Magnetic Phase Diagram of the MnxFe2−xP1−ySiy System

The phase diagram of the magnetocaloric MnxFe2−xP1−ySiy quaternary compounds was established by characterising the structure, thermal and magnetic properties in a wide range of compositions (for a Mn fraction of 0.3 ≤ x < 2.0 and a Si fraction of 0.33 ≤ y ≤ 0.60). The highest ferromagnetic transition temperature (Mn0.3Fe1.7P0.6Si0.4, TC = 470 K) is found for low Mn and high Si contents, while the lowest is found for low Fe and Si contents (Mn1.7Fe0.3P0.6Si0.4, TC = 65 K) in the MnxFe2−xP1−ySiy phase diagram. The largest hysteresis (91 K) was observed for a metal ratio close to Fe:Mn = 1:1 (corresponding to x = 0.9, y = 0.33). Both Mn-rich with high Si and Fe-rich samples with low Si concentration were found to show low hysteresis (≤2 K). These compositions with a low hysteresis form promising candidate materials for thermomagnetic applications.

Investigation of the electron and thermal transport in rare-earth nitrides

<p>Gadolinium nitride (GdN) and samarium nitride (SmN) have been widely studied to understand their ferromagnetic ordering and electronic structure, and for their promise in spintronics applications. This thesis presents experimental magnetotransport studies of GdN and SmN films in which experimental results have been compared with the existing band structure calculation. Three GdN films have been prepared in different conditions, among them two films are epitaxial quality and one film is polycrystalline in nature, and two films of SmN were also studied. Their magnetic properties were probed by SQUID magnetometry and they are found to be ferromagnetic. The transition temperature differs from sample to sample and this behaviour has been attributed to the presence of magnetic polarons that nucleate around nitrogen vacancies and give rise to an inhomogeneous ferromagnetic state. The charge transport results have been discussed for all GdN and SmN films. A full set of charge/heat transport results are obtained on only one epitaxial GdN. The difference of resistivity among these samples is noticeable. The Hall effect results show the presence of different carrier concentration with at most only weak temperature dependence. We also have noticed the presence of anomalous Hall effect in the paramagnetic region for a lower-concentration epitaxial GdN. The thermopower in both GdN and SmN was measured to provide further insight into the material’s electronic properties. In this thesis we present the first experimental investigation of the thermopower of epitaxial gadolinium nitride and samarium nitride films, measured using an experimental set-up designed for measuring the temperature dependent thermopower of thin films. Our result shows a negative thermopower for both GdN and SmN films and simple, though strong temperature dependence. At low temperatures we observe a peak near the ferromagnetic transition temperature in GdN. The results are interpreted in terms of the diffusion thermopower. Overall the results suggest that the nitrogen vacancy concentration controls the carrier concentration and plays a significant role towards the transport properties. We conclude that all films are either heavily, moderately or weakly doped semiconductors with a metallic characteristic.</p>

Investigation of the electron and thermal transport in rare-earth nitrides

<p>Gadolinium nitride (GdN) and samarium nitride (SmN) have been widely studied to understand their ferromagnetic ordering and electronic structure, and for their promise in spintronics applications. This thesis presents experimental magnetotransport studies of GdN and SmN films in which experimental results have been compared with the existing band structure calculation. Three GdN films have been prepared in different conditions, among them two films are epitaxial quality and one film is polycrystalline in nature, and two films of SmN were also studied. Their magnetic properties were probed by SQUID magnetometry and they are found to be ferromagnetic. The transition temperature differs from sample to sample and this behaviour has been attributed to the presence of magnetic polarons that nucleate around nitrogen vacancies and give rise to an inhomogeneous ferromagnetic state. The charge transport results have been discussed for all GdN and SmN films. A full set of charge/heat transport results are obtained on only one epitaxial GdN. The difference of resistivity among these samples is noticeable. The Hall effect results show the presence of different carrier concentration with at most only weak temperature dependence. We also have noticed the presence of anomalous Hall effect in the paramagnetic region for a lower-concentration epitaxial GdN. The thermopower in both GdN and SmN was measured to provide further insight into the material’s electronic properties. In this thesis we present the first experimental investigation of the thermopower of epitaxial gadolinium nitride and samarium nitride films, measured using an experimental set-up designed for measuring the temperature dependent thermopower of thin films. Our result shows a negative thermopower for both GdN and SmN films and simple, though strong temperature dependence. At low temperatures we observe a peak near the ferromagnetic transition temperature in GdN. The results are interpreted in terms of the diffusion thermopower. Overall the results suggest that the nitrogen vacancy concentration controls the carrier concentration and plays a significant role towards the transport properties. We conclude that all films are either heavily, moderately or weakly doped semiconductors with a metallic characteristic.</p>

Rare-earth tuned magnetism and magnetocaloric effects in double perovskites R2NiMnO6

We present a comprehensive experimental study of magnetization {\color {blue} ($2 < T < 300$~K, $1 < H < 8$~T)} and magnetocaloric effect in double perovskite materials $R_2$NiMnO$_6$ with $R =$ Pr, Nd, Sm, Gd, Tb, and Dy. While a paramagnetic to ferromagnetic transition, with T$_{\rm C}$ in the range $\sim 100 - 200~$K, is a common feature that can be attributed to the ordering of Mn$^{4+}$ and Ni$^{2+}$ magnetic moments, qualitatively distinct behavior depending on the choice of $R$ is observed at low temperatures. These low-temperature anomalies in magnetization are also manifest in the change in magnetic entropy, $-\Delta S_{M}$, whose sign depends on the choice of $R$. In order to understand these results, we present theoretical analysis based on mean-field approximation and Monte Carlo simulations on a minimal spin model. The model correctly captures the key features of the experimental observations.

First-Principles Investigation of Structural, Electronic, and Room Temperature Ferromagnetism in Si-Doped Monolayer BN

We performed spin-polarized density functional theory (DFT) to investigate the structural, electronic, and magnetic properties of silicon- (Si-) doped monolayer boron nitride (BN). The present study revealed that structural parameters like bond length, bond angle, and lattice parameters increase as Si-doped in the B site of monolayer BN. However, the bandgap of monolayer BN is reduced in the presence of the Si dopant. Moreover, the obtained magnetic moment and analysis of the total density of states (TDOS) show that Si-doped monolayer BN displays ferromagnetism. The calculated ferromagnetic transition temperature (Tc) value for Si concentration of 12.5% is 476 K which exceeds room temperature. The findings are avenues to enhance the application of monolayer BN for spintronics.

Magnetic and Transport Studies of Strongly Correlated Perovskite Ceramics

<p>This thesis describes the results from an experimental study of the magnetic and transport properties of two strongly correlated transition metal oxides. The firstmaterial under study is the ferromagnetic half-metal double perovskite, Sr2FeMoO6, in which we have made isoelectronic (Ba2+) and electronic (La3+) substitutions onto the strontium site. Magnetoresistance measurements on Sr2-xBaxFeMoO6 revealed that the low temperature magnetoresistance is dominated by inter-grain transport while the intra-grain contribution is evident when the temperature is close to the ferromagnetic transition temperature. Transport measurements on Sr2-xLaxFeMoO6 clearly showed that the doping dependence of the thermoelectric power is surprisingly similar to the one observed in the superconducting cuprates. In addition, it was found that the electronic doping leads to an increase in the ferromagnetic transition temperature, which supports the band filling model. Substitution on the Fe site was also investigated by partially replacing Fe with the non-magnetic aluminium element (Sr2Fe1-xAlxMoO6). It was found from thermoelectric power measurement that the Fe electronic state is below3+,which is inconsistentwith theoretical models but is in good agreement with Mossbauer measurements. In addition, magnetic measurements showed that the reduction in the ferromagnetic ordering temperature could be explained in terms of a 3D percolation model. The second compound is the oxygen deficient strontium iron oxide SrFeO3-delta . The temperature dependence of the thermoelectric power was measured in this compound for the first time and shown to be reminiscent of the charge-ordering Verwey transition observed in Fe3O4. Magnetic measurements show an increase of a weak ferromagnetic signal versus the oxygen deficiency that could originate from a Dzyaloshinsky-Moriya interaction in the distorted FeO6 octahedra. Finally, we observed a large magnetoresistance near room temperature for compounds close to the orthorhombic SrFeO2.75 phase.</p>

Magnetic and Transport Studies of Strongly Correlated Perovskite Ceramics

<p>This thesis describes the results from an experimental study of the magnetic and transport properties of two strongly correlated transition metal oxides. The firstmaterial under study is the ferromagnetic half-metal double perovskite, Sr2FeMoO6, in which we have made isoelectronic (Ba2+) and electronic (La3+) substitutions onto the strontium site. Magnetoresistance measurements on Sr2-xBaxFeMoO6 revealed that the low temperature magnetoresistance is dominated by inter-grain transport while the intra-grain contribution is evident when the temperature is close to the ferromagnetic transition temperature. Transport measurements on Sr2-xLaxFeMoO6 clearly showed that the doping dependence of the thermoelectric power is surprisingly similar to the one observed in the superconducting cuprates. In addition, it was found that the electronic doping leads to an increase in the ferromagnetic transition temperature, which supports the band filling model. Substitution on the Fe site was also investigated by partially replacing Fe with the non-magnetic aluminium element (Sr2Fe1-xAlxMoO6). It was found from thermoelectric power measurement that the Fe electronic state is below3+,which is inconsistentwith theoretical models but is in good agreement with Mossbauer measurements. In addition, magnetic measurements showed that the reduction in the ferromagnetic ordering temperature could be explained in terms of a 3D percolation model. The second compound is the oxygen deficient strontium iron oxide SrFeO3-delta . The temperature dependence of the thermoelectric power was measured in this compound for the first time and shown to be reminiscent of the charge-ordering Verwey transition observed in Fe3O4. Magnetic measurements show an increase of a weak ferromagnetic signal versus the oxygen deficiency that could originate from a Dzyaloshinsky-Moriya interaction in the distorted FeO6 octahedra. Finally, we observed a large magnetoresistance near room temperature for compounds close to the orthorhombic SrFeO2.75 phase.</p>

Unconventional critical behaviour in weak ferromagnets Fe2-xMnxCrAl (0 ≤ x < 1)

Recent investigation on weak ferromagnets Fe2-xMnxCrAl (0 ≤ x < 1) reveal the existence of a cluster glass phase (CGP) and a Griffiths-like phase (GP) below and above the ferromagnetic transition temperature (TC), respectively [(2019) Sci. Rep.9 15888]. In this work, the influence of these inhomogeneous phases on the critical behaviour (around TC) of the above-mentioned series of alloys has been investigated in detail. For the parent alloy Fe2CrAl, the critical exponent γ is estimated as ~ 1.34, which lies near to the ordered 3D Heisenberg class, whereas the obtained value of the critical exponent β ~ 0.273 does not belong to any universality class. With increment in Mn concentration, both exponents γ and β increase, where γ and β approach the disordered and ordered 3D Heisenberg class, respectively. The observed deviation of γ and unconventional value of δ can be ascribed to the increment of GP with Mn-concentration. The trend noted for β can be attributed to the increment in CGP regime with an increase in Mn-content. The estimated critical exponents are consistent and reliable as corroborated using the scaling law and equations of state. Our studies indicate that the critical phenomenon of Fe2-xMnxCrAl (0 ≤ x < 1) alloys possibly belong to a separate class, which is not described within the framework of any existing universal model.

Finite-size effects on the evolution of magnetic correlations and magnetocaloric properties of Pr0.4Bi0.2Sr0.4MnO3

The effect of particle size reduction on the magnetic correlations of Pr0.4Bi0.2Sr0.4MnO3 nanoparticles prepared by top-down approach has been studied in detail. It was observed that as the milling time increases from 0 to 240 min, particle size decreases from 160 to 12 nm. Correspondingly it was observed that the ferromagnetic transition temperature (TC) drops (264 to 213 K) and saturation magnetization (MS) decreases (2.12–0.41 $${\upmu }_{\mathrm{B}}/\mathrm{f}.\mathrm{u}.$$ μ B / f . u . ) while coercivity (HC) shows a monotonous increase (0.18–1.5 kOe) as the particle size decreases due to increase in milling. The magnetic entropy change (ΔS) also decreases (2.41–0.24 J/kg-K) as particle size decreases indicating a strong correlation between magnetism and particle size. The metamagnetic M–H response of the bulk sample, which signifies the magnetic phase coexistence, is suppressed, and the nature of magnetic interactions demonstrates a transition from long range to short range. The observed characteristics emphasizes that with particle size reduction there is an increase in the surface disorder which can be explained by considering the core–shell model for the nanoparticles. Graphic abstract