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Preparation of large Cu3Sn single crystal by Czochralski method
Authors:
Minsik Kong,
Sang-Eon Park,
Hye Jung Kim,
Sehwan Song,
Dong-Choon Ryu,
Baekjune Kang,
Changhee Sohn,
Hyun Jung Kim,
Youngwook Kim,
Sangmoon Yoon,
Ara Go,
Hyoungjeen Jeen,
Sungkyun Park,
Se-Young Jeong,
Chang-Jong Kang,
Jong Mok Ok
Abstract:
Cu3Sn was recently predicted to host topological Dirac fermions, but related research is still in its infancy. The growth of large and high-quality Cu3Sn single crystals is, therefore, highly desired to investigate the possible topological properties. In this work, we report the single crystal growth of Cu3Sn by Czochralski (CZ) method. Crystal structure, chemical composition, and transport proper…
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Cu3Sn was recently predicted to host topological Dirac fermions, but related research is still in its infancy. The growth of large and high-quality Cu3Sn single crystals is, therefore, highly desired to investigate the possible topological properties. In this work, we report the single crystal growth of Cu3Sn by Czochralski (CZ) method. Crystal structure, chemical composition, and transport properties of Cu3Sn single crystals were analyzed to verify the crystal quality. Notably, compared to the mm-sized crystals from a molten Sn-flux, the cm-sized crystals obtained by the CZ method are free from contamination from flux materials, paving the way for the follow-up works.
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Submitted 14 June, 2022;
originally announced June 2022.
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Highly ordered lead-free double perovskite halides by design
Authors:
Chang Won Ahn,
Jae Hun Jo,
Jong Chan Kim,
Hamid Ullah,
Sangkyun Ryu,
Younghun Hwang,
Jin San Choi,
Jongmin Lee,
Sanghan Lee,
Hyoungjeen Jeen,
Young-Han Shin,
Hu Young Jeong,
Ill Won Kim,
Tae Heon Kim
Abstract:
Lead-free double perovskite halides are emerging optoelectronic materials that are alternatives to lead-based perovskite halides. Recently, single-crystalline double perovskite halides were synthesized, and their intriguing functional properties were demonstrated. Despite such pioneering works, lead-free double perovskite halides with better crystallinity are still in demand for applications to no…
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Lead-free double perovskite halides are emerging optoelectronic materials that are alternatives to lead-based perovskite halides. Recently, single-crystalline double perovskite halides were synthesized, and their intriguing functional properties were demonstrated. Despite such pioneering works, lead-free double perovskite halides with better crystallinity are still in demand for applications to novel optoelectronic devices. Here, we realized highly crystalline Cs2AgBiBr6 single crystals with a well-defined atomic ordering on the microscopic scale. We avoided the formation of Ag vacancies and the subsequent secondary Cs3Bi2Br9 by manipulating the initial chemical environments in hydrothermal synthesis. The suppression of Ag vacancies allows us to reduce the trap density in the as-grown crystals and to enhance the carrier mobility further. Our design strategy is applicable for fabricating other lead-free halide materials with high crystallinity.
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Submitted 29 June, 2020;
originally announced June 2020.
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Macroscopic visualization of fast electrochemical reaction of SrCoOx oxygen sponge
Authors:
Qian Yang,
Hai Jun Cho,
Hyoungjeen Jeen,
Hiromichi Ohta
Abstract:
Strontium cobaltite (SrCoOx) is known as a material showing fast topotactic electrochemical Redox reaction so-called oxygen sponge. Although atomic scale phenomenon of the oxidation of SrCoO2.5 into SrCoO3 is known, the macroscopic phenomenon has not been clarified yet thus far. Here, we visualize the electrochemical oxidation of SrCoOx macroscopically. SrCoOx epitaxial films with various oxidatio…
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Strontium cobaltite (SrCoOx) is known as a material showing fast topotactic electrochemical Redox reaction so-called oxygen sponge. Although atomic scale phenomenon of the oxidation of SrCoO2.5 into SrCoO3 is known, the macroscopic phenomenon has not been clarified yet thus far. Here, we visualize the electrochemical oxidation of SrCoOx macroscopically. SrCoOx epitaxial films with various oxidation states were prepared by the electrochemical oxidation of SrCoO2.5 film into SrCoO3-d film. Steep decrease of both resistivity and the absolute value of thermopower of electrochemically oxidized SrCoOx epitaxial films indicated the columnar oxidation firstly occurred along with the surface normal and then spread in the perpendicular to the normal. Further, we directly visualized the phenomena using the conductive AFM. This macroscopic image of the electrochemical oxidation would be useful to develop a functional device utilizing the electrochemical redox reaction of SrCoOx.
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Submitted 24 October, 2019;
originally announced October 2019.
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Water-Quenched Effects of 5 wt.% (Fe, Ti) particle-doped MgB$_2$ Superconductor and Low Limit of Pinning Effect
Authors:
H. B. Lee,
G. C. Kim,
Hyoungjeen Jeen,
Y. C. Kim
Abstract:
\begin{abstract}
We have studied magnetic properties of water-quenched 5 wt.% (Fe, Ti) particle-doped MgB$_2$ comparing with that of air-cooled one. Generally, grain refinement is achieved by increasing cooling rate, which implies an increase of grainboundaries in the superconductor. Here we show that increased grainboundaries influence what kinds of effects on the field dependence of magnetizat…
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\begin{abstract}
We have studied magnetic properties of water-quenched 5 wt.% (Fe, Ti) particle-doped MgB$_2$ comparing with that of air-cooled one. Generally, grain refinement is achieved by increasing cooling rate, which implies an increase of grainboundaries in the superconductor. Here we show that increased grainboundaries influence what kinds of effects on the field dependence of magnetization and what is the mechanism. As a result, they are served as a pinning center at a high field whereas they are served as a pathway to facilitate the movement of fluxes pinned on volume defects at a low field. As modeling grainboundaries in a superconductor, we explained that they had a flux pinning effect as well as the flux-penetrating promotion effect. As temperature increases, the pinning ability of a grainboundaries decreases, which was caused by increased coherence length. Stacking fault planes and twin boundaries have also been considered by using the model. It explained the reason for that stacking fault planes of MgB$_2$ do not have any pinning effect and the twin boundary of HTSC have the strong pinning or strong flux-penetration effect depending on the direction of the applied field.
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Submitted 30 May, 2020; v1 submitted 13 June, 2019;
originally announced June 2019.
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Buffer layer-less fabrication of high-mobility transparent oxide semiconductor, La-doped BaSnO3
Authors:
Anup V. Sanchela,
Mian Wei,
Joonhyuk Lee,
Gowoon Kim,
Hyoungjeen Jeen,
Bin Feng,
Yuichi Ikuhara,
Hai Jun Cho,
Hiromichi Ohta
Abstract:
Transparent oxide semiconductors (TOSs) showing both high visible transparency and high electron mobility have attracted great attention towards the realization of advanced optoelectronic devices. La-doped BaSnO3 (LBSO) is one of the most promising TOSs because its single crystal exhibits a high electron mobility. However, in the LBSO films, it is very hard to obtain high mobility due to the threa…
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Transparent oxide semiconductors (TOSs) showing both high visible transparency and high electron mobility have attracted great attention towards the realization of advanced optoelectronic devices. La-doped BaSnO3 (LBSO) is one of the most promising TOSs because its single crystal exhibits a high electron mobility. However, in the LBSO films, it is very hard to obtain high mobility due to the threading dislocations, which are originated from the lattice mismatch between the film and the substrate. Therefore, many researchers have tried to improve the mobility by inserting a buffer layer. While the buffer layers increased the electron mobilities, this approach leaves much to be desired since it involves a two-step film fabrication process and the enhanced mobility values are still significantly lower than single crystal values. We show herein that the electron mobility of LBSO films can be improved without inserting any buffer layers if the films are grown under highly oxidative ozone (O3) atmospheres. The O3 environments relaxed the LBSO lattice and reduced the formation of Sn2+ states, which are known to suppress the electron mobility in LBSO. The resultant O3-LBSO films showed improved mobility values up to 115 cm2 V-1 s-1, which is among the highest in LBSO films on SrTiO3 substrates and comparable to LBSO films with buffer layers.
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Submitted 22 August, 2018;
originally announced August 2018.
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Large thickness dependence of the carrier mobility in a transparent oxide semiconductor, La-doped BaSnO3
Authors:
Anup V. Sanchela,
Mian Wei,
Haruki Zensyo,
Bin Feng,
Joonhyuk Lee,
Gowoon Kim,
Hyoungjeen Jeen,
Yuichi Ikuhara,
Hiromichi Ohta
Abstract:
We report herein that the carrier mobility of the 2%-La-doped BaSnO3 (LBSO) films on (001) SrTiO3 and (001) MgO substrates strongly depends on the thickness whereas it is unrelated to the lattice mismatch (+5.4% for SrTiO3, -2.3% for MgO). Although we observed large differences in the lattice parameters, the lateral grain size (~85 nm for SrTiO3, ~20 nm for MgO), the surface morphology and the den…
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We report herein that the carrier mobility of the 2%-La-doped BaSnO3 (LBSO) films on (001) SrTiO3 and (001) MgO substrates strongly depends on the thickness whereas it is unrelated to the lattice mismatch (+5.4% for SrTiO3, -2.3% for MgO). Although we observed large differences in the lattice parameters, the lateral grain size (~85 nm for SrTiO3, ~20 nm for MgO), the surface morphology and the density of misfit dislocations, the mobility increased almost simultaneously with the thickness in both cases and saturated at ~100 cm2 V-1 s-1, together with the approaching to the nominal carrier concentration (=[2% La3+]), clearly indicating that the behavior of mobility depends on the film thickness. The present results would be beneficial to understand the behavior of mobility and fruitful to further enhance the mobility of LBSO films.
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Submitted 3 May, 2018; v1 submitted 15 April, 2018;
originally announced April 2018.
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Electronic and magnetic properties of epitaxial SrRhO3 films
Authors:
John Nichols,
Simuck F. Yuk,
Changhee Sohn,
Hyoungjeen Jeen,
John W. Freeland,
Valentino R. Cooper,
Ho Nyung Lee
Abstract:
Strong interplay of fundamental order parameters in complex oxides are known to give rise to exotic physical phenomena. The 4d transition metal oxide SrRhO3 has generated much interest, but advances have been hindered by difficulties in preparing single crystalline phases. Here, we have epitaxially stabilized high quality single crystalline SrRhO3 films and investigated their structural, electroni…
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Strong interplay of fundamental order parameters in complex oxides are known to give rise to exotic physical phenomena. The 4d transition metal oxide SrRhO3 has generated much interest, but advances have been hindered by difficulties in preparing single crystalline phases. Here, we have epitaxially stabilized high quality single crystalline SrRhO3 films and investigated their structural, electronic, and magnetic properties. We determine that their properties significantly differ from the paramagnetic metallic ground state that governs bulk samples and are strongly related to rotations of the RhO6 octahedra.
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Submitted 16 June, 2017;
originally announced June 2017.
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Enhancing Perovskite Electrocatalysis through Strain Tuning of the Oxygen Deficiency
Authors:
Jonathan R. Petrie,
Hyoungjeen Jeen,
Sara C. Barron,
Tricia L. Meyer,
Ho Nyung Lee
Abstract:
Oxygen vacancies in transition metal oxides facilitate catalysis critical for energy storage and generation. However, it has proven elusive to promote vacancies at the lower temperatures required for operation in devices such as metal-air batteries and portable fuel cells. Here, we use thin films of the perovskite-based strontium cobaltite (SrCoOx) to show that epitaxial strain is a powerful tool…
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Oxygen vacancies in transition metal oxides facilitate catalysis critical for energy storage and generation. However, it has proven elusive to promote vacancies at the lower temperatures required for operation in devices such as metal-air batteries and portable fuel cells. Here, we use thin films of the perovskite-based strontium cobaltite (SrCoOx) to show that epitaxial strain is a powerful tool towards manipulating the oxygen content under conditions consistent with the oxygen evolution reaction, yielding increasingly oxygen deficient states in an environment where the cobaltite would normally be fully oxidized. The additional oxygen vacancies created through tensile strain enhance the cobaltite catalytic activity towards this important reaction by over an order of magnitude, equaling that of precious metal catalysts, including IrO2. Our findings demonstrate that strain in these oxides can dictate oxygen stoichiometry independent of ambient conditions, allowing unprecedented control over oxygen vacancies essential in catalysis near room temperature.
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Submitted 7 June, 2016;
originally announced June 2016.
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Strain Control of Oxygen Vacancies in Epitaxial Strontium Cobaltite Films
Authors:
Jonathan R. Petrie,
Chandrima Mitra,
Hyoungjeen Jeen,
Woo Seok Choi,
Tricia L. Meyer,
Fernando A. Reboredo,
John W. Freeland,
Gyula Eres,
Ho Nyung Lee
Abstract:
The ability to manipulate oxygen anion defects rather than metal cations in complex oxides can facilitate creating new functionalities critical for emerging energy and device technologies. However, the difficulty in activating oxygen at reduced temperatures hinders the deliberate control of important defects, oxygen vacancies. Here, strontium cobaltite (SrCoOx) is used to demonstrate that epitaxia…
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The ability to manipulate oxygen anion defects rather than metal cations in complex oxides can facilitate creating new functionalities critical for emerging energy and device technologies. However, the difficulty in activating oxygen at reduced temperatures hinders the deliberate control of important defects, oxygen vacancies. Here, strontium cobaltite (SrCoOx) is used to demonstrate that epitaxial strain is a powerful tool for manipulating the oxygen vacancy concentration even under highly oxidizing environments and at annealing temperatures as low as 300 C. By applying a small biaxial tensile strain (2%), the oxygen activation energy barrier decreases by ~30%, resulting in a tunable oxygen deficient steady-state under conditions that would normally fully oxidize unstrained cobaltite. These strain-induced changes in oxygen stoichiometry drive the cobaltite from a ferromagnetic metal towards an antiferromagnetic insulator. The ability to decouple the oxygen vacancy concentration from its typical dependence on the operational environment is useful for effectively designing oxides materials with a specific oxygen stoichiometry.
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Submitted 12 February, 2016;
originally announced February 2016.
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Structural evolution of epitaxial SrCoOx films near topotactic phase transition
Authors:
Hyoungjeen Jeen,
Ho Nyung Lee
Abstract:
Control of oxygen stoichiometry in complex oxides via topotactic phase transition is an interesting avenue to not only modifying the physical properties, but utilizing in many energy technologies, such as energy storage and catalysts. However, detailed structural evolution in the close proximity of the topotactic phase transition in multivalent oxides has not been much studied. In this work, we us…
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Control of oxygen stoichiometry in complex oxides via topotactic phase transition is an interesting avenue to not only modifying the physical properties, but utilizing in many energy technologies, such as energy storage and catalysts. However, detailed structural evolution in the close proximity of the topotactic phase transition in multivalent oxides has not been much studied. In this work, we used strontium cobaltites (SrCoOx) epitaxially grown by pulsed laser epitaxy (PLE) as a model system to study the oxidation-driven evolution of the structure, electronic, and magnetic properties. We grew coherently strained SrCoO2.5 thin films and performed post-annealing at various temperatures for topotactic conversion into the perovskite phase (SrCoO3-δ). We clearly observed significant changes in electronic transport, magnetism, and microstructure near the critical temperature for the topotactic transformation from the brownmillerite to the perovskite phase. Nevertheless, the overall crystallinity was well maintained without much structural degradation, indicating that topotactic phase control can be a useful tool to control the physical properties repeatedly via redox reactions.
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Submitted 18 December, 2015;
originally announced December 2015.
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Temperature evolution of polaron dynamics and Jahn-Teller distortion modes in strongly correlated La$_{0.67}$Ca$_{0.33}$MnO$_{3}$ manganite film
Authors:
Naween Anand,
Naveen Margankunte,
Hyoungjeen Jeen,
A. F. Hebard,
Amlan Biswas,
David B. Tanner
Abstract:
Reflectivity as a function of temperature for the La$_{0.67}$Ca$_{0.33}$MnO$_{3}$ (LCMO) film has been measured across the metal-insulator phase transition. The optical properties and their temperature dependence were determined in the infrared and visible range by fits to a Drude-Lorentz model, using exact formula for the thin film optics and the measured properties of the substrate. The phonon m…
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Reflectivity as a function of temperature for the La$_{0.67}$Ca$_{0.33}$MnO$_{3}$ (LCMO) film has been measured across the metal-insulator phase transition. The optical properties and their temperature dependence were determined in the infrared and visible range by fits to a Drude-Lorentz model, using exact formula for the thin film optics and the measured properties of the substrate. The phonon modes were identified and verified with lattice dynamical calculations for the ideal and distorted perovskite structure of the material. The optical conductivity shows agreement with the double exchange mechanism in conjunction with the Jahn-Teller distortion term in the Hamiltonian. Low temperature metallic phase is dominated by large polaron dynamics, a key component of electron-orbital coupling in a strongly corrrelated system. Free carrier dynamics in the metallic phase is described in terms of coherent heavy polaronic motion in the DC limit with incoherent and asymmetric polaronic background in the mid-IR range. The strength and line width of Jahn-Teller modes has been discussed across the phase transition and their temperature evolution is qualitatively discussed on account of existing electron-phonon coupling. The localized Holstein polaron formation in the high temperature insulative phase is identified as optical conductivity peaks in the visible range above the critical temperature.
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Submitted 29 March, 2018; v1 submitted 8 December, 2015;
originally announced December 2015.
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Symmetry-driven atomic rearrangement at a brownmillerite-perovskite interface
Authors:
Tricia L. Meyer,
Hyoungjeen Jeen,
Xiang Gao,
Jonathan R. Petrie,
Matthew F. Chisholm,
Ho Nyung Lee
Abstract:
Many of the recent advancements in oxide heterostructures have been attributed to modification of spin, charge, lattice, and orbital order parameters at atomically well-defined interfaces. However, the details on the structural, chemical, and electrostatic evolution of interfaces comprised of materials with different crystallographic symmetries remain to be understood. In this work, we have mapped…
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Many of the recent advancements in oxide heterostructures have been attributed to modification of spin, charge, lattice, and orbital order parameters at atomically well-defined interfaces. However, the details on the structural, chemical, and electrostatic evolution of interfaces comprised of materials with different crystallographic symmetries remain to be understood. In this work, we have mapped out the interfacial connectivity of atoms of two dissimilar materials, the perovskite SrTiO3 and the brownmillerite SrCoO2.5, using high resolution scanning transmission electron microscopy and geometric phase analysis. We observed unique symmetry-mismatch driven atomic displacements restricted to only the first few atomic layers, which can critically modify the properties of the system. Provided that SrCoO2.5 is a promising energy material due to its open framework structure, the improved understanding of the interfacial structure on the atomic level can lead to the rational design of novel oxide heterostructures.
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Submitted 19 November, 2015;
originally announced November 2015.
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Structural and Magnetic Phase Transitions in CeCu$_{6-x}T_x$ ($T$ = Ag, Pd)
Authors:
L. Poudel,
C. de la Cruz,
E. A. Payzant,
A. F. May,
M. Koehler,
V. O. Garlea,
A. E. Taylor,
D. S. Parker,
H. B. Cao,
M. A. McGuire,
W. Tian,
M. Matsuda,
H. Jeen,
H. N. Lee,
T. Hong,
S. Calder,
H. D. Zhou,
M. D. Lumsden,
V. Keppens,
D. Mandrus,
A. D. Christianson
Abstract:
The structural and the magnetic properties of CeCu$_{6-x}$Ag$_x$ (0 $\leq$ $x$ $\leq$ 0.85) and CeCu$_{6-x}$Pd$_x$ (0 $\leq$ $x$ $\leq$ 0.4) have been studied using neutron diffraction, resonant ultrasound spectroscopy (RUS), heat capacity, x-ray diffraction measurements and first principles calculations. The structural and magnetic phase diagrams of CeCu$_{6-x}$Ag$_x$ and CeCu$_{6-x}$Pd$_x$ as a…
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The structural and the magnetic properties of CeCu$_{6-x}$Ag$_x$ (0 $\leq$ $x$ $\leq$ 0.85) and CeCu$_{6-x}$Pd$_x$ (0 $\leq$ $x$ $\leq$ 0.4) have been studied using neutron diffraction, resonant ultrasound spectroscopy (RUS), heat capacity, x-ray diffraction measurements and first principles calculations. The structural and magnetic phase diagrams of CeCu$_{6-x}$Ag$_x$ and CeCu$_{6-x}$Pd$_x$ as a function of Ag/Pd composition are reported. The end member, CeCu$_6$, undergoes a structural phase transition from an orthorhombic ($Pnma$) to a monoclinic ($P2_1/c$) phase at 240 K. In CeCu$_{6-x}$Ag$_x$, the structural phase transition temperature (${T_{s}}$) decreases linearly with Ag concentration and extrapolates to zero at $x_{S}$ $\approx$ 0.1. The structural transition in CeCu$_{6-x}$Pd$_x$ remains unperturbed with Pd substitution within the range of our study. The lattice constant $b$ slightly decreases with Ag/Pd doping, whereas, $a$ and $c$ increase with an overall increase in the unit cell volume. Both systems, CeCu$_{6-x}$Ag$_x$ and CeCu$_{6-x}$Pd$_x$, exhibit a magnetic quantum critical point (QCP), at $x$ $\approx$ 0.2 and $x$ $\approx$ 0.05 respectively. Near the QCP, long range antiferromagnetic ordering takes place at an incommensurate wave vector ($δ_1$ 0 $δ_2$) where $δ_1 \sim 0.62$, $δ_2 \sim 0.25$, $x$ = 0.125 for CeCu$_{6-x}$Pd$_x$ and $δ_1 \sim 0.64$, $δ_2 \sim 0.3$, $x$ = 0.3 for CeCu$_{6-x}$Ag$_x$. The magnetic structure consists of an amplitude modulation of the Ce-moments which are aligned along the $c$-axis of the orthorhombic unit cell.
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Submitted 25 November, 2015; v1 submitted 1 October, 2015;
originally announced October 2015.
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Composition dependence of electronic, magnetic, transport and morphological properties of mixed valence manganite thin films
Authors:
Surendra Singh,
J. W. Freeland,
M. R. Fitzsimmons,
H. Jeen,
A. Biswas
Abstract:
We present a comparison of the in-plane length scale over which charge and magnetism are correlated in (La0.4Pr0.6)1-xCaxMnO3 films with x = 0.33 and 0.375, across the metal to insulator transition (MIT) temperature. We combine electrical transport (resistance) measurements, x-ray absorption spectroscopy (XAS), x-ray magnetic circular dichroism (XMCD), and specular/off-specular x-ray resonant magn…
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We present a comparison of the in-plane length scale over which charge and magnetism are correlated in (La0.4Pr0.6)1-xCaxMnO3 films with x = 0.33 and 0.375, across the metal to insulator transition (MIT) temperature. We combine electrical transport (resistance) measurements, x-ray absorption spectroscopy (XAS), x-ray magnetic circular dichroism (XMCD), and specular/off-specular x-ray resonant magnetic scattering (XRMS) measurements as a function of temperature to elucidate relationships between electronic, magnetic and morphological structure of the thin films. Using off-specular XRMS we obtained the charge-charge and charge-magnetic correlation length of these LPCMO films near the MIT. The charge-magnetic correlation length (~ 12000 Å) for x = 0.33 was much larger (~4 times) than the charge-charge correlation length (~ 3200 Å) at 20 K. Whereas for x = 0.375 the charge-magnetic correlation length (~ 7500 Å) was smaller than the charge-charge correlation length (~ 9000 Å).
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Submitted 28 September, 2015;
originally announced September 2015.
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Proximate transition temperatures amplify linear magnetoelectric coupling in strain-disordered multiferroic BiMnO3
Authors:
Patrick R. Mickel,
Hyoungjeen Jeen,
Pradeep Kumar,
Amlan Biswas,
Arthur F. Hebard
Abstract:
We report a giant linear magnetoelectric coupling in strained BiMnO3 thin films in which the disorder associated with an islanded morphology gives rise to extrinsic relaxor ferroelectricity that is not present in bulk centrosymmetric ferromagnetic crystalline BiMnO3. Strain associated with the disorder is treated as a local variable which couples to the two ferroic order parameters, magnetization…
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We report a giant linear magnetoelectric coupling in strained BiMnO3 thin films in which the disorder associated with an islanded morphology gives rise to extrinsic relaxor ferroelectricity that is not present in bulk centrosymmetric ferromagnetic crystalline BiMnO3. Strain associated with the disorder is treated as a local variable which couples to the two ferroic order parameters, magnetization M and polarization P. A straightforward "gas under a piston" thermodynamic treatment explains the observed correlated temperature dependencies of the product of susceptibilities and the magnetoelectric coefficient together with the enhancement of the coupling by the proximity of the ferroic transition temperatures close to the relaxor freezing temperature. Our interpretation is based on a trilinear coupling term in the free energy of the form L(PXM) where L is a hidden antiferromagnetic order parameter, previously postulated by theory for BiMnO3. This phenomenological invariant not only preserves inversion and time reversal symmetry of the strain-induced interactions but also explains the pronounced linear magnetoelectric coupling without using the more conventional higher order biquadratic interaction proportional to (PM)^2.
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Submitted 7 August, 2015;
originally announced August 2015.
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Manipulation of the magnetic order parameter and the metal-insulator-transition of a manganite thin film with applied elastic stress
Authors:
Surendra Singh,
M. R. Fitzsimmons,
T. Lookman,
H. Jeen,
A. Biswas
Abstract:
We measured the temperature dependence of the saturation magnetization (Ms) of a (La1-xPrx)1-yCayMnO3 (x ~ 0.60, y ~ 0.33) film as a function of applied bending stress. Stress producing a compressive strain of -0.01% along the magnetic easy axis increased the Curie temperature by ~6 K and the metal-insulator-transition by ~4 K. Regardless of whether or not stress is applied to the film, magnetic o…
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We measured the temperature dependence of the saturation magnetization (Ms) of a (La1-xPrx)1-yCayMnO3 (x ~ 0.60, y ~ 0.33) film as a function of applied bending stress. Stress producing a compressive strain of -0.01% along the magnetic easy axis increased the Curie temperature by ~6 K and the metal-insulator-transition by ~4 K. Regardless of whether or not stress is applied to the film, magnetic ordering occurs at temperatures significantly higher than the metal-insulator-transition temperature. The magnetization of the sample at the temperature of the metal-insulator-transition is approximately the site percolation threshold for a two-dimensional spin lattice.
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Submitted 26 March, 2014;
originally announced March 2014.
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Tunneling Electroresistance Induced by Interfacial Phase Transitions in Ultrathin Oxide Heterostructures
Authors:
Lu Jiang,
Woo Seok Choi,
Hyoungjeen Jeen,
Shuai Dong,
Yunseok Kim,
Myung-Geun Han,
Yimei Zhu,
Sergei V. Kalinin,
Elbio Dagotto,
Takeshi Egami,
Ho Nyung Lee
Abstract:
The ferroelectric (FE) control of electronic transport is one of the emerging technologies in oxide heterostructures. Many previous studies in FE tunnel junctions (FTJs) exploited solely the differences in the electrostatic potential across the FTJs that are induced by changes in the FE polarization direction. Here, we show that in practice the junction current ratios between the two polarization…
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The ferroelectric (FE) control of electronic transport is one of the emerging technologies in oxide heterostructures. Many previous studies in FE tunnel junctions (FTJs) exploited solely the differences in the electrostatic potential across the FTJs that are induced by changes in the FE polarization direction. Here, we show that in practice the junction current ratios between the two polarization states can be further enhanced by the electrostatic modification in the correlated electron oxide electrodes, and that FTJs with nanometer thin layers can effectively produce a considerably large electroresistance ratio at room temperature. To understand these surprising results, we employed an additional control parameter, which is related to the crossing of electronic and magnetic phase boundaries of the correlated electron oxide. The FE-induced phase modulation at the heterointerface ultimately results in an enhanced electroresistance effect. Our study highlights that the strong coupling between degrees of freedom across heterointerfaces could yield versatile and novel applications in oxide electronics.
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Submitted 19 November, 2013;
originally announced November 2013.
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Orienting oxygen vacancies for fast catalytic reaction
Authors:
Hyoungjeen Jeen,
Zhonghe Bi,
Woo Seok Choi,
Matthew F. Chisholm,
Craig A. Bridges,
M. Parans Paranthaman,
Ho Nyung Lee
Abstract:
Catalysis is indispensable to chemical processes and relevant to many aspects of modern life. Owing to the intriguing electronic structures and good ionic properties, multivalent transition metal oxides have attracted attention as key catalysts for various energy and environmental applications. Here, we demonstrate that brownmillerite strontium cobaltite (SrCoO2.5) can be a good cathode material f…
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Catalysis is indispensable to chemical processes and relevant to many aspects of modern life. Owing to the intriguing electronic structures and good ionic properties, multivalent transition metal oxides have attracted attention as key catalysts for various energy and environmental applications. Here, we demonstrate that brownmillerite strontium cobaltite (SrCoO2.5) can be a good cathode material for sold oxide fuel cells and rechargeable batteries due to the open oxygen frameworks. When the orientation of oxygen vacancy channels (OVCs) is properly controlled, one can drastically increase the surface oxygen exchange rate approximately up to two orders of magnitude. The improved oxygen reduction kinetics is attributed to a substantial decrease in the thermal activation energy. Importantly, the strong enhancement of crystallographic orientation-dependent oxygen reduction reaction required the creation of neither structural disorders nor chemical doping. Thus, our epitaxial approach can pave a novel pathway to providing precise interpretation of oxygen reduction reactions and to developing oxide-based energy materials.
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Submitted 3 October, 2013;
originally announced October 2013.
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Reversible redox reactions in an epitaxially stabilized SrCoOx oxygen sponge
Authors:
Hyoungjeen Jeen,
Woo Seok Choi,
Michael D. Biegalski,
Chad M. Folkman,
I-Cheng Tung,
Dillon D. Fong,
John W. Freeland,
Dongwon Shin,
Hiromichi Ohta,
Matthew F. Chisholm,
Ho Nyung Lee
Abstract:
Fast, reversible redox reactions in solids at low temperatures without thermomechanical degradation are a promising strategy for enhancing the overall performance and lifetime of many energy materials and devices. However, the robust nature of the cation's oxidation state and the high thermodynamic barrier have hindered the realization of fast catalysis and bulk diffusion at low temperatures. Here…
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Fast, reversible redox reactions in solids at low temperatures without thermomechanical degradation are a promising strategy for enhancing the overall performance and lifetime of many energy materials and devices. However, the robust nature of the cation's oxidation state and the high thermodynamic barrier have hindered the realization of fast catalysis and bulk diffusion at low temperatures. Here, we report a significant lowering of the redox temperature by epitaxial stabilization of strontium cobaltites (SrCoOx) grown directly as one of two distinct crystalline phases, either the perovskite SrCoO3-δ or the brownmillerite SrCoO2.5. Importantly, these two phases can be reversibly switched at a remarkably reduced temperature (200~300 °C) in a considerably short time (< 1 min) without destroying the parent framework. The fast, low temperature redox activity in SrCoO3-δ is attributed to a small Gibbs free energy difference between two topotatic phases. Our findings thus provide useful information for developing highly sensitive electrochemical sensors and low temperature cathode materials.
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Submitted 26 August, 2013;
originally announced August 2013.
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Reversal of the lattice structure in SrCoOx epitaxial thin films studied by real-time optical spectroscopy and first-principles calculations
Authors:
Woo Seok Choi,
Hyoungjeen Jeen,
Jun Hee Lee,
S. S. Ambrose Seo,
Valentino R. Cooper,
Karin M. Rabe,
Ho Nyung Lee
Abstract:
Using real-time spectroscopic ellipsometry, we directly observed a reversible lattice and electronic structure evolution in SrCoOx (x = 2.5 - 3) epitaxial thin films. Drastically different electronic ground states, which are extremely susceptible to the oxygen content x, are found in the two topotactic phases, i.e. the brownmillerite SrCoO2.5 and the perovskite SrCoO3. First principles calculation…
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Using real-time spectroscopic ellipsometry, we directly observed a reversible lattice and electronic structure evolution in SrCoOx (x = 2.5 - 3) epitaxial thin films. Drastically different electronic ground states, which are extremely susceptible to the oxygen content x, are found in the two topotactic phases, i.e. the brownmillerite SrCoO2.5 and the perovskite SrCoO3. First principles calculations confirmed substantial differences in the electronic structure, including a metal-insulator transition, which originates from the modification in the Co valence states and crystallographic structures. More interestingly, the two phases can be reversibly controlled by changing the ambient pressure at greatly reduced temperatures. Our finding provides an important pathway to understanding the novel oxygen-content-dependent phase transition uniquely found in multivalent transition metal oxides.
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Submitted 10 August, 2013;
originally announced August 2013.
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Topotactic phase transformation of the brownmillerite SrCoO2.5 to the perovskite SrCoO3-δ
Authors:
Hyoungjeen Jeen,
Woo Seok Choi,
John W. Freeland,
Hiromichi Ohta,
Chang Uk Jung,
Ho Nyung Lee
Abstract:
Oxygen stoichiometry is one of the most important elements in determining the physical properties of transition metal oxides (TMOs). A small fractional change in the oxygen content, resulting in the variation of valence state of the transition metal, can drastically modify the materials functionalities. In particular, TMOs with mixed valences have attracted attention for many energy applications.…
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Oxygen stoichiometry is one of the most important elements in determining the physical properties of transition metal oxides (TMOs). A small fractional change in the oxygen content, resulting in the variation of valence state of the transition metal, can drastically modify the materials functionalities. In particular, TMOs with mixed valences have attracted attention for many energy applications. Previous studies also showed that the ability to control the number of d-band electron populations and detailed spin configurations is critical for improved catalytic performance of TMOs. In this context, SrCoO$_{x}$ (2.5 < x < 3.0) is an ideal class of materials due to the existence of two structurally distinct topotatic phases, i.e. the brownmillerite SrCoO$_{2.5}$(BM-SCO) and the perovskite SrCoO$_{3}$. Especially, BM-SCO has atomically-ordered one-dimensional vacancy channels, which can accommodate additional oxygen. Moreover, SrCoO$_{x}$ exhibits a wide spectrum of physical properties depending on the oxygen stoichiometry. Since SrCoOx has only a single knob to control the Co valence state without cation doping, it is an attractive material for studying the valence state dependent physical properties. However, so far, the growth of high quality single crystalline materials has not been much studied due to difficulty in controlling the right oxidation state. In this work, we report on the epitaxial growth of BM-SCO single crystalline films on SrTiO3 by pulsed laser epitaxy. In order to examine the topotactic phase transformation to the perovskite SrCoO$_{3-δ}$, some of samples were subsequently in-situ annealed at various oxygen pressure P(O$_{2}$). We found that post-annealing in high P(O$_{2}$) (> several hundreds of Torr) could fill some of oxygen vacancies accompanying systematic evolution in electronic, magnetic, and thermoelectric properties.
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Submitted 15 July, 2013;
originally announced July 2013.
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Strain-Induced Spin States in Atomically Ordered Cobaltites
Authors:
Woo Seok Choi,
Ji-Hwan Kwon,
Hyoungjeen Jeen,
Jorge E. Hamann-Borrero,
Abdullah Radi,
Sebastian Macke,
Ronny Sutarto,
Feizhou He,
George A. Sawatzky,
Vladimir Hinkov,
Miyoung Kim,
Ho Nyung Lee
Abstract:
Epitaxial strain imposed in complex oxide thin films by heteroepitaxy is recognized as a powerful tool for identifying new properties and exploring the vast potential of materials performance. A particular example is LaCoO3, a zero spin, nonmagnetic material in the bulk, whose strong ferromagnetism in a thin film remains enigmatic despite a decade of intense research. Here, we use scanning transmi…
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Epitaxial strain imposed in complex oxide thin films by heteroepitaxy is recognized as a powerful tool for identifying new properties and exploring the vast potential of materials performance. A particular example is LaCoO3, a zero spin, nonmagnetic material in the bulk, whose strong ferromagnetism in a thin film remains enigmatic despite a decade of intense research. Here, we use scanning transmission electron microscopy complemented by X-ray and optical spectroscopy to study LaCoO3 epitaxial thin films under different strain states. We observed an unconventional strain relaxation behavior resulting in stripe-like, lattice modulated patterns, which did not involve uncontrolled misfit dislocations or other defects. The modulation entails the formation of ferromagnetically ordered sheets comprising intermediate or high spin Co3+, thus offering an unambiguous description for the exotic magnetism found in epitaxially strained LaCoO3 films. This observation provides a novel route to tailoring the electronic and magnetic properties of functional oxide heterostructures.
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Submitted 16 August, 2012;
originally announced August 2012.
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Strongly coupled phase transition in ferroelectric/correlated electron oxide heterostructures
Authors:
Lu Jiang,
Woo Seok Choi,
Hyoungjeen Jeen,
Takeshi Egami,
Ho Nyung Lee
Abstract:
We fabricated ultrathin ferroelectric/correlated electron oxide heterostructures composed of the ferroelectric Pb(Zr0.2Ti0.8)O3 and the correlated electron oxide (CEO) La0.8Sr0.2MnO3 on SrTiO3 substrates by pulsed laser epitaxy. The hole accumulation in the ultrathin CEO layer was substantially modified by heterostructuring with the ferroelectric layer, resulting in an insulator-metal transition.…
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We fabricated ultrathin ferroelectric/correlated electron oxide heterostructures composed of the ferroelectric Pb(Zr0.2Ti0.8)O3 and the correlated electron oxide (CEO) La0.8Sr0.2MnO3 on SrTiO3 substrates by pulsed laser epitaxy. The hole accumulation in the ultrathin CEO layer was substantially modified by heterostructuring with the ferroelectric layer, resulting in an insulator-metal transition. In particular, our thickness dependent study showed that drastic changes in transport and magnetic properties were strongly coupled to the modulation of charge carriers by ferroelectric field effect, which was confined to the vicinity of the interface. Thus, our results provide crucial evidence that strong ferroelectric field effect control can be achieved in ultrathin (10 nm) heterostructures, yielding at least a 100,000-fold change in resistivity.
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Submitted 19 July, 2012;
originally announced July 2012.
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Images of metallic and insulating domains on the surface of a (La0.4Pr0.6)0.67Ca0.33MnO3 film
Authors:
Surendra Singh,
M. R. Fitzsimmons,
H. Jeen,
A. Biswas,
M. E. Hawley
Abstract:
Using conductive atomic force microscopy, we observed non-uniform distributions of metallic and insulating domains on the surface of a single crystalline (La0.4Pr0.6)0.67Ca0.33MnO3 film grown on a (110) NdGaO3 substrate. The electronic properties of the surface exhibit thermal hysteresis. The hysteresis is similar to that of the transport and magnetism of the film bulk.
Using conductive atomic force microscopy, we observed non-uniform distributions of metallic and insulating domains on the surface of a single crystalline (La0.4Pr0.6)0.67Ca0.33MnO3 film grown on a (110) NdGaO3 substrate. The electronic properties of the surface exhibit thermal hysteresis. The hysteresis is similar to that of the transport and magnetism of the film bulk.
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Submitted 9 May, 2012; v1 submitted 20 January, 2012;
originally announced January 2012.
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Measurement of the coupling between applied stress and magnetism in a manganite thin film
Authors:
Surendra Singh,
M. R. Fitzsimmons,
T. Lookman,
H. Jeen,
A. Biswas,
M. A. Roldan,
M. Varela
Abstract:
We measured the magnetization depth profile of a (La1-xPrx)1-yCayMnO3 (x = 0.60\pm0.04, y = 0.20\pm0.03) film as a function of applied bending stress using polarized neutron reflectometry. From these measurements we obtained a coupling coefficient relating strain to the depth dependent magnetization. We found application of compressive (tensile) bending stress along the magnetic easy axis increase…
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We measured the magnetization depth profile of a (La1-xPrx)1-yCayMnO3 (x = 0.60\pm0.04, y = 0.20\pm0.03) film as a function of applied bending stress using polarized neutron reflectometry. From these measurements we obtained a coupling coefficient relating strain to the depth dependent magnetization. We found application of compressive (tensile) bending stress along the magnetic easy axis increases (decreases) the magnetization of the film.
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Submitted 19 January, 2012;
originally announced January 2012.
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Magnetic non-uniformity and thermal hysteresis of magnetism in a manganite thin film
Authors:
Surendra Singh,
M. R. Fitzsimmons,
T. Lookman,
J. D. Thompson,
H. Jeen,
A. Biswas,
M. A. Roldan,
M. Varela
Abstract:
We measured the chemical and magnetic depth profiles of a single crystalline (La$_{1-x}$Pr$_x$)$_{1-y}$Ca$_y$MnO$_{3-δ}$ (x = 0.52\pm0.05, y = 0.23\pm0.04, δ = 0.14\pm0.10) film grown on a NdGaO3 substrate using x-ray reflectometry, electron microscopy, electron energy-loss spectroscopy and polarized neutron reflectometry. Our data indicate that the film exhibits coexistence of different magnetic…
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We measured the chemical and magnetic depth profiles of a single crystalline (La$_{1-x}$Pr$_x$)$_{1-y}$Ca$_y$MnO$_{3-δ}$ (x = 0.52\pm0.05, y = 0.23\pm0.04, δ = 0.14\pm0.10) film grown on a NdGaO3 substrate using x-ray reflectometry, electron microscopy, electron energy-loss spectroscopy and polarized neutron reflectometry. Our data indicate that the film exhibits coexistence of different magnetic phases as a function of depth. The magnetic depth profile is correlated with a variation of chemical composition with depth. The thermal hysteresis of ferromagnetic order in the film suggests a first order ferromagnetic transition at low temperatures.
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Submitted 14 December, 2011;
originally announced December 2011.
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Growth of atomically smooth thin films of the electronically phase separated manganite (La$_{0.5}$Pr$_{0.5}$)$_{0.67}$Ca$_{0.33}$MnO$_{3}$
Authors:
Hyoungjeen Jeen,
Rafiya Javed,
Amlan Biswas
Abstract:
Atomically flat, epitaxial, and stoichiometric thin films of the electronically phase separated compound (La$_{0.5}$Pr$_{0.5}$)$_{0.67}$Ca$_{0.33}$MnO$_{3}$ were grown on as-received and treated NdGaO$_{3}$ substrates by fine tuning of oxygen pressure during deposition. Optimal thin films with step flow growth mode show superior physical properties compared to thin films grown in off-optimal oxyge…
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Atomically flat, epitaxial, and stoichiometric thin films of the electronically phase separated compound (La$_{0.5}$Pr$_{0.5}$)$_{0.67}$Ca$_{0.33}$MnO$_{3}$ were grown on as-received and treated NdGaO$_{3}$ substrates by fine tuning of oxygen pressure during deposition. Optimal thin films with step flow growth mode show superior physical properties compared to thin films grown in off-optimal oxygen pressures, {\em viz.} the highest maximum temperature coefficient of resistance, the highest peak-resistivity temperature, and reduced coercive fields. Transport, magnetization, and x-ray diffraction measurements indicate that the oxygen pressure during growth plays a critical role in the formation of oxygen vacancies, cation vacancies, and grain boundaries.
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Submitted 14 September, 2011;
originally announced September 2011.
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Single domain to multi-domain transition due to in-plane magnetic anisotropy in phase separated (La$_{0.4}$Pr$_{0.6}$)$_{0.67}$Ca$_{0.33}$MnO$_{3}$ thin films
Authors:
Hyoungjeen Jeen,
Amlan Biswas
Abstract:
Phase separated perovskite manganites have competing phases with different crystal structures, magnetic and electronic properties. Hence, strain effects play a critical role in determining the magnetic properties of manganite thin films. Here we report the effect of anisotropic stress on the magnetic properties of the phase separated manganite (La$_{0.4}$Pr$_{0.6}$)$_{0.67}$Ca$_{0.33}$MnO$_{3}$. T…
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Phase separated perovskite manganites have competing phases with different crystal structures, magnetic and electronic properties. Hence, strain effects play a critical role in determining the magnetic properties of manganite thin films. Here we report the effect of anisotropic stress on the magnetic properties of the phase separated manganite (La$_{0.4}$Pr$_{0.6}$)$_{0.67}$Ca$_{0.33}$MnO$_{3}$. Thin films of (La$_{0.4}$Pr$_{0.6}$)$_{0.67}$Ca$_{0.33}$MnO$_{3}$ grown under anisotropic in-plane stress on (110) NdGaO$_{3}$ substrates display in-plane mangetic anisotropy and single domain to multidomain transition as a function of temperature. Angle dependent magnetization measurements also show that the magnetization reversal occurs mainly through the nucleation $&$ propagation mechanism. By comparing the results with (La$_{0.4}$Pr$_{0.6}$)$_{0.67}$Ca$_{0.33}$MnO$_{3}$ thin films grown on (001) SrLaGaO$_{4}$ substrates, we have confirmed that the magnetic anisotropy is mainly due to substrate induced anisotropic stress. Our results suggest novel avenues for storing magnetic information in nanoscale magnetic media.
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Submitted 26 October, 2010;
originally announced October 2010.
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Growth and characterization of multiferroic BiMnO$_3$ thin films
Authors:
Hyoungjeen Jeen,
Guneeta Singh-Bhalla,
Patrick R. Mickel,
Kristen Voigt,
Chelsey Morien,
Sefaattin Tongay,
A. F. Hebard,
Amlan Biswas
Abstract:
We have grown epitaxial thin films of multiferroic BiMnO$_3$ using pulsed laser deposition. The films were grown on SrTiO$_3$ (001) substrates by ablating a Bi-rich target. Using x-ray diffraction we confirmed that the films were epitaxial and the stoichiometry of the films was confirmed using Auger electron spectroscopy. The films have a ferromagnetic Curie temperature ($T_C$) of 85$\pm$5 K and a…
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We have grown epitaxial thin films of multiferroic BiMnO$_3$ using pulsed laser deposition. The films were grown on SrTiO$_3$ (001) substrates by ablating a Bi-rich target. Using x-ray diffraction we confirmed that the films were epitaxial and the stoichiometry of the films was confirmed using Auger electron spectroscopy. The films have a ferromagnetic Curie temperature ($T_C$) of 85$\pm$5 K and a saturation magnetization of 1 $μ_B$/Mn. The electric polarization as a function of electric field ($P-E$) was measured using an interdigital capacitance geometry. The $P-E$ plot shows a clear hysteresis that confirms the multiferroic nature of the thin films.
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Submitted 28 May, 2010;
originally announced May 2010.