Magnetic and structural phase transitions of multiferroic boracites M3B7O13X (M =3 d transition metal Cr-Zn or Mg; X =halogen Cl, Br, I)
Abstract
The specific heat capacity of mostly single-crystalline samples of 21 boracite compounds M3B7O13X with M a 3 d 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 M2 + ions at TN 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 M2 + 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 TN caused by low-dimensional or frustrated magnetic interactions. Co boracites display additional broad anomalies below TN 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.
- Publication:
-
Physical Review B
- Pub Date:
- May 2015
- DOI:
- 10.1103/PhysRevB.91.184411
- Bibcode:
- 2015PhRvB..91r4411S
- Keywords:
-
- 75.40.Cx;
- 77.84.-s;
- 75.80.+q;
- 61.50.Ks;
- Static properties;
- Dielectric piezoelectric ferroelectric and antiferroelectric materials;
- Magnetomechanical and magnetoelectric effects magnetostriction;
- Crystallographic aspects of phase transformations;
- pressure effects