly drops to zero. The
post-annealing, etc. on the growth mode and crystalline quality of M–H curve recorded at 272 K (inset) indicates that the sample is ferro-
YBaCo2O5+δ films. magnetic between TC and T⁎. These results suggest a ferromagnetic to
The top view FESEM micrograph shown in Fig. 2(a) suggests uniform antiferromagnetic transition at T*. In turn, the dependence of the in-
covering of the substrate by the film with the absence of effects caused plane magnetization on the temperature for an YBaCo2O5 +δ film
by serious defects such as cracking, pores and pits, or large-size precip- (~ 230 nm in thickness) deposited on a (001)-oriented substrate is
itates. The granular character of the film surface, along with a uniform shown in Fig. 3(b). It can be seen from this plot that a spontaneous mag-
distribution of the grain size, can be seen in the micrograph shown in netization, M, appears below 275 K (TC) and decreases abruptly below

Fig. 2. (a) Typical FESEM micrograph of the surface of an YBaCo2O5+δ film grown on a (001)-oriented SrTiO3 substrate. (b) High-resolution FESEM micrograph of film shown in (a).
(c) Energy dispersive X-ray spectrum for the tested YBaCo2O5+δ film.
4 V. Galeano et al. / Thin Solid Films 609 (2016) 1–5

Fig. 3. Temperature dependence of the magnetization in ZFC mode for the YBaCo2O5+δ target. The data were recorded under warming conditions in a field of 0.1 T. Inset: Field dependence
of the magnetization of the YBaCo2O5+δ target measured at 272 K. In-plane temperature dependence of the magnetization in ZFC mode for an YBaCo2O5+δ film deposited on (001)-SrTiO3
substrate. Inset: Magnetization as a function of the magnetic field at 265 K for the YBaCo2O5+δ film.

266 K (T⁎). Although the transition temperatures are slightly lower than is different from 0.5. For instance, the presence of extra oxygen in the
those encountered for the bulk material, the behavior of the M(T)-curve structure would tend to locally increase the coordination of the cobalt
closely follows that observed for the bulk material. The difference in the cations with the formal oxidation state Co3 + (δ = 0.5). This, in turn,
values of the transition temperatures could result from the intrinsic will create a more disordered local crystallographic structure, which
strain in the textured films, as reported for other compounds belonging can suppress the metal–insulator transition. The electric transport
to the same family [17]. It is also possible that the observed difference is mechanism in the cobaltite films was tested using different models,
associated with tiny variations in the oxygen content in the films. It is such as simple thermal activation transport, small polaron hopping,
widely known that oxygen non-stoichiometry plays a central role in and Mott's VRH model [ρ(T) = ρ∞ exp.[(T*/T)1/4] [20]. In the latter equa-
the transport and magnetic properties of YBaCo2O5+δ cobaltites [18]. tion, T* represent a typical temperature scale that is related to the local-
The inset of Fig. 3(b) shows a M(H) hysteresis loop taken at 265 K for ization length ξ. The experimental data show a better agreement with
the YBaCo2O5 + δ thin film. Tendency to saturation is observed at a the VRH model, as is shown in the inset of Fig. 4. The fit of the VRH
field higher than ~2000 Oe, which is consistent with the results obtain- model to the experimental data yields a temperature scale T⁎ =
ed for the target. Thus although the TC and T⁎ of the film are slightly re- 9.1 × 105 K, about one order of magnitude lower than that reported
duced, the fact that the ferromagnetic component is retained in the for other transition metal oxides [21].
films indicates that this system undergoes a PM–FM and a FM–AFM
phase transition at TC and T⁎, respectively.
Fig. 4 shows the temperature dependence of the resistivity of a rep- 4. Summary and conclusions
resentative YBaCo2O5+δ film grown on an (001)-SrTiO3 substrate. The
semiconducting character of the sputtered YBaCo2O5 +δ film at a low High-quality YBaCo2O5+δ targets were fabricated via the standard
temperature can clearly be seen from this plot (dρ / dt b 0). In this com- solid-state reaction. YBaCo2O5 + δ thin films were then grown by
pound, the conventional semiconducting transport occurs due to the means of DC magnetron sputtering on (001)-oriented SrTiO3 substrates
mobility of the thermally excited hole and the electron corresponding heated to 1053 K. No ex-situ annealing was undertaken on the thin
to the Co4 + and Co2 + species, deriving from the ground state Co3 + films. The XRD patterns showed that the films were (00ℓ)-oriented
ions [19]. At room temperature, the resistivity value amounted to without affectation by impurities or secondary phases. Results of mag-
~3 × 10−3 Ωm. Resistivity values of ~5 × 10−2 Ωm have been reported netic measurements performed on both the bulk and the thin films
for cobaltite thin films with stoichiometry 114 (YBaCo4O7+δ) [15]. In- showed the typical PM–FM–AFM transitions expected for samples
terestingly, no anomaly, generally associated with structural phase with oxygen content δ ≈ 0.5. The isothermal M(H) curves showed the
transitions [3], is observed in the ρ(T) dependence within the tempera- existence of a ferromagnetic phase at 272 and 265 K for bulk and thin
ture range measured. For polycrystalline YBaCo2O5.5 samples, a pro- films, respectively. The small difference in the transition temperatures
nounced change in the magnitude of the resistivity around 300 K has could be associated with the intrinsic strain in the thin films and/or
been reported [19]. The absence of the transition in the YBaCo2O5 +δ the variation in the oxygen content in the thin films. Transport mea-
film suggests that this is non-stoichiometric oxygen, i.e. the value of δ surements in zero field showed semiconductor-like behavior at low
temperatures. No transitions were observed within the temperature
range measured. The Mott VRH model allowed describing the electric
transport in the films. Although the results presented in this paper are
encouraging, new experiments are under way to optimize the
sputtering growth parameters and to study fundamental aspects of
these oxides, such as the relation between the oxygen vacancies config-
uration and the spin state of the Co atoms.

Acknowledgments

This research was supported by the Universidad Nacional de

Colombia, Medellín Campus. V. G. acknowledges the financial support
of the Dirección Nacional de Investigaciones of the Universidad Nacional
de Colombia (grant number 201010013249). The collaboration of Dr. A.
Fig. 4. Temperature dependent resistivity of a representative YBaCo2O5+δ film in zero Rosales (Universidad Nacional de Colombia, Manizales Campus) with
field. The corresponding insets show the T-1/4 dependence of the resistivity. the VSM measurements is gratefully acknowledged.
 V. Galeano et al. / Thin Solid Films 609 (2016) 1–5 5

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