skip to main content


Title: A Pressure‐Induced Inverse Order–Disorder Transition in Double Perovskites
Abstract

Given the consensus that pressure improves cation ordering in most of known materials, a discovery of pressure‐induced disordering could require recognition of an order–disorder transition in solid‐state physics/chemistry and geophysics. Double perovskites Y2CoIrO6and Y2CoRuO6polymorphs synthesized at 0, 6, and 15 GPa show B‐site ordering, partial ordering, and disordering, respectively, accompanied by lattice compression and crystal structure alteration from monoclinic to orthorhombic symmetry. Correspondingly, the long‐range ferrimagnetic ordering in the B‐site ordered samples are gradually overwhelmed by B‐site disorder. Theoretical calculations suggest that unusual unit‐cell compressions under external pressures unexpectedly stabilize the disordered phases of Y2CoIrO6and Y2CoRuO6.

 
more » « less
NSF-PAR ID:
10143246
Author(s) / Creator(s):
 ;  ;  ;  ;  ;  ;  ;  ;  ;  ;  ;  ;  
Publisher / Repository:
Wiley Blackwell (John Wiley & Sons)
Date Published:
Journal Name:
Angewandte Chemie
Volume:
132
Issue:
21
ISSN:
0044-8249
Page Range / eLocation ID:
p. 8317-8323
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract

    Given the consensus that pressure improves cation ordering in most of known materials, a discovery of pressure‐induced disordering could require recognition of an order–disorder transition in solid‐state physics/chemistry and geophysics. Double perovskites Y2CoIrO6and Y2CoRuO6polymorphs synthesized at 0, 6, and 15 GPa show B‐site ordering, partial ordering, and disordering, respectively, accompanied by lattice compression and crystal structure alteration from monoclinic to orthorhombic symmetry. Correspondingly, the long‐range ferrimagnetic ordering in the B‐site ordered samples are gradually overwhelmed by B‐site disorder. Theoretical calculations suggest that unusual unit‐cell compressions under external pressures unexpectedly stabilize the disordered phases of Y2CoIrO6and Y2CoRuO6.

     
    more » « less
  2. Abstract

    Double perovskite oxides, with generalized formula A2BB$$^{\prime}$$O6, attract wide interest due to their multiferroic and charge transfer properties. They offer a wide range of potential applications such as spintronics and electrically tunable devices. However, great practical limitations are encountered, since a spontaneous order of the B-site cations is notoriously hard to achieve. In this joint experimental-theoretical work, we focused on the characterization of double perovskites La2TiFeO6and La2VCuO6films grown by pulsed laser deposition and interpretation of the observed B-site disorder and partial charge transfer between the B-site ions. A random structure sampling method was used to show that several phases compete due to their corresponding configurational entropy. In order to capture a representative picture of the most relevant competing microstates in realistic experimental conditions, this search included the potential formation of non-stoichiometric phases as well, which could also be directly related to the observed partial charge transfer. We optimized the information encapsulated in the potential energy landscape, captured via structure sampling, by evaluating both enthalpic and entropic terms. These terms were employed as a metric for the competition of different phases. This approach, applied herein specifically to La2TiFeO6, highlights the presence of highly entropic phases above the ground state which can explain the disorder observed frequently in the broader class of double perovskite oxides.

     
    more » « less
  3. Abstract

    Metallic glasses are expected to have quite tunable structures in their configuration space, without the strict constraints of a well-defined crystalline symmetry and large energy barriers separating different states in crystals. However, effectively modulating the structure of metallic glasses is rather difficult. Here, using complementary in situ synchrotron x-ray techniques, we reveal thermal-driven structural ordering in a Ce65Al10Co25metallic glass, and a reverse disordering process via a pressure-induced rejuvenation between two states with distinct structural order characteristics. Studies on other metallic glass samples with different compositions also show similar phenomena. Our findings demonstrate the feasibility of two-way structural tuning states in terms of their dramatic ordering and disordering far beyond the nearest-neighbor shells with the combination of temperature and pressure, extending accessible states of metallic glasses to unexplored configuration spaces.

     
    more » « less
  4. Abstract

    We report the pulsed‐laser deposition of epitaxial double‐perovskite Bi2FeCrO6(BFCO) films on the (001)‐, (110), and (111)‐oriented single‐crystal SrTiO3substrates. All of the BFCO films with various orientations show theandsuperlattice‐diffraction peaks. The intensity ratios between the‐superlattice and the main 111‐diffraction peak can be tailored by simply adjusting the laser repetition rate and substrate temperature, reaching up to 4.4%. However, both optical absorption spectra and magnetic measurements evidence that the strong superlattice peaks are not correlated with theB‐site Fe3+/Cr3+cation ordering. Instead, the epitaxial (111)‐oriented Bi2FeCrO6films show an enhanced remanent polarization of 92 μC/cm2at 10 K, much larger than the predicted values by density‐functional theory calculations. Positive‐up‐negative‐down (PUND) measurements with a time interval of 10 μs further support these observations. Therefore, our experimental results reveal that the strong superlattice peaks may come fromA‐ orB‐site cation shifts along the pseudo‐cubic [111] direction, which further enhance the ferroelectric polarization of the BFCO thin films.

     
    more » « less
  5. null (Ed.)
    Exotic perovskites significantly enrich materials for multiferroic and magnetoelectric applications. However, their design and synthesis is a challenge due to the mostly required recipe conditions at extremely high pressure. Herein, we presented the Ca 2−x Mn x MnTaO 6 (0 ≤ x ≤ 1.0) solid solutions stabilized by chemical pressure assisted with intermediate physical pressure up to 7 GPa. The incorporation of Mn 2+ into the A-site neither drives any cationic ordering nor modifies the orthorhombic Pbnm structure, namely written as (Ca 1−x/2 Mn x/2 )(Mn 1/2 Ta 1/2 )O 3 with disordered A and B site cationic arrangements. The increment of x is accompanied by a ferromagnetic to antiferromagnetic transition around x = 0.2, which is attributed to the double-exchange interactions between A-site Mn 2+ and B-site Mn 3+ . Partial charge disproportionation of the B-site Mn 3+ into Mn 2+ and Mn 4+ occurs for x above 0.8 samples as manifested by X-ray spectrum and magnetic behaviors. The coexistence of B-site Mn 3+ (Jahn–Teller distortion ion) and B′-site Ta 5+ (second-order Jahn–Teller distortion ion) could be energetically responsible for the absence of A-site columnar ordering as observed in other quadruple perovskites with half of the A-sites occupied by small transition-metal cations. These exceptional findings indicate that exotic perovskites can be successfully stabilized at chemical and intermediate physical pressure, and the presence of Jahn–Teller distortion cations at the same lattice should be avoided to enable cationic ordering. 
    more » « less