Effect of carbon co-doping on the magnetic properties of bulk Mn doped ZnO

We report the systematic study on the effect of C-doping and annealing atmosphere (air, O₂, N₂ and Ar) on the magnetic properties of pure ZnO as well as Zn_0.98Mn_0.02O (ZMO). We found diamagnetic behavior for pure ZnO samples in all the annealing atmospheres whereas all ZMO samples are paramagnetic except the one, which is annealed in argon. While maintaining the same annealing atmospheres and varying the C content we found that on increasing the C-doping concentration the ferromagnetic fraction in the sample increases. The observed RTFM in C-doped ZMO is possibly due to carriers introduced into the samples due to oxygen vacancies and the substitution of C at O sites.     

Synthesis and positron characterizations of ferromagnetic Zn0.98Mn0.02O and paramagnetic Zn0.98Mn0.02O samples

Room temperature ferromagnetic and paramagnetic Zn_0.98Mn_0.02O samples have been synthesized by the solid state reaction method and by selecting the final annealing temperature. Employing positron annihilation techniques, defects for both samples have been characterized. The results indicate that the presence of cation vacancy type defects is relatively less in the ferromagnetic Zn_0.98Mn_0.02O sample than in the paramagnetic Zn_0.98Mn_0.02O sample.     

退火对Mn和N共掺杂的Zn0.88Mn0.12O:N薄膜特性的影响

以NH₃为掺N源,采用电子束反应蒸发技术生长了Mn和N共掺杂的Zn_1-xMn_xO:N薄膜,生长温度为300℃,然后在O₂气氛中400℃退火0.5 h.X射线衍射测量表明,Zn_0.88Mn_0.12O(Mn掺杂)薄膜或Zn_0.88Mn_0.12O:N(Mn和N共掺杂)薄膜仍具有单一晶相纤锌矿结构,未检测到杂质相 关键词： ZnO薄膜 Mn和N共掺杂 电学特性 磁特性     

No room temperature ferromagnetism in Mn over-doped Zn1−xMnxO (x>0.02)

Mn-doped ZnO samples having composition Zn_1−xMn_xO (x=0.02, 0.04 and 0.05) were synthesized by solid state reaction technique with varying concentration of Mn from 0.02 to 0.05. Evidence of room temperature ferromagnetism was observed only in the composition Zn_0.98Mn_0.02O sintered at 500 °C. Our XRD pattern confirms the presence of Mn₃O₄ impurity phase in all the Zn_1−xMn_xO samples with the exception of Zn_0.98Mn_0.02O. We emphasize that the appearance of Mn₃O₄ phase in the system forbids the exchange type of interaction between the Mn ions and suppresses the ferromagnetism in all the Mn over-doped Zn_1−xMn_xO (x>0.02) system. SEM microstructure study also supports the interruption of exchange type of interaction inside the system with the increase in Mn concentration in the sample. Interestingly, for this particular composition, Zn_0.98Mn_0.02O sintered at 500 °C, glassy ferromagnetism type of transition is observed at low temperature. This type of transition is attributed to the formation of the oxides of Mn clusters at low temperature.     

Effect of annealing treatment on the magnetic properties of mechanochemical synthesized La0.8Pb0.2MnO3 manganites

In this paper, we have investigated the effect of annealing on structural and magnetic properties of La_0.8Pb_0.2MnO₃ (LPMO) polycrystalline samples. Mechanochemical procedure has been used to produce LPMO nanocrystalline samples from oxide precursors. From the AC susceptibility measurements we found that the magnitude of susceptibility increases and the paramagnetic–ferromagnetic (PM–FM) transition width decreases by annealing the ball milled powders. Also, reentrant spin glass (RSG) behavior has been found in high temperature annealed samples. It seems that, due to the evaporation of PbO in high temperature annealed samples, vacancies created in perovskite structure and portion of the Mn³⁺–O–Mn⁴⁺ network is broken. So the FM double-exchange interaction is weakened due to the magnetic dilution and the antiferromagnetc (AFM) phase fraction increases in high temperature annealed samples. The competition between FM double-exchange interaction and AFM super-exchange interaction produces spin frustration and is responsible for the occurrence of RSG.     

Ferromagnetism of MnxLiyZn1−x−yO films

We had prepared Mn-doped ZnO and Li, Mn codoped-ZnO films with different concentrations using spin coating method. Crystal structure and magnetic measurements demonstrate that the impurity phases (ZnMnO₃) are not contributed to room temperature ferromagnetism and the ferromagnetism in Mn-doped ZnO film is intrinsic. Interesting, saturated magnetization decreases with Mn or Li concentration increase, showing that some antiferromagnetism exists in the samples with high Mn or Li concentration. In addition, Mn_0.05Zn_0.95O film annealed in vaccum shows larger ferromagnetism than the as-prepared sample and more oxygen vacancies induced by annealing in reducing atmosphere enhance ferromagnetism, which supports the bound magnetic polaron model on the origin of room temperature ferromagnetism.     

Room-temperature ferromagnetism and optical properties of Zn1−xMnxO nanoparticles

The room-temperature ferromagnetism is observed in Zn_0.98Mn_0.02O nanoparticles, which is related to the host-lattice defects induced by doping Mn. The ferromagnetism in Zn_0.95Mn_0.05O nanoparticles can be suppressed by Mn clusters. The additional peak at 519 cm^?1 is observed in Raman scattering spectra of the Zn_1?xMn_xO nanoparticles associated with intrinsic host-lattice defects, which become activated due to the Mn doping. The decrease in band gap and the weak intensity of absorption peak in the nanoparticles may be due to the sp–d interaction between transition metal and Zn anions.     

Role of Mn doping for obtaining of hexagonal phase in Ba0.98Zn0.02TiO3 ceramics

This paper reports the observation of hexagonal phase of barium titanate by Mn doping and its effect on dielectric and magnetic properties. Ceramic samples of Ba_0.98Zn_0.02Ti_1−xMn_xO₃ (where, x= 0.04, 0.06 and 0.08) were prepared by traditional solid-state reaction route. The hexagonal phase is stabilized in the composition Ba_0.98Zn_0.02Ti_0.92Mn_0.08O₃ and a very feeble M–H loop is also observed in that composition. This induced magnetism is expected due to the exchange interactions between magnetic polarons formed by oxygen vacancies with Mn ions. The dielectric constant as well as the ferroelectric to paraelectric transition temperature is systematically decreased with increasing of Mn doping concentration. Further to that, the temperature dependent dielectric constant curve is also broadened at transition temperature with increasing of Mn concentration. However, the ferroelectric to paraelectric transition temperature is well above room temperature.     

Vacancy defects in (Zn, Mn)O

We have used positron annihilation spectroscopy to study the vacancy defects in (Zn, Mn)O crystals grown by chemical vapor transport (CVT). Our results show that Zn vacancies are present in both as-grown and high temperature annealed ZnO and Zn_0.985Mn_0.015O. In addition, we observe O vacancies in ZnO with no Mn. After annealing in O₂ at 1000 C, there is no change in the vacancy distribution in ZnO, while the Zn vacancy concentration increases by an order of magnitude in Zn_0.985Mn_0.015O.     

Structural and magnetic properties of Mn-doped ZnO powders

A mixture of bi(acetylacetonato) zinc(II)hydrate and tris(acetylacetonato) manganese(III) complexes was thermally co-dissociated to synthesize Mn-doped ZnO powders. In order to examine the effect of oxygen vacancies on the ferromagnetic coupling of Mn ions, two preparation routes were used: in route (I) the preparation was done in an open environment, whereas in route (II) the preparation was done in a closed environment. The X-ray diffraction (XRD) and the X-ray fluorescence (XRF) measurements indicate that the Mn content in the three samples are 3.9% (I), 3.3% (II) and 4.2% (II). The XRD results showed that the Mn ions were incorporated in the ZnO crystal and that a Zn_1−xMn_xO solid solution has formed. The magnetic characterization indicated that only samples prepared via route (II) exhibited a room temperature ferromagnetic component of magnetization. Furthermore, magnetic analysis showed that the magnetic moment per dopant ion in the samples examined was in the range of 4.2-6.1 μ_B/Mn. The percentages of coupled Mn atoms to the total number of Mn atoms were found to be extremely small (less than 0.1%), which by itself cannot explain the observed RT hysteresis loops. Thus, in order to produce long-range ferromagnetic order in these samples, the FM coupling has to be mediated via defects. The observed FM in this study may be attributed to the presence of oxygen vacancies, which mediate the ferromagnetic exchange between the coupled Mn ions. This is consistent with the bound magnetic polarons (BMP) model where defects like oxygen vacancies cause the polarons to overlap and give rise to a long-range ferromagnetic order in dilute magnetic semiconductors (DMS).     

Theoretical study of the magnetic interaction of Cr-doped ZnO with and without vacancies

First-principles density-functional theory (DFT) calculations have been performed to study the magnetic properties of ZnO:Cr with and without vacancies. The results indicate that the doping of Cr in ZnO induces obvious spin polarization around the Fermi level and a total magnetic moment of 3.77μ_B. The ferromagnetism (FM) exchange interaction between Cr atoms is short-ranged and decreases with increasing Cr separation distance. It is suggested that the FM state is not stable with low concentration of Cr. The presence of O vacancies can make the half-metallic FM state of the system more stable, so that higher Curie temperature ferromagnetism may be expected. Nevertheless, Zn vacancies can result in the FM stability decreasing slightly. The calculated formation energy shows that V_Zn+Cr_Zn complex forms spontaneously under O-rich conditions. However, under Zn-rich conditions, the complex of V_O+Cr_Zn forms more easily. Thus, ZnO doped with Cr may exhibit a concentration of vacancies that influence the magnetic properties.     

Effect of oxygen annealing on the Mn properties in ZnMnO Films

We studied the influence of thermal annealing in oxygen on the physical properties of MOCVD grown Zn_1−xMn_xO thin layers. Annealing in the 300–1000 °C temperature range modifies both lattice parameters and magnetic properties of the layers. Correlation of the results from X-ray diffraction, EPR studies and Raman spectroscopy indicate a modification of the Mn⁺²-related features in the ZnO matrix.     

Excitons and photoluminescence in ZnO and Zn0.99Mn0.01O nanocrystals

The photoluminescence and photoluminescence excitation spectra for Zn_1?x Mn _x O nanocrystals are presented. After annealing of powders in air, the intensity of the bands attributable to manganese decreases noticeably. This suggests that the oxygen vacancies affect the Zhang-Rice-like states appearing due to strong d-p-hybridization, which is confirmed by an increase in the band gap of Zn_1?x Mn _x O for low x. The origin of the 2.9-eV peak and the shape of its excitation spectrum are discussed qualitatively. For Zn_1?x Mn _x O nanocrystals, the shape of the excitation spectrum is as unusual as the intense absorption in the range (2.2–3.0) eV.     

Room temperature ferromagnetism in Ni-doped ZnO films

Zn_1−xNi_xO (x = 0.02, 0.03, 0.04, 0.05, 0.07) films were prepared using magnetron sputtering. X-ray diffraction indicates that all samples have a wurtzite structure with c-axis orientation. X-ray photoelectron spectroscopy results reveal that the Ni ion is in a +2 charge state in these films. Magnetization measurements indicate that all samples have room temperature ferromagnetism. In order to elucidate the origin of the ferromagnetism, Zn_0.97Ni_0.03O films were grown under different atmospheric ratios of argon to oxygen. The results show that as the fraction of oxygen in the atmosphere decreases, both the saturation magnetization and the number of oxygen vacancies increase, confirming that the ferromagnetism is correlated with the oxygen vacancy level.     

Structural,optical and magnetic properties of Cu and V co-doped ZnO nanoparticles

Zn_0.98−xCu_xV_0.02O (x=0, 0.01, 0.02 and 0.03) samples were synthesized by the sol–gel technology to dope up to 3% Cu in ZnO. Investigations of structural, optical and magnetic properties of the samples have been done. The results of X-ray diffraction (XRD), transmission electron microscope (TEM) and X-ray photoelectron spectroscopy (XPS) indicated that the V and Cu ions were incorporated into the crystal lattices of ZnO. With Cu doping concentration increasing up to 2 at%, the XRD results showed that all diffraction peaks corresponded to the wurtzite structure of ZnO. Photoluminescence (PL) measurements showed that Zn_0.98−xCu_xV_0.02O powders exhibited that the position of the ultraviolet (UV) emission peak of the samples showed an obvious red-shift and the green emission peak enhanced significantly with Cu doping in ZnVO nanoparticle. Magnetic measurements indicated that room temperature ferromagnetism (RTFM) of Zn_0.98−xCu_xV_0.02O was an intrinsic property when Cu concentration was less than 3 at%. The saturation magnetization (M_s) of Zn_0.98−xCu_xV_0.02O (x=0, 0.01 and 0.02) increased with the increase of the Cu concentration.     

NMR investigations of ion distribution in real structure of manganese-zinc ferrites

Using the nuclear magnetic resonance, X-ray and electromagnetic methods we investigated structure and properties of the single- and polycrystalline manganous and manganese-zinc ferrites: MnFe₂O₄, Mn_0.8Zn_0.2Fe₂O₄, Mn_0.6−xCu_xZn_0.3Fe_2.1O₄ (0 ≤x ≤ 0.3). The real structure of the manganous and manganese-zinc ferrites is found to contain simultaneously vacancies in cationic and anionic sublattices. The analysis of the NMR spectra of⁵⁵Mn,⁵⁷Fe,^63,65Cu and⁶⁷Zn ions allowed us to find the magnetic and valence states of all ions and their distribution in the real spinel structure. It was shown that the Fe³⁺ paramagnetic ions, Zn²⁺ diamagnetic ions and cationic vacancies in tetrapositions are distributed statistically. The Mn³⁺ and Cu²⁺ Jahn-Teller ions and presumably Fe²⁺ in octahedral positions are distributed nonstatistically forming cluster-type mesoscopic inhomogeneities. The correlation between distribution of ions and vacancies in the real structure of manganese-zinc ferrites and their functional electromagnetic properties was found.     

Influence of annealing atmosphere on the properties of La0.5Sr0.5MnO3

The structure, magnetic and electrical transport properties of La_0.5Sr_0.5MnO₃ annealed in different atmosphere have been investigated. No evident change of structural symmetry and the Curie temperature is observed for the samples. The resistivity at zero magnetic field of the samples annealed in air and nitrogen exhibits a metal–insulator transition, while no metal–insulator transition is observed for the sample annealed in oxygen, and for which the resistivity decreases monotonously with increasing temperature. Surprisingly, when an external magnetic field is applied, a metal–insulator transition appears for the sample annealed in oxygen. It is suggested that the annealing atmosphere affects the competition between FM and AFM phases due to the change of Mn⁴⁺/Mn³⁺ ratio and the oxygen/cation vacancies, and has a great influence on the electrical transport properties of La_0.5Sr_0.5MnO₃.     

Effect of annealing atmosphere on ferromagnetism in Mn doped ZnO films

This paper reports that Zn_0.97Mn_0.03O thin films have been prepared by radio-frequency sputtering technology followed by rapid thermal processing in nitrogen and oxygen ambient respectively. Magnetic property investigation indicates that the films are ferromagnetic and that the Curie temperature (T_c) is over room temperature. It is observed that the saturation magnetization of the films increases after annealing in nitrogen ambience but decreases after annealing in oxygen. Room temperature photoluminescence spectra indicate that the amount of defects in the films differs after annealing in the different ambiences. This suggests that the ferromagnetism in Zn_0.97Mn_0.03O films is strongly related to the defects in the films.     

Multiglass order and magnetoelectricity in Mn<Superscript>2+</Superscript> doped incipient ferroelectrics

“Multiglass” materials with simultaneous occurrence of two different glassy states extend the frame of conventional multiferroicity, which is devoted to crystalline materials with coexisting uniform long-range electric and magnetic ordering. The concept applies to Sr_0.98Mn_0.02TiO₃ ceramics, where A-site substituted Mn²⁺ ions are at the origin of both a polar and a spin cluster glass. Spin freezing is initiated below the dipolar glass temperature, T_g ^e ≈ 38 K, which is seemingly indicated by a divergence of the nonlinear susceptibility, χ₃. Below T_g ^m ≈ 34 K both glass phases are independently verified by memory and rejuvenation effects. Biquadratic interaction of the Mn²⁺ spins with ferroelectric correlations of their off-center pseudospins in the incipient ferroelectric host crystal SrTiO₃ explains the high spin glass temperature and comparably strong third-order magnetoelectric coupling between the polar and the magnetic degrees of freedom. Preliminary results on the related compound K_0.97Mn_0.03TaO₃ favorably comply with the magnetoelectric multiglass concept.     

Room-temperature ferromagnetism of diamagnetically-doped ZnO aligned nanorods fabricated by vapor reaction

Large-scale monocrystalline oxide-diluted magnetic semiconductor (ODMS) Zn_1−x Bi _x O nanorods arrays (NAs) were prepared within a large doping concentration range from 5% to 20% by a simple chemical vapor deposition. X-ray diffraction and high-resolution transmission electron microscopy reveal the monotonous expansion of the lattice constants with increasing Bi content, due to the effective Bi doping. In particular, room-temperature ferromagnetic (RTFM) behavior with Curie temperature over 363.7 K has been observed based on Bi-doped ZnO nanoarrays, whereas undoped ZnO NAs disappear. The RTFM origin is suggested, in which vacancies can be controlled to tune the FM. The as-formed RTFM NAs would have potential applications in many areas of advanced nanotechnology, such as new spintronic devices and magneto-optic components.