Spin and lattice excitations of a BiFeO3 thin film and ceramics

International audience2 count the nearest and next-nearest neighbor exchange interactions, two Dzyaloshinskii-Moriya interactions and an easy-axis anisotropy. 31,35 The same model successfully described the low-energy inelastic neutron scattering spectra. 30 In contrast, Komandin et al. 15 showed IR transmission spectra with an excitation at approximately 47 cm −1 which had not been previously reported by experimental or theoretical studies. The intensive discussion in the literature concerning the nature of the spin ex-citations raises the question: which excitations are pure magnons (i.e., contribute only to the magnetic perme-ability µ) and which are electromagnons (i.e., influence at least partially the permittivity ε *)? It is worth noting that according to a recent symmetry analysis, 36 BiFeO 3 allows directional dichroism and therefore spin waves can be simultaneously excited by the electric and magnetic components of electromagnetic radiation. For more details on BiFeO 3 spin dynamics, see the review of Park et al. 37 In the current work, we report spin and lattice exci-tations in BiFeO 3 ceramics, as measured by the combination of IR reflectivity and time-domain THz transmission spectroscopy, in a temperature range from 10 to 900 K. All 13 IR-active phonon modes are observed, exhibiting softening on heating. Five low-frequency spin modes are detected from 5 K up to RT, the highest two appearing at 53 and 56 cm −1. This corresponds to the frequency range where such excitations were theoretically predicted, 31,32,35 but not experimentally confirmed up to now. At 5 K, the low-energy spin dynamics in the THz range were also studied in a varying magnetic field of up to 7 T. Softening of the (electro)magnon frequencies upon increasing the magnetic field was observed. Additionally, a BiFeO 3 epitaxial thin film grown on an orthorhombic (110) TbScO 3 single crystal substrate was studied for the first time via IR reflectance spectroscopy. II. EXPERIMENTAL DETAILS BiFeO 3 ceramics were prepared by the solid-state route. A stoichiometric mixture of Fe 2 O 3 and Bi 2 O 3 powder oxides with a purity of 99.99% was ground and uniaxially cold-pressed under 20-30 MPa pressure into 8 mm diameter pellets. The pellets were then covered by sacrificial BFO powder to avoid bismuth oxide loss from the pellet, and sintered in a tube furnace at 825 • C for8 h in air. To avoid any secondary phase formation, the samples were quenched to RT. Polished disks with a diameter of 4 mm and thicknesses of ca. 600 and 338 µm were used for the IR reflectivity and THz transmission measurements, respectively. An epitaxial BiFeO 3 thin film with a thickness of 300 nm was grown by reactive molecular-beam epitaxy on a (110) single crystal substrate. The growth parameters were the same as for the samples reported in Ref. 38. Near-normal incidence IR reflectivity spectra of the BiFeO 3 ceramics and film were obtained using a Fourier-transform IR spectrometer Bruker IFS 113v in the frequency range 20-3000 cm −1 (0.6-90 THz) at RT; for the low and high temperature measurements the spectral range was reduced to 650 cm −1. Pyroelectric deuterated triglycine sulfate detectors were used for the room-and high-temperature measurements up to 900 K, whereas a He-cooled (operating temperature 1.6 K) Si bolometer was used for the low-temperature measurements down to 10 K. A commercial high-temperature cell (SPECAC P/N 5850) was used for the high-temperature experiments. The thermal radiation from the hot sample entering the interferometer was taken into account in our spectra evaluation. THz measurements from 3 cm −1 to 60 cm −1 (0.09-1.8 THz) were performed in the transmission mode with the use of a custom-made time-domain terahertz spectrometer. In this spectrometer, a femtosecond Ti:sapphire laser oscillator (Coherent, Mira) produces a train of femtosecond pulses which generates linearly polarized broadband THz pulses in a photoconduct-ing switch TeraSED (Giga-Optics). A gated detection scheme based on electrooptic sampling with a 1 mm thick [110] ZnTe crystal as a sensor allows us to measure the time profile of the electric field of the transmitted THz pulse. The same high-temperature cell as for the IR reflectivity was used for the THz range high-temperature measurements. Oxford Instruments Opti-stat optical cryostats with mylar and polyethylene windows were used for the low-temperature THz and IR measurements , respectively. THz experiments in an external magnetic field H ext ≤ 7 T were performed upon decreasing H with an Oxford Instruments Spectromag cryostat in the Voigt configuration, where the electric component of the THz radiation E THz was set perpendicular to H ext. The IR reflectivity and THz complex (relative) per-mittivity spectra ε * (ω) were carefully fit assuming the factorized form of the dielectric function based on a generalized damped-harmonic-oscillator model: 39 ε * (ω) = ε ∞ N j=1 ω 2 LOj − ω 2 + iωγ LOj ω 2 TOj − ω 2 + iωγ TOj , (1) where ω TOj and ω LOj are the frequencies of the j-th transverse optical (TO) and longitudinal optical (LO) phonons, γ TOj and γ LOj are the corresponding damping constants, and ε ∞ denotes the high-frequency (elec-tronic) contribution to the permittivity, determined from the RT frequency-independent reflectivity tail above the phonon frequencies. The reflectivity R(ω) is related to the complex dielectric function ε * (ω) by: R(ω) = ε * (ω) − 1 ε * (ω) + 1. (2) To evaluate the IR reflectance spectra of the BiFeO 3 /TbScO 3 thin film, a model corresponding to a two-layer optical system was used. 40 The IR reflectivity spectra of the bare TbScO 3 substrate were fit first at eac