We study ferromagnetic ordering and microscopic inhomogeneity in tensile strained LaCoO$_3$ using numerical simulations. We argue that both phenomena originate from effective superexchange interactions between atoms in the high-spin (HS) state mediated by the intermediate-spin excitations. We derive a model of the HS excitation as a bare atomic state dressed by electron and electron-hole fluctuations on the neighbor atoms. We construct a series of approximations to account for electron correlation effects responsible for HS fluctuations and magnetic exchange. The obtained amplitudes and directional dependence of magnetic couplings between the "dressed" HS states show a qualitative agreement with experimental observations and provide a new physical picture of LaCoO$_3$ films.
The enigma of the emergent ferromagnetic state in tensile-strained LaCoO3 thin films remains to be explored because of the lack of a well agreed explanation. The direct magnetic imaging technique using a low-temperature magnetic force microscope (MFM) is critical to reveal new aspects of the ferromagnetism by investigating the lateral magnetic phase distribution. Here we show the experimental demonstration of the rare halved occupation of the ferromagnetic state in tensile-strained LaCoO3 thin films on SrTiO3 substrates using the MFM. The films have uniformly strained lattice structure and min…
Ferromagnetic insulators play a crucial role in the development of low-dissipation quantum magnetic devices for spintronics. Epitaxial LaCoO3 thin film is a prominent ferromagnetic insulator, in which the robust ferromagnetic ordering emerges owing to epitaxial strain. Whereas it is evident that strong spin-lattice coupling induces ferromagnetism, the reported ferromagnetic properties of epitaxially strained LaCoO3 thin films were highly consistent. For example, even under largely modulated degree of strain, the reported Curie temperatures of epitaxially strained LaCoO3 thin films lie within 8…
The origin of strain-induced ferromagnetism, which is robust regardless of the type and degree of strain in LaCoO3 (LCO) thin films, is enigmatic despite intensive research efforts over the past decade. Here, by combining scanning transmission electron microscopy with ab initio density functional theory plus U calculations, we report that the ferromagnetism does not emerge directly from the strain itself, but rather from the creation of compressed structural units within ferroelastically formed twin-wall domains. The compressed structural units are magnetically active with the rocksalt-type hi…
Magnetism in lanthanum cobaltite (LCO, LaCoO$_3$) appears to be strongly dependent on strain, defects, and nanostructuring. LCO on strontium titanate (STO, SrTiO$_3$) is a ferromagnet with an interesting strain relaxation mechanism that yields a lattice modulation. However, the driving force of the ferromagnetism is still controversial. Experiments debate between a vacancy-driven or strain-driven mechanism for the ferromagnetism of epitaxial LCO. We found that a weak lateral modulation of the superstructure is sufficient to promote ferromagnetism. We find that ferromagnetism appears under unia…
We have studied ultrafast dynamics of thin films of LaCoO$_3$ and La$_{0.5}$Sr$_{0.5}$CoO$_3$ with femtosecond pump-probe ellipsometry in the energy range of 1.6-3.4 eV. We have observed a large pump-induced transfer of spectral weight in LaCoO$_3$ that corresponds to an insulator-to-metal transition. The photo-induced metallic state initially relaxes via a fast process with a decay constant of about 200 fs. Both LaCoO$_3$ and La$_{0.5}$Sr$_{0.5}$CoO$_3$ exhibit a significant secondary transient structure in the 1-30 ps range. Results of measurements on films with different thicknesses demonst…
The spin states of Co$^{3+}$ ions in perovskite-type LaCoO$_3$, governed by complex interplay between the electron-lattice interactions and the strong electron correlations, still remain controversial due to the lack of experimental techniques which can detect directly. In this letter, we revealed the tensile-strain dependence of spin states, $i. e.$ the ratio of the high- and low-spin states, in epitaxial thin films and a bulk crystal of LaCoO$_3$ via resonant inelastic soft x-ray scattering. The tensile-strain as small as 1.0% was found to realize different spin states from that in the bulk.
We investigate the structure and magnetic properties of thin films of the LaCoO$_{3}$ compound. Thin films are deposited by pulsed laser deposition on various substrates in order to tune the strain from compressive to tensile. Single-phase (001) oriented LaCoO$_{3}$ layers were grown on all substrates despite large misfits. The tetragonal distortion of the films covers a wide range from -2% to 2.8%. Our LaCoO$_{3}$ films are ferromagnetic with Curie temperature around 85 K, contrary to the bulk. The total magnetic moment is below $1μ_{B}$/Co$^{3+}$, a value relatively small for an exited spin-…
Epitaxial thin films of LaCoO_{3} (E-LCO) exhibit ferromagnetic order with a transition temperature T_c = 85 K, while polycrystalline thin LaCoO_{3} films (P-LCO) remain paramagnetic. The temperature-dependent spin-state structure for both E-LCO and P-LCO was studied by x-ray absorption spectroscopy at the Co L_{2,3} and O K edges. Considerable spectral redistributions over temperature are observed for P-LCO. The spectra for E-LCO, on the other hand, do not show any significant changes for temperatures between 30 K and 450 K at both edges, indicating that the spin state remains constant and th…
Epitaxial thin films of undoped LaCoO$_{3}$\@, of electron-doped La$_{0.7}$Ce$_{0.3}$CoO$_{3}$\@, and of hole-doped La$_{0.7}$Sr$_{0.3}$CoO$_{3}$\@ exhibit ferromagnetic order with a transition temperature $T_{\rm{C}}$ $\approx$ 85 K, 22 K, and 240 K, respectively. The spin-state structure for these compounds was studied by soft x-ray magnetic circular dichroism at the Co $L_{2,3}$ and O $K$ edges. It turns out that a higher spin state of the Co$^{3+}$ ions is responsible for the magnetism in LaCoO$_{3}$\@ while for La$_{0.7}$Ce$_{0.3}$CoO$_{3}$ the Co$^{3+}$ ions are in a low-spin state and t…
The electronic structure of epitaxial films on LaCoO3(LCO) has been studied within first principle electronic structure calculations. A spin state transition is found to take place as a function of lattice strain which freezes in the intermediate spin state for non zero strain. In contrast to earlier speculations this is found to arise from substrate strain alone and angle variations are small. The intermediate spin state also stabilizes ferromagnetism in the ground state. The anomalous temperature dependence of the X-ray absorption spectra for films of LCO on LCO and its absence in films of L…
With local density approximation + Hubbard $U$ (LDA+$U$) calculations, we show that the ferromagnetic (FM) insulating state observed in tensile-strained LaCoO$_3$ epitaxial thin films is most likely a mixture of low-spin (LS) and high-spin (HS) Co, namely, a HS/LS mixture state. Compared with other FM states, including the intermediate-spin (IS) state (\textit{metallic} within LDA+$U$), which consists of IS Co only, and the insulating IS/LS mixture state, the HS/LS state is the most favorable one. The FM order in HS/LS state is stabilized via the superexchange interactions between adjacent LS …
We report an investigation of transverse Hall resistance and longitudinal resistance on Pt thin films sputtered on epitaxial LaCoO$_3$ (LCO) ferromagnetic insulator films. The LaCoO$_3$ films were deposited on several single crystalline substrates [LaAlO$_3$ (LAO), (La,Sr)(Al,Ta)O$_3$ (LSAT), and SrTiO$_3$ (STO)] with (001) orientation. The physical properties of LaCoO$_3$ films were characterized by the measurements of magnetic and transport properties. The LaCoO$_3$ films undergo a paramagnetic to ferromagnetic (FM) transition at Curie temperatures ranging from 40 K to 85 K, below which the …
Magnetization has been measured for polycrystalline samples of LaCo1-xRhxO3 (0 {\leq} x {\leq} 0.9) in order to investigate magnetism induced in the solid solution of two nonmagnetic end phases of LaCoO3 and LaRhO3. It is found that a ferromagnetic transition is observed below 15 K in the range of x from 0.1 to 0.4. The effective Bohr magnetic moment evaluated from the temperature dependence of magnetic susceptibility at around room temperature is independent of x for 0 < x < 0.5 (approximately 3 μB per formula unit), and rapidly decreases above x = 0.5. On the basis of detailed magnetization …
A GaN film doped with 8.2 % Mn was grown by the molecular-beam-epitaxy technique. Magnetization measurements show that this highly Mn-doped GaN film exhibits ferromagnetism above room temperature. It is also revealed that the high-temperature ferromagnetic state is significantly suppressed below 10 K, accompanied by an increase of the electrical resistivity with decreasing temperature. This observation clearly demonstrates a close relation between the ferromagnetism with extremely high-Tc and the carrier transport in the Mn-doped GaN film.
We report the bulk sensitive Hard X-ray (hv=5.95keV) core level photoemission spectroscopy to investigate the intrinsic electronic structure of strained (La0.85Ba0.15)MnO3 thin films. In a 20nm thick well-strained film with strongly enhanced ferromagnetism, a new sharp satellite peak appeared at the low energy site of the Mn 2p3/2 main peak, whereas a broader signal was observed for the unstrained film with 300nm thickness. Cluster calculations revealed that the intensity corresponded to the density of the state at the Fermi level relating to the magnitude of the ferromagnetic order. The satel…
We report room-temperature ferromagnetism in highly conducting transparent anatase Ti1-xTaxO2 (x~0.05) thin films grown by pulsed laser deposition on LaAlO3 substrates. Rutherford backscattering spectrometry (RBS), x-ray diffraction (XRD), proton induced x-ray emission (PIXE), x-ray absorption spectroscopy (XAS) and time-of-flight secondary ion mass spectrometry (TOF-SIMS) indicated negligible magnetic contaminants in the films. The presence of ferromagnetism with concomitant large carrier densities was determined by a combination of superconducting quantum interference device (SQUID) magnetom…
Epitaxial strain imposed in complex oxide thin films by heteroepitaxy is recognized as a powerful tool for identifying new properties and exploring the vast potential of materials performance. A particular example is LaCoO3, a zero spin, nonmagnetic material in the bulk, whose strong ferromagnetism in a thin film remains enigmatic despite a decade of intense research. Here, we use scanning transmission electron microscopy complemented by X-ray and optical spectroscopy to study LaCoO3 epitaxial thin films under different strain states. We observed an unconventional strain relaxation behavior re…
The magnetic behavior of thin ferromagnetic itinerant-electron films is investigated within the strongly correlated single-band Hubbard model. For its approximate solution we apply a generalization of the modified alloy analogy (MAA) to deal with the modifications due to the reduced translational symmetry. The theory is based on exact results in the limit of strong Coulomb interaction which are important for a reliable description of ferromagnetism. Within the MAA the actual type of the alloy analogy is determined selfconsistently. The MAA allows, in particular, the investigation of quasiparti…
The temperature-driven reorientation transition which, up to now, has been studied by use of Heisenberg-type models only, is investigated within an itinerant-electron model. We consider the Hubbard model for a thin fcc(100) film together with the dipole interaction and a layer-dependent anisotropy field. The isotropic part of the model is treated by use of a generalization of the spectral-density approach to the film geometry. The magnetic properties of the film are investigated as a function of temperature and film thickness and are analyzed in detail with help of the spin- and layer-dependen…
The 5$d$ based SrIrO$_3$ represents prototype example of nonmagnetic correlated metal which mainly originates from a combined effect of spin-orbit coupling, lattice dimensionality and crystal structure. Therefore, tuning of these parameters results in diverse physical properties in this material. Here, we study the structural, magnetic and electrical transport behavior in epitaxial SrIrO$_3$ film ($\sim$ 40 nm) grown on SrTiO$_3$ substrate. Opposed to bulk material, the SrIrO$_3$ film exhibits a ferromagnetic ordering at low temperature below $\sim$ 20 K. The electrical transport data indicate…
Nitrogen embedded ZnO:N films prepared by pulsed laser deposition exhibit significant ferromagnetism. The nitrogen ions contained in ZnO confirmed by Secondary Ion Microscopic Spectrum and Raman experiments and the embedded nitrogen ions can be regarded as defects. According to the experiment results, a mechanism is proposed based on one of the electrons in the completely filled d-orbits of Zn that compensates the dangling bonds of nitrogen ions and leads to a net spin of one half in the Zn orbits. These one half spins strongly correlate with localized electrons that are captured by defects to…
Ultrathin films of the itinerant ferromagnet SrRuO$_3$ were studied using transport and magnto-optic polar Kerr effect. We find that below 4 monolayers the films become insulating and their magnetic character changes as they loose their simple ferromagnetic behavior. We observe a strong reduction in the magnetic moment which for 3 monolayers and below lies in the plane of the film. Exchange-bias behavior is observed below the critical thickness, and may point to induced antiferromagnetism in contact with ferromagnetic regions.
Here we present polarized neutron reflectometry measurements exploring thin film heterostructures comprised of a strongly correlated Mott state, GdTiO$_3$, embedded with SrTiO$_3$ quantum wells. Our results reveal that the net ferromagnetism inherent to the Mott GdTiO$_3$ matrix propagates into the nominally nonmagnetic SrTiO$_3$ quantum wells and tracks the magnetic order parameter of the host Mott insulating matrix. Beyond a well thickness of 5 SrO layers, the magnetic moment within the wells is dramatically suppressed, suggesting that quenched well magnetism comprises the likely origin of q…
By combining genetic algorithm optimizations, first-principles calculations and the double-exchange model studies, we have unveiled that the exotic insulating ferromagnetism in LaMnO3 thin film originates from the previously unreported G-type d_{3z^2-r^2}/d_{x^2-y^2} orbital ordering. An insulating gap opens as a result of both the orbital ordering and the strong electron-phonon coupling. Therefore, there exist two strain induced phase transitions in the LaMnO3 thin film, from the insulating A-type antiferromagnetic phase to the insulating ferromagnetic phase and then to the metallic ferromagn…
We present Hall effect, $R_{xy}(H)$, and magnetoresistance, $R_{xx}(H)$, measurements of ultrathin films of Ni, Co and Fe with thicknesses varying between 0.2-8 nm and resistances between 1 M$Ω$ - 100 $Ω.$ Both measurements show that films having resistance above a critical value, $R_{C}$, (thickness below a critical value, $d_{C}$) show no signs for ferromagnetism. Ferromagnetism appears only for films with $R<R_{C}$, where $R_{C}$ is material dependent. We raise the possibility that the reason for the absence of spontaneous magnetization is suppression of itinerant ferromagnetism by electron…
Magneto-optic studies of ZnO doped with transition metals Co, Mn, V and Ti indicate a significant magnetic circular dichroism (MCD) at the ZnO band edge at room temperature, together with an associated dispersive Faraday rotation. Similar spectra occur for each dopant which implies that the ferromagnetism is an intrinsic property of the bulk ZnO lattice. At 10 K additional paramagnetic contributions to the MCD are observed, but above about 150K, the magnitude of the MCD signal is dominated by the ferromagnetism and is almost temperature independent. The MCD at the ZnO band edge shows room temp…
We show that a ferromagnetic (FM) order in the orthorhombic CaRuO3, which is a non-magnetic and iso-structural analog of FM system SrRuO3, can be established and stabilized by the means of tensile epitaxial strain. Investigations on the structural and magnetic property correlations in the CaRuO3 films with different degrees of strain reveal that the FM moment increases with increasing the tensile strain. This is an experimental verification to the theoretical predictions of scaling of the tensile epitaxial strain and the magnetic order in this system. Our studies further establish that the ten…
Experimental efforts to stabilize ferromagnetism in ultrathin films of transition metal oxides have so far failed, despite expectations based on density functional theory (DFT) and DFT+U. Here, we investigate one of the most promising materials, SrRuO$_3$, and include correlation effects beyond DFT by means of dynamical mean field theory. In agreement with experiment we find an intrinsic thickness limitation for metallic ferromagnetism in SrRuO$_3$ thin films. Indeed, we demonstrate that the realization of ultrathin ferromagnetic films is out of reach of standard thin-film techniques. Proposin…
The realization of semiconductors that are ferromagnetic above room temperature will potentially lead to a new generation of spintronic devices with revolutionary electrical and optical properties. Transition temperatures in doped ZnO are high but, particularly for Mn doping, the reported moments have been small. We show that by careful control of both oxygen deficiency and aluminium doping the ferromagnetic moments measured at room temperature in n-type ZnMnO and ZnCoO are close to the ideal values of 5mB and 3mB respectively. Furthermore a clear correlation between the magnetisation per tran…
Atomically sharp oxide heterostructures often exhibit unusual physical properties that are absent in the constituent bulk materials. The interplay between electrostatic boundary conditions, strain and dimensionality in ultrathin epitaxial films can result in monolayer-scale transitions in electronic or magnetic properties. Here we report an atomically sharp antiferromagnetic-to-ferromagnetic phase transition when atomically growing polar antiferromagnetic LaMnO3 (001) films on SrTiO3 substrates. For a thickness of five unit cells or less, the films are antiferromagnetic, but for six unit cells…
Epitaxial strain provides important pathways to control the magnetic and electronic states in transition metal oxides. However, the large strain is usually accompanied by a strong reduction of the oxygen vacancy formation energy, which hinders the direct manipulation of their intrinsic properties. Here using a post-deposition ozone annealing method, we obtained a series of oxygen stoichiometric SrCoO3 thin films with the tensile strain up to 3.0%. We observed a robust ferromagnetic ground state in all strained thin films, while interestingly the tensile strain triggers a distinct metal to insu…
Low-dimensional quantum materials that remain strongly ferromagnetic down to mono layer thickness are highly desired for spintronic applications. Although oxide materials are important candidates for next generation of spintronic, ferromagnetism decays severely when the thickness is scaled to the nano meter regime, leading to deterioration of device performance. Here we report a methodology for maintaining strong ferromagnetism in insulating LaCoO3 (LCO) layers down to the thickness of a single unit cell. We find that the magnetic and electronic states of LCO are linked intimately to the struc…
We have used low energy implanted muons as a volume sensitive probe of the magnetic properties of EuO_{1-x} thin films. We find that static and homogeneous magnetic order persists up to the elevated T_C in the doped samples and the muon signal displays the double dome feature also observed in the sample magnetization. Our results appear incompatible with either the magnetic phase separation or bound magnetic polaron descriptions previously suggested to explain the elevated T_C, but are compatible with an RKKY-like interaction mediating magnetic interactions above 69 K.
Magnetotransport and superconducting properties are investigated for uniformly La-doped SrTiO3 films and GdTiO3/SrTiO3 heterostructures, respectively. GdTiO3/SrTiO3 interfaces exhibit a high-density two-dimensional electron gas on the SrTiO3-side of the interface, while for the SrTiO3 films carriers are provided by the dopant atoms. Both types of samples exhibit ferromagnetism at low temperatures, as evidenced by a hysteresis in the magnetoresistance. For the uniformly doped SrTiO3 films, the Curie temperature is found to increase with doping and to coexist with superconductivity for carrier c…
X-ray photoemission spectroscopy measurements were performed on thin-film samples of rutile Ti_{1-x}Co_{x}O_{2-delta} to reveal the electronic structure. The Co 2p core level spectra indicate that the Co ions take the high-spin Co 2+ configuration, consistent with substitution on the Ti site. The high spin state and the shift due to the exchange splitting of the conduction band suggest strong hybridization between carriers in the Ti 3d t2g band and the t2g states of the high-spin Co 2+. These observations support the argument that room temperature ferromagnetism in Ti_{1-x}Co_{x}O_{2-delta} is…
We report on the evolution of the average and depth-dependent magnetic order in thin film samples of biaxially stressed and electron-doped EuTiO$_3$ for samples across a doping range $<$0.1 to 7.8 $\times 10^{20}$ cm$^{-3}$. Under an applied in-plane magnetic field, the G-type antiferromagnetic ground state undergoes a continuous spin-flop phase transition into in-plane, field-polarized ferromagnetism. The critical field for ferromagnetism slightly decreases with an increasing number of free carriers, yet the field evolution of the spin-flop transition is qualitatively similar across the dopin…
Topological transport phenomena in magnetic materials are a major topic of current condensed matter research. One of the most widely studied phenomena is the ``topological Hall effect'' (THE), which is generated via spin-orbit interactions between conduction electrons and topological spin textures such as skyrmions. We report a comprehensive set of Hall effect and magnetization measurements on epitaxial films of the prototypical ferromagnetic metal SrRuO$_3$ the magnetic and transport properties of which were systematically modulated by varying the concentration of Ru vacancies. We observe Hal…
We have examined whether the Co ions crystallographically substitute on the Ti sites in rutile and anatase Ti_{1-x}$Co$_{x}$O$_{2-delta}$ thin films that exhibit room-temperature ferromagnetism. Intensities of the x-ray Bragg reflection from the films were measured around the $K$-absorption-edge of Co. If the Co ions randomly substitute on the Ti sites, the intensity should exhibit an anomaly due to the anomalous dispersion of the atomic scattering factor of Co. However, none of the anatase and rutile samples did exhibit an anomaly, unambiguously showing that the Co ions in Ti$_{1-x}$Co$_{x}$O…
The intrinsic magnetic state (ferromagnetic or antiferromagnetic) of ultra-thin LaMnO$_3$ films on the mostly used SrTiO$_3$ substrate is a long-existing question under debate. Either strain effect or non-stoichiometry was argued to be responsible for the experimental ferromagnetism. In a recent experiment [Science \textbf{349}, 716 (2015)], one more mechanism, namely the self-doping due to polar discontinuity, was argued to be the driving force of ferromagnetism beyond the critical thickness. Here systematic first-principles calculations have been performed to check these mechanisms in ultra-…
We have used high-resolution Extended X-ray Absorption Fine-Structure and diffraction techniques to measure the local structure of strained La$_{0.5}$Sr$_{0.5}$CoO$_3$ films under compression and tension. The lattice mismatch strain in these compounds affects both the bond lengths and the bond angles, though the larger effect on the bandwidth is due to the bond length changes. The popular double exchange model for ferromagnetism in these compounds provides a correct qualitative description of the changes in Curie temperature $T_C$, but quantitatively underestimates the changes. A microscopic m…
Thin films of the optimally electron-doped $T'$-phase superconductor La$_{1.89}$Ce$_{0.11}$CuO$_{4\pm \d}$ are investigated by dilute Co doping, formed as La$_{1.89}$Ce$_{0.11}$(Cu$_{1-x}$Co$_{x}$)O$_{4\pm\d}$ (LCCCO) with $x$ = 0.01 -- 0.05. The following results are obtained for the first time: for the whole dilute Co doping range, LCCCO thin films show long-range ferromagnetic ordering at the temperature range from 5 K to 300 K, which is likely due to the RKKY interaction; in the very dilute Co doping, $x$ = 0.01 and 0.02, the superconductivity is maitained, the system shows the coexistence…
We discuss recent experiments in which fine particles of the organic superconductor Rb$_3$C$_{60}$ or the cuprate superconductor YBa$_2$Cu$_3$O$_{6+x}$ are held in a polystyrene film that is spin-coated on to a silicon substrate with or without an intervening gold, or another inert metallic layer. From SQUID magnetisation data for Rb$_3$C$_{60}$ there appears to be a striking and completely unexpected increase in the superconducting transition temperature from $30$ to $45$~K, which is ascribed to coupling between the electrons in the superconductor and vacuum fluctuations in the electromagneti…
In view of the recent experimental reports of unexpected ferromagnetism in HfO$_{2}$ thin films, we carried out first principles investigations looking for magnetic order possibly brought about by the presence of small concentrations of intrinsic point defects. {\it Ab initio} electronic structure calculations using density functional theory (DFT) show that isolated cation vacancy sites in HfO$_{2}$ lead to the formation of high spin defect states. Furthermore these appear to be ferromagnetically coupled with a rather short range magnetic interaction, resulting in a ferromagnetic ground state …
