The Dice - Stone Der Würfelstein: Some Personal Souvenirs Around the Discovery of the First Ferromagnetic Ferroelectric

Schmid, Hans

doi:10.1080/00150193.2012.673896

Cited by 16 publications

(11 citation statements)

References 71 publications

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“…Following the discovery of simultaneous ferroelectricity and weak ferromagnetism in nickel iodine boracite Ni 3 B 7 O 13 I [23][24][25]-the first material in which the spontaneous magnetization was switched by an electric field and the spontaneous polarization by a magnetic field-the group of 3d-transition-* walter.schnelle@cpfs.mpg.de † Deceased. metal boracites has attracted particular interest in the past fifty years.…”

Section: Introductionmentioning

confidence: 99%

Magnetic and structural phase transitions of multiferroic boracitesM3B7O13X(M=

Schnelle

Schmid

2015

Phys. Rev. B

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The specific heat capacity of mostly single-crystalline samples of 21 boracite compounds M 3 B 7 O 13 X with M a 3d transition metal (Cr, Mn, Fe, Co, Ni, Cu, Zn) or Mg and X a halogen (Cl, Br, I) is determined. In combination with magnetic susceptibility data the magnetic ordering of the M 2+ ions at T N is investigated in detail. The fully ferroelectric/fully ferroelastic structural phase transitions at higher temperatures are measured by differential scanning calorimetry. In the Cr-Br, Cr-I, Cu-Cl, and Cu-Br compounds, previously unknown magnetic phases were found. Magnetic order in the boracites is characterized by the quantum and classical spin states of the M 2+ ions, a variable degree of structural distortion, orbital effects, and competing exchange interactions. The Cu-Cl, Cu-Br, and Ni-Cl boracites exhibit broad maxima of magnetic specific heat and of magnetic susceptibility above T N caused by low-dimensional or frustrated magnetic interactions. Co boracites display additional broad anomalies below T N originating from continuous spin reorientations and effective S = 1/2 ground states. Indications for spin reorientations are also observed for Fe boracites. New phases appear in high magnetic fields for some Co and Fe boracites, which is not the case for the Mn compounds. Stronger magnetic frustration is deduced for the cubic Cr compounds. For the latter compounds and Ni-I boracite magnetostructural phase transitions are observed.

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Section: Introductionmentioning

confidence: 99%

Magnetic and structural phase transitions of multiferroic boracitesM3B7O13X(M=

Schnelle

Schmid

2015

Phys. Rev. B

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“…in the sense Cl → Br → I of decreasing ionic bond strength and hence chemical and mechanical stability. Copper and chromium boracites are outsiders because Cu 2+ and Cr 2+ are Jahn-Teller ions, which find their ideal environment in the center of the X 2 O 4 bipyramid of the cubic phase, which remains stable for Cr-Br, Cr-Br, and Cu-I to at least 4 K. [3] At low temperatures, many boracites exhibit magnetic ordering, which classifies them as multiferroic materials [4][5][6][7] Figure 1 shows the crystallographic structure of most studied boracites at room temperature.…”

Section: Introductionmentioning

confidence: 99%

Raman spectroscopy of M₃B₇O₁₃X boracites (M = Cr,Co,Ni,Cu,Zn,Cd; X = Cl,Br,I)

Iliev

Schmid

2014

J Raman Spectroscopy

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We report results of a Raman study on single crystals of 16 boracites M3B7O13X (M = Cr,Co,Ni,Cu,Zn,Cd; X = Cl,Br,I) over a broad temperature range. The Raman modes for all boracites in their high‐temperature prototype cubic (Fbold-italic4true¯3c) phase are compared. With decreasing temperature, most (but not all) compounds present a transition to the low‐temperature orthorhombic phase (Pca21) or to a sequence of orthorhombic, monoclinic (Pa), and trigonal (R3c) phases. The variations of the Raman spectra through different phases are studied in detail. Special attention is paid to the temperature hysteresis near the transitions and the dependence of transition temperature on the direction of crystal growth for the same material. Copyright © 2014 John Wiley & Sons, Ltd.

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“…In 1964, Hans Schmid was the first to observe the simultaneous existence of ferroelectricity and ferromagnetism in a single material: the synthetic boracite Ni 3 B 7 O 13 I . Two years later, Ascher et al revealed that the magnetic moment and polarization in this boracite were coupled, such that an applied magnetic field could cause complete reversal of the ferroelectric polarization.…”

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The Nature of Magnetoelectric Coupling in Pb(Zr,Ti)O₃–Pb(Fe,Ta)O₃

et al. 2015

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The coupling between magnetization and polarization in a room temperature multiferroic (Pb(Zr,Ti)O3 -Pb(Fe,Ta)O3 ) is explored by monitoring the changes in capacitance that occur when a magnetic field is applied in each of three orthogonal directions. Magnetocapacitance effects, consistent with P(2) M(2) coupling, are strongest when fields are applied in the plane of the single crystal sheet investigated.

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The Dice - Stone Der Würfelstein: Some Personal Souvenirs Around the Discovery of the First Ferromagnetic Ferroelectric

Cited by 16 publications

References 71 publications

Magnetic and structural phase transitions of multiferroic boracitesM3B7O13X(M=

Magnetic and structural phase transitions of multiferroic boracitesM3B7O13X(M=

Raman spectroscopy of M₃B₇O₁₃X boracites (M = Cr,Co,Ni,Cu,Zn,Cd; X = Cl,Br,I)

The Nature of Magnetoelectric Coupling in Pb(Zr,Ti)O₃–Pb(Fe,Ta)O₃

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The Dice - Stone Der Würfelstein: Some Personal Souvenirs Around the Discovery of the First Ferromagnetic Ferroelectric

Cited by 16 publications

References 71 publications

Magnetic and structural phase transitions of multiferroic boracitesM3B7O13X(M=

Magnetic and structural phase transitions of multiferroic boracitesM3B7O13X(M=

Raman spectroscopy of M3B7O13X boracites (M = Cr,Co,Ni,Cu,Zn,Cd; X = Cl,Br,I)

The Nature of Magnetoelectric Coupling in Pb(Zr,Ti)O3–Pb(Fe,Ta)O3

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Raman spectroscopy of M₃B₇O₁₃X boracites (M = Cr,Co,Ni,Cu,Zn,Cd; X = Cl,Br,I)

The Nature of Magnetoelectric Coupling in Pb(Zr,Ti)O₃–Pb(Fe,Ta)O₃