Transport Properties of Rare Earth Nitrides

<p>In this thesis we investigate the transport properties of SmN, NdN and GdN, members of the rare earth nitride series of intrinsic ferromagnetic semiconductors. GdN is the central member of the series with seven occupied majority spin 4f states and seven empty minority spin 4f states. Both the filled and unfilled 4f states are some few eV away from the conduction and valence band extrema, resulting in transport properties which are dominated by the extended Gd 5d band. The half filled 4f shell, with zero net orbital angular momentum, furthermore simplifies calculations and as such GdN is the most studied both experimentally and in theory. As one moves to lighter members, the filled 4f states become unfilled states in the conduction band and the 4f shell now has a net orbital angular momentum. Calculations concerning these members are now significantly more complicated, and as such there exists a wide range of predictions concerning the conduction band minima in the lighter rare earth nitrides. To inform the current theoretical and experimental literature we report on three studies concerning the transport properties of SmN, NdN and GdN. To begin we report on the anomalous Hall effect in SmN, NdN and GdN. Under the symmetry of the rock-salt rare earth nitrides the magnitude of the anomalous Hall effect can imply the wave function of the conduction electron (i.e. d or f band). Measurements of the anomalous Hall effect in moderately doped samples are used to show the conduction channel in SmN and NdN is an f band or hybridised f/d band. Furthermore the sign of the anomalous Hall effect can be used to determine the orientation of the spin magnetic moment of the conduction electrons. Optical measurements of SmN, NdN and GdN films are then reported. Optical measurements provide a probe of the band structure of a material via direct transitions between the valence and conduction bands. Measurements of reflectivity and transmission on undoped SmN and NdN films were used to locate the unfilled majority spin 4f bands which form the conduction band minima in each material. Finally a preliminary study of heavily doped SmN, NdN and GdN is discussed. Structural measurements show a reduced lattice parameter while transport results find a significantly enhanced conductivity in heavily doped films. The Curie temperature is found to be enhanced and optical measurements show an increased absorption and red-shifted optical edge in doped films. The superconducting state of SmN is discussed and it is shown only to be present in moderately doped films, i.e. superconductivity is not present in undoped or degenerately doped SmN, within our measurement limits.</p>

Structural, Electronic and Magnetic Properties of GaMnN, MnN and Rare-Earth Nitride Thin Films

<p>Materials that combine the useful properties of magnetic and semiconducting behaviours are sought for new and developing applications in electronics. In this thesis experimental studies of the properties of disordered thin films of several potentially magnetic semiconducting materials are presented. Previous research on the diluted magnetic semiconductor GaMnN is reviewed as an introduction to a study of GaMnN thin films grown with an ion-assisted deposition technique. Several complementary compositional and structural analysis techniques are used to determine that films can be grown with as much as 18 at. % Mn content and that contain no impurity phases, as are often detected in single crystalline GaMnN preparations with high Mn concentrations. The effects of varying Mn contents on the resistive, optical and magnetic properties of the thin films are investigated. The structural, electronic and magnetic properties of thin films of the potential impurity phase MnN have also been investigated and compared with band structure calculations. Recent predictions that the rare earth nitrides may have extremely useful electronic properties have been almost untested in the literature. A procedure for growing rare earth nitride thin films and capping them to protect from reaction with water vapour allows their resistivity, structural and magnetic properties to be established. The results on GdN, SmN, ErN and DyN support the recent predictions, and a more thorough study on GdN reveals that this material is a ferromagnetic semiconductor below 69 K.</p>

Structural, Electronic and Magnetic Properties of GaMnN, MnN and Rare-Earth Nitride Thin Films

<p>Materials that combine the useful properties of magnetic and semiconducting behaviours are sought for new and developing applications in electronics. In this thesis experimental studies of the properties of disordered thin films of several potentially magnetic semiconducting materials are presented. Previous research on the diluted magnetic semiconductor GaMnN is reviewed as an introduction to a study of GaMnN thin films grown with an ion-assisted deposition technique. Several complementary compositional and structural analysis techniques are used to determine that films can be grown with as much as 18 at. % Mn content and that contain no impurity phases, as are often detected in single crystalline GaMnN preparations with high Mn concentrations. The effects of varying Mn contents on the resistive, optical and magnetic properties of the thin films are investigated. The structural, electronic and magnetic properties of thin films of the potential impurity phase MnN have also been investigated and compared with band structure calculations. Recent predictions that the rare earth nitrides may have extremely useful electronic properties have been almost untested in the literature. A procedure for growing rare earth nitride thin films and capping them to protect from reaction with water vapour allows their resistivity, structural and magnetic properties to be established. The results on GdN, SmN, ErN and DyN support the recent predictions, and a more thorough study on GdN reveals that this material is a ferromagnetic semiconductor below 69 K.</p>

Transport Properties of Rare Earth Nitrides

<p>In this thesis we investigate the transport properties of SmN, NdN and GdN, members of the rare earth nitride series of intrinsic ferromagnetic semiconductors. GdN is the central member of the series with seven occupied majority spin 4f states and seven empty minority spin 4f states. Both the filled and unfilled 4f states are some few eV away from the conduction and valence band extrema, resulting in transport properties which are dominated by the extended Gd 5d band. The half filled 4f shell, with zero net orbital angular momentum, furthermore simplifies calculations and as such GdN is the most studied both experimentally and in theory. As one moves to lighter members, the filled 4f states become unfilled states in the conduction band and the 4f shell now has a net orbital angular momentum. Calculations concerning these members are now significantly more complicated, and as such there exists a wide range of predictions concerning the conduction band minima in the lighter rare earth nitrides. To inform the current theoretical and experimental literature we report on three studies concerning the transport properties of SmN, NdN and GdN. To begin we report on the anomalous Hall effect in SmN, NdN and GdN. Under the symmetry of the rock-salt rare earth nitrides the magnitude of the anomalous Hall effect can imply the wave function of the conduction electron (i.e. d or f band). Measurements of the anomalous Hall effect in moderately doped samples are used to show the conduction channel in SmN and NdN is an f band or hybridised f/d band. Furthermore the sign of the anomalous Hall effect can be used to determine the orientation of the spin magnetic moment of the conduction electrons. Optical measurements of SmN, NdN and GdN films are then reported. Optical measurements provide a probe of the band structure of a material via direct transitions between the valence and conduction bands. Measurements of reflectivity and transmission on undoped SmN and NdN films were used to locate the unfilled majority spin 4f bands which form the conduction band minima in each material. Finally a preliminary study of heavily doped SmN, NdN and GdN is discussed. Structural measurements show a reduced lattice parameter while transport results find a significantly enhanced conductivity in heavily doped films. The Curie temperature is found to be enhanced and optical measurements show an increased absorption and red-shifted optical edge in doped films. The superconducting state of SmN is discussed and it is shown only to be present in moderately doped films, i.e. superconductivity is not present in undoped or degenerately doped SmN, within our measurement limits.</p>

Rare earth nitrides and their applications in magnetic tunnel junctions

<p>In this thesis, we investigate the rare earth nitrides, a family of materials containing many intrinsic ferromagnetic semiconductors, with a particular focus on GdN and SmN.We investigate the rare earth nitride formation reaction, explore some properties of GdN and SmN, and finally manufacture and measure magnetic tunnel junctions which incorporate rare earth nitrides. The investigations of the reaction and properties of the materials are used to improve and understand the magnetic tunnel junctions. All samples and devices are grown at room temperature, giving polycrystalline rare earth nitride films. We show that a rare earth surface can catalytically break theN2 molecule at ambient temperature and low pressures. We follow the nitrogen reacting with the rare earth to form a rare earth nitride in real time via conductance measurements. By comparing the N2 cracking, reaction, and diffusion at both a RE and a REN surface we propose a pressure range in which the nitrogen content in SmN can be manipulated and conclude that the nitrogen in the top monolayers in a SmN film is mobile. In the investigation of GdN and SmN, we find that the conductivity of SmN follows the same behaviour as GdN when changing the N2 pressure during deposition. We follow the conductance change in SmN during deposition and propose a minimum thickness for room temperature deposited SmN films for consistent conductivity measurements. We report structural and magnetic changes in GdN which has been exposed to N-ions. We also present data on materials making ohmic contact to both GdN and SmN. Finally, we report the manufacturing and investigation of magnetic tunnel junctions using GdN and SmN electrodes with a GaN tunnel barrier. A new pattern design produces 20 devices, in a single deposition, which show consistent behaviour and expands on previous work on this topic. The main focus of the investigation is the J-V characteristics of the magnetic tunnel junctions which shows clear non-linear behaviour arising from tunnelling through the GaN. A Simmons fit to the J-V characteristics yields a barrier height of 0:8 eV and barrier thicknesses close to experimentally determined thicknesses. The J-V characteristics are investigated with changing temperature and changing applied magnetic field to investigate the effect of the ferromagnetism of the GdN and SmN electrodes. The tunnel magnetoresistance (TMR) of the devices show two contributions, a low-temperature TMR contribution and a 50K TMR contribution, and the maximum TMR for all devices are between 100% to 600%. The devices can withstand current densities up to 4000A/cm² and voltages up to 5V which is promising for a wide range of future applications.</p>

Rare earth nitrides and their applications in magnetic tunnel junctions

<p>In this thesis, we investigate the rare earth nitrides, a family of materials containing many intrinsic ferromagnetic semiconductors, with a particular focus on GdN and SmN.We investigate the rare earth nitride formation reaction, explore some properties of GdN and SmN, and finally manufacture and measure magnetic tunnel junctions which incorporate rare earth nitrides. The investigations of the reaction and properties of the materials are used to improve and understand the magnetic tunnel junctions. All samples and devices are grown at room temperature, giving polycrystalline rare earth nitride films. We show that a rare earth surface can catalytically break theN2 molecule at ambient temperature and low pressures. We follow the nitrogen reacting with the rare earth to form a rare earth nitride in real time via conductance measurements. By comparing the N2 cracking, reaction, and diffusion at both a RE and a REN surface we propose a pressure range in which the nitrogen content in SmN can be manipulated and conclude that the nitrogen in the top monolayers in a SmN film is mobile. In the investigation of GdN and SmN, we find that the conductivity of SmN follows the same behaviour as GdN when changing the N2 pressure during deposition. We follow the conductance change in SmN during deposition and propose a minimum thickness for room temperature deposited SmN films for consistent conductivity measurements. We report structural and magnetic changes in GdN which has been exposed to N-ions. We also present data on materials making ohmic contact to both GdN and SmN. Finally, we report the manufacturing and investigation of magnetic tunnel junctions using GdN and SmN electrodes with a GaN tunnel barrier. A new pattern design produces 20 devices, in a single deposition, which show consistent behaviour and expands on previous work on this topic. The main focus of the investigation is the J-V characteristics of the magnetic tunnel junctions which shows clear non-linear behaviour arising from tunnelling through the GaN. A Simmons fit to the J-V characteristics yields a barrier height of 0:8 eV and barrier thicknesses close to experimentally determined thicknesses. The J-V characteristics are investigated with changing temperature and changing applied magnetic field to investigate the effect of the ferromagnetism of the GdN and SmN electrodes. The tunnel magnetoresistance (TMR) of the devices show two contributions, a low-temperature TMR contribution and a 50K TMR contribution, and the maximum TMR for all devices are between 100% to 600%. The devices can withstand current densities up to 4000A/cm² and voltages up to 5V which is promising for a wide range of future applications.</p>

Growth and Structural Properties of Rare Earth Nitride Thin Films

<p>In this thesis aspects of the growth of rare earth nitride thin films and characterisation of the resulting structural, electronic and magnetic properties of the film are investigated. The rare earth nitrides are a class of materials which combine interesting electronic and magnetic properties with potential applications in novel spintronic device structures. We study the formation of a preferential orientation in polycrystalline thin films of GdN deposited by electron-beam physical vapour deposition. X-ray diffraction is used to characterise the crystalline structure of films of varying thickness to identify a preference to grow along the [111] crystal direction, understood in terms of an evolutionary selection process. Variations in the film microstructure as a result of growth parameter variation are also correlated to electronic and magnetic properties. Investigation of the epitaxial growth of SmN on AlN surfaces revealed a novel growth orientation transition, controllable only via the growth temperature. Epitaxial integration of rare earth nitrides with III-nitride surfaces has previously only resulted in (111)-oriented growth on the (0001) surface as is expected from matching of the close-packed planes in the different crystal structures. High growth temperatures (≥800 ℃) induce (001)-oriented growth of SmN on the same (0001) AlN surface. This unexpected cube-on-hexagon geometry is confirmed through ex situ x-ray and in situ electron diffraction, the latter for which a computational simulation tool was developed to model and understand. The viability of using Sm as a temporary capping layer for rare earth nitride thin film samples is investigated. Capping layers are required to passivate samples due to their high reactivity, limiting the range of ex situ characterisation techniques that can be performed on them. Elemental Sm is relatively volatile raising the possibility of removing a Sm cap in situ using moderate annealing temperatures (400 °C to 600 ℃). The ability to remove the capping layer would allow in situ characterisation techniques to be performed in ultra high vacuum systems not directly connected to the growth system. In situ electron diffraction is used to characterise the growth and thermal annealing of Sm grown on top of epitaxial GdN layers, and the effects of the thermal removal process on the structural, electronic and magnetic properties of the GdN layer are investigated.</p>

Growth and Structural Properties of Rare Earth Nitride Thin Films

<p>In this thesis aspects of the growth of rare earth nitride thin films and characterisation of the resulting structural, electronic and magnetic properties of the film are investigated. The rare earth nitrides are a class of materials which combine interesting electronic and magnetic properties with potential applications in novel spintronic device structures. We study the formation of a preferential orientation in polycrystalline thin films of GdN deposited by electron-beam physical vapour deposition. X-ray diffraction is used to characterise the crystalline structure of films of varying thickness to identify a preference to grow along the [111] crystal direction, understood in terms of an evolutionary selection process. Variations in the film microstructure as a result of growth parameter variation are also correlated to electronic and magnetic properties. Investigation of the epitaxial growth of SmN on AlN surfaces revealed a novel growth orientation transition, controllable only via the growth temperature. Epitaxial integration of rare earth nitrides with III-nitride surfaces has previously only resulted in (111)-oriented growth on the (0001) surface as is expected from matching of the close-packed planes in the different crystal structures. High growth temperatures (≥800 ℃) induce (001)-oriented growth of SmN on the same (0001) AlN surface. This unexpected cube-on-hexagon geometry is confirmed through ex situ x-ray and in situ electron diffraction, the latter for which a computational simulation tool was developed to model and understand. The viability of using Sm as a temporary capping layer for rare earth nitride thin film samples is investigated. Capping layers are required to passivate samples due to their high reactivity, limiting the range of ex situ characterisation techniques that can be performed on them. Elemental Sm is relatively volatile raising the possibility of removing a Sm cap in situ using moderate annealing temperatures (400 °C to 600 ℃). The ability to remove the capping layer would allow in situ characterisation techniques to be performed in ultra high vacuum systems not directly connected to the growth system. In situ electron diffraction is used to characterise the growth and thermal annealing of Sm grown on top of epitaxial GdN layers, and the effects of the thermal removal process on the structural, electronic and magnetic properties of the GdN layer are investigated.</p>

Device Applications of Rare-Earth Nitrides

<p>In this thesis the properties of thin film spintronic devices are investigated. These devices incorporate rare-earth nitrides as the active elements in a geometry with vertical transport perpendicular to the layers. Many rare-earth nitrides are ferromagnetic semiconductors with a rich range of magnetic properties arising from their 4-f magnetic moments. These magnetic moments contain both spin and orbital contributions, in contrast to the quenched, spin-based magnetism frequently exploited in spintronic devices based on transition metals. Magnetic tunnel junctions are demonstrated with the ferromagnetic electrodes made from the intrinsic ferromagnetic semiconductor GdN surrounding GaN and AlN barriers. Fitting of the current-voltage characteristics of a GdN/GaN/GdN device determines a barrier height of 1.5 eV at room temperature. This puts the GdN Fermi level close to the GaN mid-gap, consistent with recent theoretical predictions of the band alignment at the GdN/GaN interface [Kagawa et al., Phys. Rev. Applied 2, 054009 (2014)]. This barrier height is found to scale with the band gap of the group-III nitride barrier, being approximately twice as large for AlN barriers. It was observed that the barrier height reduces as the AlN barrier thickness increases, signalling the formation of Schottky barriers at the interface. These polycrystalline junctions exhibit a tunnel magnetoresistance of a few percent but do not show clear signs of homogeneous switching. The transport properties of the GdN/GaN/GdN junctions are heavily influenced by the electronic structure of the semiconducting GdN layers, making junctions based on rare-earth nitrides promising candidates for further investigation. A fully semiconductor-based magnetic tunnel junction that uses spin-orbit coupled materials made of intrinsic ferromagnetic semiconductors is then presented. Unlike more common approaches, one of the electrodes consists of a near-zero magnetic moment ferromagnetic semiconductor, samarium nitride, with the other electrode comprised of the more conventional ferromagnetic semiconductor gadolinium nitride. Fabricated tunnel junctions exhibit magnetoresistances as high as 200%, implying strong spin polarisation in both electrodes. In contrast to conventional tunnel junctions, the resistance is largest at high fields, a direct result of the orbital-dominant magnetisation in samarium nitride that requires the spin in this electrode aligns opposite to that in the gadolinium nitride when the magnetisation is saturated. The magnetoresistance at intermediate fields is controlled by the formation of a twisted magnetisation phase in the samarium nitride, a direct result of the orbital-dominant ferromagnetism. Thus, new functionality can be brought to magnetic tunnel junctions by use of novel electrode materials, in contrast to the usual focus on tuning the barrier properties. Finally, highly resistive GdN films intentionally doped with Mg are demonstrated. These films are found to have increased resistivities and decreased carrier concentrations, with no observed degradation in crystal quality as compared with undoped films. An increase of the Curie temperature in conductive films is observed which is consistent with the existence of magnetic polarons centred on nitrogen vacancies. The prospect of doping rare-earth nitride films in this manner promises greater control of the material properties and future device applications.</p>