When the rare earth mononitrides (RENs) first burst onto the scientific scene in the middle of last century, there were feverish dreams that their strong magnetic moment would afford a wide range of applications. For decades research was frustrated by poor stoichiometry and the ready reaction of the materials in ambient conditions, and only recently have these impediments finally been overcome by advances in thin film fabrication with ultra-high vacuum based growth technology. Currently, the field of research into the RENs is growing rapidly, motivated by the materials demands of proposed electronic and spintronic devices. Both semiconducting and ferromagnetic properties have been established in some of the RENs which thus attract interest for the potential to exploit the spin of charge carriers in semiconductor technologies for both fundamental and applied science. In this review, we take stock of where progress has occurred within the last decade in both theoretical and experimental fields, and which has led to the point where a proof-of-concept spintronic device based on RENs has already been demonstrated. The article is organized into three major parts. First, we describe the epitaxial growth of REN thin films and their structural properties, with an emphasis on their prospective spintronic applications. Then, we conduct a critical review of the different advanced theoretical calculations utilised to determine both the electronic structure and the origins of the magnetism in these compounds. The rest of the review is devoted to the recent experimental results on optical, electrical and magnetic properties and their relation to current theoretical descriptions. These results are discussed particularly with regard to the controversy about the exact nature of the magnetic state and conduction processes in the RENs.Comment: 34 pages, 14 figure

We report the growth of GdN thin films and a study of their structure and magnetic and conducting properties. It is demonstrated that they are semiconducting at ambient temperature with nitrogen vacancies the dominant dopant. The films are ferromagnetic below 68 K, and a significant narrowing of the band gap is signaled by more than a doubling of its conductivity. The conductivity in the low-temperature ferromagnetic state remains typical of a doped semiconductor, supporting the view that this material is semiconducting in its ground state and that no metal-insulator transition occurs at the Curie temperature.

We report measurements of the optical gap in a GdN film at temperatures from 300 to 6K, covering both the paramagnetic and ferromagnetic phases. The gap is 1.31eV in the paramagnetic phase and red-shifts to 0.9eV in the spin-split bands below the Curie temperature. The paramagnetic gap is larger than was suggested by very early experiments, and has permitted us to refine a (LSDA+U)-computed band structure. The band structure was computed in the full translation symmetry of the ferromagnetic ground state, assigning the paramagnetic-state gap as the average of the majority- and minority-spin gaps in the ferromagnetic state. That procedure has been further tested by a band structure in a 32-atom supercell with randomly-oriented spins. After fitting only the paramagnetic gap the refined band structure then reproduces our measured gaps in both phases by direct transitions at the X point.Comment: 5 pages, 4 figure

Epitaxial gadolinium nitride films with well-oriented crystallites of up to 30 nm have been grown on yttria-stabilized ziconia substrates using a plasma-assisted pulsed laser deposition technique. We observe that the epitaxial GdN growth proceeds on top of a gadolinium oxide buffer layer that forms via reaction between deposited Gd and mobile oxygen from the substrate. Hall effect measurements show the films are electron doped to degeneracy, with carrier concentrations of 4×1020 cm−3. Magnetic measurements establish a TC of 70 K with a coercive field that can be tuned from 200 Oe to as low as 10 Oe.

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Polycrystalline GdN thin films have been grown at room temperature with varying N2 pressure. By varying the nitrogen pressure during growth we alter the carrier concentrations of the films. Films grown at low nitrogen pressures display onset of magnetization at temperatures as high as 200 K and a resistivity of 0.3 mΩ cm, whereas films grown at high nitrogen pressures all show a Curie temperature very close to 70 K and resistivity ranges over 1–1000 Ω cm are observed. For all GdN films a peak in the resistivity occurs at TC.

We investigate the electronic band structure of two of the rare-earth nitrides, DyN and SmN. Resistivity measurements imply that both materials have a semiconducting ground state, and both show resistivity anomalies coinciding with the magnetic transition, despite the different magnetic states in DyN and SmN. X-ray absorption and emission measurements are in excellent agreement with densities of states obtained from LSDA+U calculations, although for SmN the calculations predict a zero band gap.

The magnetic behavior of SmN has been investigated in stoichiometric polycrystalline films. All samples show ferromagnetic order with Curie temperature ͑T C ͒ of 27Ϯ 3 K, evidenced by the occurrence of hysteresis below T C . The ferromagnetic state is characterized by a very small moment and a large coercive field, exceeding even the maximum applied field of 6 T below about 15 K. The residual magnetization at 2 K, measured after cooling in the maximum field, is 0.035 B per Sm. Such a remarkably small moment results from a near cancellation of the spin and orbital contributions for Sm +3 in SmN. Coupling to an applied field is therefore weak, explaining the huge coercive field. The susceptibility in the paramagnetic phase shows temperatureindependent Van Vleck and Curie-Weiss contributions. The Van Vleck contribution is in quantitative agreement with the field-induced admixture of the J = 7 2 excited state and the 5 2 ground state. The Curie-Weiss contribution returns a Curie temperature that agrees with the onset of ferromagnetic hysteresis, and a conventional paramagnetic moment with an effective moment of 0.4 B per Sm ion, in agreement with expectations for the crystal-field modified effective moment on the Sm +3 ions.