We report room temperature ferromagnetism in boron-doped ZnO both experimentally and theoretically. The single phase Zn1-xBxO films deposited under high oxygen pressure by pulsed-laser deposition show ferromagnetic behavior at room temperature. The saturation magnetization increases monotonously from 0 to 1.5 emu/cm3 with the increasing of B component x from 0 to 6.8%. The first-principles calculations based on density functional theory demonstrate that the ferromagnetism in B-doped ZnO originates from the induced magnetic moments of oxygen atoms in the nearest neighbor sites to the B-Zn vacancy pair. The calculated total magnetic moment increasing tendency with B component is well consistent with experiments.
We report room temperature ferromagnetism in as-implanted Eu doped ZnO (ZnO:Eu). To address the origin of ferromagnetism ab initio calculations of ZnO:Eu system are performed. Results show that the ferromagnetism is induced by ZnO point defects as Eu ions in perfect ZnO tend to align antiferromagnetically.
A close link between the charge transfer electronic structures and polarity dependent high-TC ferromagnetism of TM2+:ZnO DMSs (TM2+ = 3d ions) is demonstrated. Trends in ferromagnetism across the 3d series of TM2+:ZnO DMSs predicted from their charge transfer energies reproduce experimental trends well. These results provide a unified basis for understanding both n- and p-type ferromagnetic oxide DMSs.
We have investigated electronic structures and magnetic properties of potential ZnO based diluted magnetic semiconductors: (Fe, Co) and (Fe, Cu) codoped ZnO. The origins of ferromagnetism are shown to be different between two. (Fe, Co) codoped ZnO does not have a tendency of Fe-O-Co ferromagnetic cluster formation, and so the double exchange mechanism will not be effective. In contrast, (Fe, Cu) codoped ZnO has a tendency of the Fe-O-Cu ferromagnetic cluster formation with the charge transfer between Fe and Cu, which would lead to the ferromagnetism through the double-exchange mechanism. The f…
Unexpected ferromagnetism has been observed in carbon doped ZnO films grown by pulsed laser deposition [Phys. Rev. Lett. 99, 127201 (2007)]. In this letter, we introduce carbon into ZnO films by ion implantation. Room temperature ferromagnetism has been observed. Our analysis demonstrates that (1) C-doped ferromagnetic ZnO can be achieved by an alternative method, i.e. ion implantation, and (2) the chemical involvement of carbon in the ferromagnetism is indirectly proven.
Structural and magnetic properties have been studied for polycrystalline Zn_1-xMn_xO (x=0.02, 0.03, 0.05). Low-temperature (~500 oC) synthesis leaves unreacted starting ZnO and manganese oxides. Contrary to a recent report, no bulk ferromagnetism was observed for single-phase materials synthesized in air at temperatures above 900 oC. Single-phase samples show paramagnetic Curie-Weiss behavior.
We report a surfactant assisted synthesis of Mn doped ZnO polycrystalline samples showing robust room temperature ferromagnetism as characterized by X-ray diffraction analysis, Transmission Electron Microscopy, Electron Paramagnetic Resonance and DC magnetization mearurements. This surfactant assisted synthesis method, developed by us, is found to be highly reproducible. Further, it can also be extended to the synthesis of other transition metal doped ZnO.
Following the theoretical predictions of ferromagnetism in Mn- and Co-doped ZnO, several workers reported ferromagnetism in thin films as well as in bulk samples of these materials. While some observe room-temperature ferromagnetism, others find magnetization at low temperatures. Some of the reports, however, cast considerable doubt on the magnetism of Mn- and Co-doped ZnO. In order to conclusively establish the properties of Mn- and Co-doped ZnO, samples with 6 percent and 2 percent dopant concentrations, have been prepared by the low-temperature decomposition of acetate solid solutions. The …
We present the results of a computational study of ZnO in the presence of Co and Mn substitutional impurities. The goal of our work is to identify potential ferromagnetic ground states within the (Zn,Co)O or (Zn,Mn)O material systems that are also good candidates for piezoelectricity. We find that, in contrast to previous results, robust ferromagnetism is not obtained by substitution of Co or Mn on the Zn site, unless additional carriers (holes) are also incorporated. We propose a practical scheme for achieving such $p$-type doping in ZnO.
We report here enhancement of ferromagnetism in pure ZnO upon thermal annealing with the ferromagnetic transition temperature Tc above room temperature. We observe a finite coercive field upto 300K and a finite thermoremanent magnetization upto 340K for the annealed sample. We propose that magnetic moments can form at anionic vacancy clusters. Ferromagnetism can occur due to either superexchange between vacancy clusters via isolated F+ centers, or through a limited electron delocalization between vacancy clusters. Isolated vacancy clusters or isolated F+ centers give rise to a strong paramagne…
We report on the magnetic properties of thoroughly characterized Zn1-xCoxO epitaxial thin films, with low Co concentration, x=0.003-0.005. Magnetic and EPR measurements, combined with crystal field theory, reveal that isolated Co2+ ions in ZnO possess a strong single ion anisotropy which leads to an "easy plane" ferromagnetic state when the ferromagnetic Co-Co interaction is considered. We suggest that the peculiarities of the magnetization process of this state can be viewed as a signature of intrinsic ferromagnetism in ZnO:Co materials.
We have developed a simple, surfactant assisted synthesis route for the preparation, in gram quantities, of Co and Li doped ZnO nanocrystalline samples showing robust room temperature ferromagnetism. Our studies show that RTF is intrinsic to Zn0.85Co0.05Li0.10O and not due to any segregated secondary phases. In addition, it has been shown that the defects play an important role in activating RTF in these oxide systems. This also provide an explanation for the widely varying results observed in the literature. The method can also be extended for the synthesis of other transition metal doped ZnO…
We investigated ZnO(0001) single crystals annealed in high vacuum with respect to their magnetic properties and cluster formation tendency after implant-doping with Fe. While metallic Fe cluster formation is suppressed, no evidence for the relevance of the Fe magnetic moment for the observed ferromagnetism was found. The latter along with the cluster suppression is discussed with respect to defects in the ZnO host matrix, since the crystalline quality of the substrates was lowered due to the preparation as observed by x-ray diffraction.
Magnetic 3d-ions doped into wide-gap oxides show signatures of room temperature ferromagnetism, although their concentration is two orders of magnitude smaller than that in conventional magnets. The prototype of these exceptional materials is Co-doped ZnO, for which an explanation of the room temperature ferromagnetism is still elusive. Here we demonstrate that magnetism originates from Co2+ oxygen-vacancy pairs with a partially filled level close to the ZnO conduction band minimum. The magnetic interaction between these pairs is sufficiently long-ranged to cause percolation at moderate concen…
The structural and magnetic properties of V doped ZnO are presented. V ions were introduced into hydrothermal ZnO single crystals by ion implantation with fluences of 1.2*10^16 to 6*10^16 cm^-2. Post-implantation annealing was performed in high vacuum from 823 K to 1023 K. The ZnO host material still partly remains in a crystalline state after irradiation, and is partly recovered by annealing. The V ions show a thermal mobility as revealed by depth profile Auger electron spectroscopy. Synchrotron radiation x-ray diffraction revealed no secondary phase formation which indicates the substitution…
We report the structural and magnetic properties of ZnO single crystals implanted at 623 K with up to 10 at. % of Ni. As revealed by X-ray diffraction, crystalline fcc-Ni nanoparticles were formed inside ZnO. The magnetic behavior (magnetization with field reversal and with different temperature protocol) of all samples is well explained by a magnetic Ni-nanoparticle system. Although the formation of Ni:ZnO based diluted magnetic semiconductor cannot be ruled out, the major contribution to the magnetic properties stems from crystalline nanoparticles synthesized under these implantation conditi…
The prediction of ferromagnetism at room temperature in Co-ZnO thin films has generated a large interest in the community due to the possible applications. However, the results are controversial, going from ferromagnetism to non-ferromagnetism, leading to a large debate about its origin (secondary phase, Co clusters or not). By carefully studying the micro-structure of various Co-ZnO films, we show that the Co2+ partly substitutes the ZnO wurtzite matrix without forming Co clusters. Surprisingly, the ferromagnetism nature of the films disappears as the Co content increases. In addition, our re…
Fe-doped ZnO nanocrystals are successfully synthesized and structurally characterized by using x-ray diffraction and transmission electron microscopy. Magnetization measurements on the same system reveal a ferromagnetic to paramagnetic transition temperature > 450 K with a low-temperature transition from ferromagnetic to spin-glass state due to canting of the disordered surface spins in the nanoparticle system. Local magnetic probes like EPR and Mossbauer indicate the presence of Fe in both valence states Fe2+ and Fe3+. We argue that the presence of Fe3+ is due to the possible hole doping in t…
We report here on the magnetic properties of ZnO:Mn and ZnO:Co doped nanoparticles. We have found that the ferromagnetism of ZnO:Mn can be switched on and off by consecutive low-temperature annealings in O2 and N2 respectively, while the opposite phenomenology was observed for ZnO:Co. These results suggest that different defects (presumably n-type for ZnO:Co and p-type for ZnO:Mn) are required to induce a ferromagnetic coupling in each case. We will argue that ferromagnetism is likely to be restricted to a very thin, nanometric layer, at the grain surface. These findings reveal and give insigh…
Cobalt and silver co-doping has been undertaken in ZnO thin films grown by pulsed laser deposition in order to investigate the ferromagnetic properties in ZnO-based diluted magnetic materials and to understand the eventual relation between ferromagnetism and charge carriers. Hall transport measurements reveal that Ag doping up to 5% leads to a progressive compensation of the native n-type carriers. The magnetization curves show ferromagnetic contributions for all samples at both 5 K and room temperature, decreasing with increasing the Ag concentration. First principles modeling of the possible…
The electronic structure and magnetic coupling properties of rare-earth metals (Gd, Nd) doped ZnO have been investigated using first-principles methods. We show that the magnetic coupling between Gd or Nd ions in the nearest neighbor sites is ferromagnetic. The stability of the ferromagnetic coupling between Gd ions can be enhanced by appropriate electron doping into ZnO:Gd system and the room-temperature ferromagnetism can be achieved. However, for ZnO:Nd system, the ferromagnetism between Nd ions can be enhanced by appropriate holes doping into the sample. The room-temperature ferromagnetism…
Several experimental studies have referred to the grain boundary (GB) defect as the origin of the ferromagnetism in ZnO. However, the mechanism of this hypothesis has never been confirmed. Present study investigates the atomic structure and the effect of point defects in a ZnO GB using the GGA+U approximation. The relaxed GB possesses large periodicity and channels with 8 and 10 numbered atoms having 4 and 3 fold coordination. Unlike O vacancy (VO), Zn vacancy (VZn) is preferentially aggregated at the GB, relative to the bulk-like region, indicating the possibility of obtaining p-type conducti…
A density functional theory study of substitutional carbon impurities in ZnO has been performed, using both the generalized gradient approximation (GGA) and a hybrid functional (HSE06) as exchange-correlation functional. It is found that the non-spinpolarized C$_\mathrm{Zn}$ impurity is under almost all conditions thermodynamically more stable than the C$_\mathrm{O}$ impurity which has a magnetic moment of $2μ_{\mathrm{B}}$, with the exception of very O-poor and C-rich conditions. This explains the experimental difficulties in sample preparation in order to realize $d^{0}$-ferromagnetism in C-…
The nature of the often reported room temperature ferromagnetism in transition metal doped oxides is still a matter of huge debate. Herein we report on room temperature ferromagnetism in high quality Co-doped ZnO (Zn1-xCoxO) bulk samples synthesized via standard solid-state reaction route. Reference paramagnetic Co-doped ZnO samples with low level of structural defects are subjected to heat treatments in a reductive atmosphere in order to introduce defects in the samples in a controlled way. A detailed structural analysis is carried out in order to characterize the induced defects and their co…
We discuss the properties of semiconducting bulk ZnO when substituted with the magnetic transition metal ions Mn and Co, with substituent fraction ranging from $x$ = 0.02 to $x$ = 0.15. The magnetic properties were measured as a function of magnetic field and temperature and we find no evidence for magnetic ordering in these systems down to $T$ = 2 K. The magnetization can be fit by the sum of a Curie-Weiss term with a Weiss temperature of $Θ\gg$100 K and a Curie term. We attribute this behavior to contributions from both \textit{t}M ions with \textit{t}M nearest neighbors and from isolated sp…
The origin of room temperature (RT) ferromagnetism (FM) in Ni doped ZnO samples are systematically investigated through physical, optical, and magnetic properties of nanostructure, prepared by simple low-temperature wet chemical method. Reitveld refinement of X-ray diffraction pattern displays an increase in lattice parameters with strain relaxation and contraction in Zn/O occupancy ratio by means of Ni-doping. Similarly scanning electron microscope demonstrates modification in the morphology from nanorods to nanoflakes with Ni doping, suggests incorporation of Ni ions in ZnO. More interesting…
We studied structural, optical and magnetic properties of high-quality 5 and 15% Co-doped ZnO films grown by plasma-assisted molecular beam epitaxy (MBE) on (0001)-sapphire substrates. Magnetic force microscopy (MFM) and magnetic measurements with SQUID magnetometer show clear ferromagnetic behavior of the films up to room temperature whereas they are antiferromagnetic below 200 K approximately. Temperature dependence of the carrier mobility was determined using Raman line shape analysis of the longitudinal-optical-phonon-plasmon coupled modes. It shows that the microscopic mechanism for ferro…
We report structural and magnetic properties of pure ZnO rods using X-ray diffraction (XRD), magnetization hysteresis (M-H) loop and near edge x-ray fine structure spectroscopy (NEXAFS) study at O K edge. Sample of ZnO was prepared by co-precipitation method. XRD and selective area electron diffraction measurements infer that ZnO rods exhibit a single phase polycrystalline nature with wurtzite lattice. Field emission transmission electron microscopy, field emission scanning electron microscopy micrographs infers that ZnO have rod type microstructures with dimension 200 nm in diameter and 550 n…
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…
Single phase Mn doped (2 at %) ZnO samples have been synthesized by solid-state reaction technique. Before the final sintering at 500 C, the mixed powders have been milled for different milling periods (6, 24, 48 and 96 hours). The grain sizes of the samples are very close to each other (~ 32 \pm 4 nm). However, the defective state of the samples is different from each other as manifested from the variation of magnetic properties and electrical resistivity with milling time. All the samples have been found to be ferromagnetic with clear hysteresis loops at room temperature. The maximum value f…
We have investigated the magnetic properties of non-doped ZnO nanostructures by using {\it ab initio} total energy calculations. Contrary to many proposals that ferromagnetism in non-doped semiconductors should be induced by intrinsic point defects, we show that ferromagnetism in nanostructured materials should be mediated by extended defects such as surfaces and grain boundaries. This kind of defects create delocalized, spin polarized states that should be able to warrant long-range magnetic interactions.
II-oxide and III-nitride semiconductors doped by nonmagnetic 2p light elements are investigated as potential dilute magnetic semiconductors (DMS). Based on our first-principle calculations, nitrogen doped ZnO, carbon doped ZnO, and carbon doped AlN are predicted to be ferromagnetic. The ferromagnetism of such DMS materials can be attributed to a p-d exchange-like p-p coupling interaction which is derived from the similar symmetry and wave function between the impurity (p-like t_2) and valence (p) states. We also propose a co-doping mechanism, using beryllium and nitrogen as dopants in ZnO, to …
The effect of hydrogenation on magnetic properties of Zn0.85Co0.05Li0.10O nanoparticles is presented. It was found that the sample hydrided at room temperature (RT) showed weak ferromagnetism (FM) while that hydrided at 400oC showed robust ferromagnetism at room temperature. In both cases reheating the sample at 400oC in air converts it back into paramagnetic state (P) completely. The characterization of samples by X-ray and electron diffraction (ED) showed that room temperature ferromagnetism observed in the samples hydrogenated at RT is intrinsic in nature whereas that observed in the sample…
Recently, d0 ferromagnetic materials have been projected as one of the promising novel materials for spintronics applications. In this work, we have studied Li-doped ZnO compounds, i.e. Zn1-xLixO (x=0, 0.02, 0.04, and 0.06) samples, prepared by the solid-state reaction route method. From the study of crystal structure using X-ray diffraction (XRD) patterns, it is evident that the prepared materials have been formed in a single-phase of the hexagonal wurtzite structure. The refinement of the XRD patterns suggests that there are very small changes in the lattice parameters upon Li-incorporation …
We have studied the structural, magnetic and electronic properties of Co-implanted ZnO (0001) films grown on Al2O3 (1120) substrates for different implantation doses and over a wide temperature range. Strong room temperature ferromagnetism is observed with magnetic parameters depending on the cobalt implantation dose. A detailed analysis of the structural and magnetic properties indicates that there are two magnetic phases in Co-implanted ZnO films. One is a ferromagnetic phase due to the formation of long range ferromagnetic ordering between implanted magnetic cobalt ions in the ZnO layer, th…
We recently reported the observation of room temperature ferromagnetism in mixtures of ZnO and Co3O4 despite the diamagnetic and antiferromagnetic character of these oxides respectively. Here we present a detailed study on the electronic structure of this material in order to account for this unexpected ferromagnetism. Electrostatic interactions between both oxides lead to a dispersion of Co3O4 particles over the surface of ZnO larger ones. As a consequence, the reduction of Co+3 to Co2+ at the particle surface takes place as evidenced by XAS measurements and optical spectrocopy. This reductio…
We have investigated the electronic structure of ZnO:Mn and ZnO:Mn,N thin films using x-ray magnetic circular dichroism (XMCD) and resonance-photoemission spectroscopy. From the Mn 2$p$$\rightarrow3d$ XMCD results, it is shown that, while XMCD signals only due to paramagnetic Mn$^{2+}$ ions were observed in ZnO:Mn, nonmagnetic, paramagnetic and ferromagnetic Mn$^{2+}$ ions coexist in ZnO:Mn,N. XMCD signals of ZnO:Mn,N revealed that the localized Mn$^{2+}$ ground state and Mn$^{2+}$ state hybridized with ligand hole coexisted, implying $p$-$d$ exchange coupling. In the valence-band spectra, spe…
Based on the first-principles evolutionary materials design, we report a stable boron Kagome lattice composed of triangles in triangles on a two-dimensional sheet. The Kagome lattice can be synthesized on a silver substrate, with selecting Mg atoms as guest atoms. While the isolated Kagome lattice is slightly twisted without strain, it turns into an ideal triangular Kagome lattice under tensile strain. In the triangular Kagome lattice, we find the exotic electronic properties, such as topologically non-trivial flat band near the Fermi energy and half-metallic ferromagnetism, and predict the qu…
Experimental studies of Zn1-xCoxO as thin films or nanocrystals have found ferromagnetism and Curie temperatures above room temperature and that p- or n-type doping of Zn1-xCoxO can change its magnetic state. Bulk Zn1-xCoxO with a low defect density and x in the range used in experimental thin film studies exhibits ferromagnetism only at very low temperatures. Therefore defects in thin film samples or nanocrystals may play an important role in promoting magnetic interactions between Co ions in Zn1-xCoxO. The electronic structures of Co substituted for Zn in ZnO, Zn and O vacancies, substituted…
Successful synthesis of room-temperature ferromagnetic semiconductors, Zn$_{1-x}$Fe$_{x}$O, is reported. The essential ingredient in achieving room-temperature ferromagnetism in bulk Zn$_{1-x}$Fe$_{x}$O was found to be additional Cu doping. A transition temperature as high as 550 K was obtained in Zn$_{0.94}$Fe$_{0.05}$Cu$_{0.01}$O; the saturation magnetization at room temperature reached a value of $0.75 μ_{\rm B}$ per Fe. Large magnetoresistance was also observed below $100 $K.
In the last decade, transition-metal-doped ZnO has been intensively investigated as a route to room-temperature diluted magnetic semiconductors (DMSs). However, the origin for the reported ferromagnetism in ZnO-based DMS remains questionable. Possible options are diluted magnetic semiconductors, spinodal decomposition, or secondary phases. In order to clarify this question, we have performed a thorough characterization of the structural and magnetic properties of Co- and Ni-implanted ZnO single crystals. Our measurements reveal that Co or Ni nanocrystals (NCs) are the major contribution of the…
It is shown that substitution of C or N for O recently proposed as a way to create ferromagnetism in otherwise nonmagnetic oxide insulators is curtailed by formation of impurity pairs, and the resultant C2 spin=1 dimers as well as the isoelectronic N2^{2+} interact antiferromagneticallly in p-type MgO. For C-doped ZnO, however, we demonstrate using the HSE hybrid functional that a resonance of the spin-polarized C2 ppπ* states with the host conduction band results in a long-range ferromagnetic interaction. Magnetism of open-shell impurity molecules is proposed as a possible route to d0-ferroma…
We report magnetism in carbon doped ZnO. Our first-principles calculations based on density functional theory predicted that carbon substitution for oxygen in ZnO results in a magnetic moment of 1.78 $μ_B$ per carbon. The theoretical prediction was confirmed experimentally. C-doped ZnO films deposited by pulsed laser deposition with various carbon concentrations showed ferromagnetism with Curie temperatures higher than 400 K, and the measured magnetic moment based on the content of carbide in the films ($1.5 - 3.0 μ_B$ per carbon) is in agreement with the theoretical prediction. The magnetism …
We report on the structural and magnetic properties of a cobalt-implanted ZnO film grown on a sapphire substrate. X-ray diffraction and transmission electron microscopy reveal the presence of a (10-10)-oriented hexagonal Co phase in the Al2O3 sapphire substrate, but not in the ZnO film. Co clusters, with a diameter of is about 5-6 nm, form a Co rich layer in the substrate close to the ZnO/Al2O3 interface. Magnetization measurements indicate that there exist two different magnetic phases in the implanted region. One originates from the Co clusters in Al2O3, the other one belongs to a homogeneou…
The adsorption of hydrogen on the polar Zn-ended ZnO(0001) surface has been investigated by density functional {\it ab-initio} calculations. An on top H(1x1) ordered overlayer with genuine H-Zn chemical bonds is shown to be energetically favorable. The H covered surface is metallic and spin-polarized, with a noticeable magnetic moment at the surface region. Lower hydrogen coverages lead to strengthening of the H-Zn bonds, corrugation of the surface layer and to an insulating surface. Our results explain experimental observations of hydrogen adsorption on this surface, and not only predict a me…
The role of intrinsic defects has been investigated to determine binding energies and the electronic structure of Gd complexes in ZnO. We use density-functional theory and the GW method to show that the presence of vacancies and interstitials affect the electronic structure of Gd doped ZnO. However, the strong localization of the Gd-$f$ and $d$ states suggest that carrier mediated ferromagnetism in this material may be difficult to achieve.
We have studied zig-zag boron nitride (BN) nanotubes doped with the Ni hexagonal-closepacked nanowire. The doped BN nanotubes are ferromagnetic metals with substantial magnetism. Some special magnetic properties resulting from the interaction between the Ni nanowire and BN nanotubes are found. The Ni doped BN(9,0) nanotube shows semi-half-metallic behavior, which could become half-metallic after doping electrons more than 1.4 e/unit cell. The intrinsic halfmetallic behavior could be achieved by two dierent ways: one is coating the Ni nanowire with a smaller BN nanotube, i.e., BN(8,0), the othe…
We review pitfalls in recent efforts to make a conventional semiconductor, namely ZnO, ferromagnetic by means of doping with transition metal ions. Since the solubility of those elements is rather low, formation of secondary phases and the creation of defects upon low temperature processing can lead to unwanted magnetic effects. Among others, ion implantation is a method of doping, which is highly suited for the investigation of those effects. By focussing mainly on Fe, Co or Ni implanted ZnO single crystals we show that there are manifold sources for ferromagnetism in this material which can …
Nowadays ferromagnetism is often found in potential diluted magnetic semiconductor systems. However, many authors argue that the observed ferromagnetism stems from ferromagnetic precipitates or spinodal decomposition rather than from carrier mediated magnetic impurities, as required for a diluted magnetic semiconductor. In the present paper we answer this question for Fe-implanted ZnO single crystals comprehensively. Different implantation fluences and temperatures and post-implantation annealing temperatures have been chosen in order to evaluate the structural and magnetic properties over a w…
Recently theoretical works predict that some semiconductors (e.g. ZnO) doped with magnetic ions are diluted magnetic semiconductors (DMS). In DMS magnetic ions substitute cation sites of the host semiconductor and are coupled by free carriers resulting in ferromagnetism. One of the main obstacles in creating DMS materials is the formation of secondary phases because of the solid-solubility limit of magnetic ions in semiconductor host. In our study transition metal ions were implanted into ZnO single crystals with the peak concentrations of 0.5-10 at.%. We established a correlation between stru…
We report the synthesis of colloidal Mn2+-doped ZnO (Mn2+:ZnO) quantum dots and the preparation of room-temperature ferromagnetic nanocrystalline thin films. Mn2+:ZnO nanocrystals were prepared by a hydrolysis and condensation reaction in DMSO under atmospheric conditions. Synthesis was monitored by electronic absorption and electron paramagnetic resonance (EPR) spectroscopies. Zn(OAc)2 was found to strongly inhibit oxidation of Mn2+ by O2, allowing the synthesis of Mn2+:ZnO to be performed aerobically. Mn2+ ions were removed from the surfaces of as-prepared nanocrystals using dodecylamine to …
Recently the point defect responsible for the intra-3$d$ luminescence of cobalt in doped ZnO samples has been indentified\,\cite{pssb2019}. In this work we further extend our investigation to other point defects in Co-doped ZnO. We use density-functional theory and GW calculations to determined the orbital-resolved band structure of cobalt doped zinc oxide (ZnO). We show that mainly O-p and Co-d orbitals take part in the process and confirm that an oxygen interstitial nearby a cobalt atom is a likely defect to occur in Co-implanted ZnO samples. We also rule out that other common point defects …
The role of Cr incorporation into the ZnO were probed through investigations into the structural, optical and magnetic properties. Zn1-xCrxO with x = 0, 0.01, 0.03 and 0.05, nanoparticles were prepared by solution combustion method. Powder x-ray diffraction (XRD) results reveal, all the synthesized samples are in single hexagonal wurtzite crystal structures, indicating that Cr3+ ions substitute the Zn2+ ions without altering the structure. The crystallite size and microstrain were calculated using the Willamson-Hall method and found to be 36 +- 2 nm for ZnO and it reduced with the increase of …
We use point contact Andreev reflection measurements to determine the spin polarization of the transport current in pulse laser deposited thin films of ZnO with 1% Al and with and without 2%Mn. Only films with Mn are ferromagnetic and show spin polarization of the transport current of up to 55 $\pm$ 0.5% at 4.2 K, in sharp contrast to measurements of the nonmagnetic films without Mn where the polarization is consistent with zero. Our results imply strongly that ferromagnetism in these Al doped ZnO films requires the presence of Mn.
We present results of a density functional theory study of MnO in the wurtzite structure. Our motivation is provided by recent experiments reporting ferromagnetism in Mn-doped wurtzite structure ZnO. We find that wurtzite MnO a) is not strongly energetically disfavored as compared with the ground state rocksalt MnO, b) shows strong magnetostructural coupling and c) has a piezoelectric response that is larger than that of ZnO. These predictions augur well for the creation of ferromagnetic piezoelectric semiconductor based on Mn-doped ZnO.
Room-temperature ferromagnetism is observed in (110) oriented ZnO films containing 5 at % of Sc, Ti, V, Fe, Co or Ni, but not Cr, Mn or Cu ions. There are large moments, 1.9 and 0.5 muB/atom for Co- and Ti-substituted oxides, respectively. Sc-substituted ZnO shows also a moment of 0.3 muB/Sc. Magnetization is very anisotropic, with variations of up to a factor three depending on the orientation of the applied field relative to the R-cut sapphire substrates. Results are interpreted in terms of a spin-split donor impurity band model, which can account for ferromagnetism in insulating or conducti…
Room-temperature ferromagnetism has been induced within ZnO single crystals by implant-doping with Fe ions. For an implantation temperature of 620 K and an ion fluence of 4x10^16 cm^-2, very tiny Fe particles, formed inside the host matrix, are responsible for the ferromagnetic properties. They were identified using synchrotron X-ray diffraction and Moessbauer spectroscopy. On the other hand, Fe ions implanted at a temperature of 253 K and an ion fluence of 4x10^15 cm^-2 are incorporated into the host matrix and develop a room temperature diluted magnetic semiconductor (DMS).
In transition metal doped ZnO, the energy position of dopant 3$d$ states relative to host conduction and valence bands is crucial in determining the possibilty of long range ferromagnetism. Density functional theory based estimates of the energy position of Co-3$d$ states in Co doped ZnO differ substantially depending upon the choice of exchange-correlation functional. In this work we investigate many-body $GW$ corrections on top of DFT$+U$ and hybrid-DFT groundstates to provide a theoretical benchmark for the quasiparticle energies in wurtzite ZnO:Co. Both single shot $G_0W_0$ as well as part…
During the past years there has been renewed interest in the wide-bandgap II-VI semiconductor ZnO, triggered by promising prospects for spintronic applications. First, ferromagnetism was predicted for dilute magnetic doping. In comprehensive investigation of ZnO:Co thin films based on the combined measurement of macroscopic and microscopic properties, we find no evidence for carrier-mediated itinerant ferromagnetism. Phase-pure, crystallographically excellent ZnO:Co is uniformly paramagnetic. Superparamagnetism arises when phase separation or defect formation occurs, due to nanometer-sized met…
We investigate the influence of impurities and vacancies in the formation of magnetic moment in CaB6 using full potential ab initio band structure calculations. CaB6 is found to be a band insulator with a band gap of about 0.2 eV. The calculated results indicate that carbon and oxygen substitution in boron sublattice, usually expected as impurity in low purity borons, do not play significant role in the local moment formation. Boron vacancy in the boron sublattice, on the other hand, leads to the formation of an impurity band in the vicinity of the Fermi level, which exhibit finite exchange sp…
We investigated the electronic and optical properties of bilayer AB stacked Boron and Nitrogen vacancies in hexagonal Boron Nitride (h-BN) using density functional theory (DFT). The density of states (DOS) and electronic band structure showed that Boron vacancy in bilayer h-BN results in a magnetic and conducting ground state. The band gap energy ranges from 4.56 eV for the pristine BN bilayer to 0.12 eV for a single Nitrogen vacancy in the bilayer. Considering the presence of 1,3,4-Boron vacancy, half metallic character is observed. However, the 2-boron vacancy configuration resulted in metal…
