Anomalies in thermal expansion and heat capacity of TmB50 at low temperatures: magnetic phase transition and crystal electric field effect
We experimentally study the heat capacity and thermal expansion of thulium boride (TmB50) at temperatures of 2–300 K. The wide temperature range (2–180 K) of boride negative expansion was revealed. We found the anomalies in C(T) heat capacity temperature dependence, attributed to the Schottky contribution (i.e. the influence of the crystal electric field: CEF), as well as the magnetic phase transition. CEF-splitting of the f-levels of the Tm3+ ion was described by the Schottky function of heat capacity with a quasi-quartet in the ground state. Excited multiplets are separated from the ground state by energy gaps δ1 = 100 K, and δ2 ≈ 350 K. The heat capacity maximum at Tmax ≈ 2.4 K may be attributed to the possible magnetic transition in TmB50. Other possible causes of the low-temperature maximum of C(T) dependence are the nonspherical surroundings of rare earth atoms due to the boron atoms in the crystal lattice of the boride and the emergence of two-level systems, as well as the splitting of the ground multiplet due to local magnetic fields of the neighboring ions of thulium. Anomalies in heat capacity are mapped with the thermal expansion features of boride. It is found that the TmB50 thermal expansion characteristic features are due to the influence of the CEF, as well as the asymmetry of the spatial arrangement of boron atoms around the rare earth atoms in the crystal lattice of RB50. The Grüneisen parameters, corresponding to the excitation of different multiplets of CEF-splitting, were determined. A satisfactory accordance between the experimental and estimated temperature dependencies of the boride thermal expansion coefficient was achieved.