Effect of oxygen vacancy and dopant concentration on the magnetic properties of high spin Co doped TiO2 nanoparticles

Co doped TiO₂ nanoparticles have been synthesized by a simple sol-gel route taking 7.5, 9.5 and 10.5 mol% of cobalt concentration. Formation of nanoparticles is confirmed by XRD and TEM. Increase in d-spacing occurs for (0 0 4) and (2 0 0) peak with increase in impurity content. Valence states of Co and its presence in the doped material is confirmed by XPS and EDX. The entire vacuum annealed samples show weak ferromagnetism. Increased magnetization is found for 9.5 mol% but this value again decreases for 10.5 mol% due to antiferromagnetic interactions. A blocking temperature of 37.9 K is obtained, which shows shifting to high temperature as the dopant concentration is increased. The air annealed sample shows only paramagnetic behavior. Temperature dependent magnetic measurements for the air annealed sample shows antiferromagnetic behavior with a Curie-Weiss temperature of −16 K. Here we report that oxygen vacancy and cobalt aggregates are a key factor for inducing ferromagnetism-superparamagnetism in the vacuum annealed sample. Appearance of negative Curie-Weiss temperature reveals the presence of antiferromagnetic Co₃O₄, which is the oxidation result of metallic Co or cobalt clusters present on the host TiO₂.     

Synthesis and magnetic properties of Mn doped ZnO nanowires

Mn doped ZnO nanowires have been synthesized using a simple autocombustion method. The as-synthesized Mn doped ZnO nanowires were characterized by X-ray diffraction and transmission electron microscopy. An increase in the hexagonal lattice parameters of ZnO is observed on increasing the Mn concentration. Optical absorption studies show an increment in the band gap with increasing Mn content, and also give evidence for the presence of Mn²⁺ ions in tetrahedral sites. All Zn_1−xMn_xO (0≤x≤0.25) samples are paramagnetic at room temperature. However, a large increase in the magnetization is observed below 50 K. This behavior, along with the negative value of the Weiss constant obtained from the linear fit to the susceptibility data below room temperature, indicate ferrimagnetic behavior. The origin of ferrimagnetism is likely to be either the intrinsic characteristics of the Mn doped samples, or due to some spinel-type impurity phases present in the samples that could not be detected.     

Synthesis and magnetic properties of Mn doped CuO nanowires

Study of diluted magnetic semiconductor nanowires is one of the important topics in materials science. By using Mn-Cu alloy as the starting material, Mn doped CuO nanowire arrays have been synthesized in air at the temperature of 550 °C. X-ray diffraction measurements and scanning electron microscopic study shows that the nanowires were grown on Cu₂O substrate. Transmission electron microscopic study shows the single crystal property of the nanowires. Magnetic measurements show ferromagnetic property in the Mn doped CuO nanowires with the critical temperature higher than 80 K.     

Structural and magnetic properties of Cr and Mn doped InN

We present a detailed magnetic characterization of Cr and Mn doped InN films be means of superconducting quantum interference device magnetometry and X-ray magnetic circular dichroism. The InN:Cr films exhibit ferromagnetic behavior up to 300 K in a doping region from 2% to 8% without detectable phase segregation. The easy axis of magnetization is found to be in the film plane. On the contrary, Mn-doped films show signatures of phase segregation and paramagnetic behavior.     

Mn掺杂ZnO纳米棒阵列的制备及其磁学性质研究

在95 ℃条件下通过水热方法制备出垂直于ITO基底高密度均匀生长的Mn掺杂ZnO（ZnO：Mn）纳米棒阵列. 纳米棒的直径约为100纳米,长约1微米,且沿［001］方向生长. XRD和XPS结果证实了Mn以替位方式掺杂到纳米棒中,并且掺杂浓度与反应物中的Mn离子浓度似呈正比关系. 所制备的ZnO：Mn纳米棒在室温均有铁磁性,其饱和磁化强度随反应物中Mn离子浓度的提高,饱和磁化强度呈现出先增大,5at.%时达到最大值,0.11 emu/g,然后减小. 铁磁性来源于取代Zn离子的Mn离子之间的铁磁交换相互作用.     

Effects of cerium dopant concentration on structural properties and photocatalytic activity of electrospun Ce-doped TiO2 nanofibers

Electrospun \(\hbox {TiO}_2\) and Ce-doped \(\hbox {TiO}_2\) nanofibers were prepared with 0.5, 2.0 and 8.0 % weight Ce. The structural properties and phase composition were characterized using high-resolution transmission electron microscopy (HR-TEM), X-ray diffraction and X-ray absorption near edge spectroscopy (XANES) at the Ti K-edge. The undoped nanofibers are composed of an assembly of \(\hbox {TiO}_2\) nanoparticles and their crystal structure is a mixture of anatase and rutile phases with an anatase:rutile volume ratio close to 3:1. As Ce is introduced, the nanoparticles decrease in size and the rutile phase volume decreases. Ce \(\hbox {L}_3\) -edge XANES probed the local structure of Ce dopants. At 0.5 % Ce, most Ce ions are incorporated in the \(\hbox {Ce}^{3+}\) charge state but, at 2 % Ce, the majority are \(\hbox {Ce}^{4+}\) . Visible light absorption indicated that \(\hbox {Ce}^{3+}\) act as shallow acceptors that only participate in absorption of wavelengths below 420 nm but \(\hbox {Ce}^{4+}\) impurity states are associated with absorption of wavelengths up to 550 nm. Photocatalytic performance of the nanofibers was assessed by measuring the degradation of adsorbed Rhodamine B in aqueous solution under visible and ultraviolet light. The 0.5 % Ce-doped \(\hbox {TiO}_2\) nanofiber showed the best visible-light photocatalytic activity, which is probably due to the majority presence of \(\hbox {Ce}^{3+}\) . At higher Ce concentration, the photocatalytic reaction rate was lower than undoped nanofibers, indicating that recombination at the \(\hbox {Ce}^{4+}\) sites is rate limiting.     

p，n型掺杂剂与Mn共掺杂GaN的电磁性质

采用基于密度泛函理论的第一性原理平面波赝势法计算Mg,Zn,Si,O和Mn共掺GaN,分析比较共掺杂后的电子结构和磁学性质,并分别用平均场近似的海森伯模型和Zener理论估算共掺杂后体系的居里温度（T_C）.计算表明：共掺杂后体系均在能隙深处产生自旋极化杂质带,具有半金属性,能产生自旋注入.p型共掺杂（GaN：Mn-Mg＼Zn）后体系具有较GaN：Mn更稳定的FM态且能使T_C升高;而n型共掺杂（GaN：Mn-Si＼O）后体系FM态稳定性 关键词： Mg Zn Si O和Mn共掺GaN 第一性原理 T_C）')" href="#">居里温度（T_C）     

本征空位缺陷对ZnO:Mn体系电子特性及磁性的影响

本文采用基于密度泛函理论的第一性原理赝势法,分析了ZnO:Mn掺杂体系中本征空位缺陷V_(Zn)和V_O分别出现在相对Mn为近邻、次近邻、远次近邻位置时体系的晶体结构、能带分布、态密度和磁性.结果表明:ZnO:Mn体系中V_(Zn)比V_O更容易产生,且两种缺陷均更容易在Mn的近邻位置形成.其中V_(Zn)的出现没有明显改变ZnO:Mn体系的带隙,然而会使体系的导电性增加,且V_(Zn)与Mn的距离越远,导电性越强.同时,V_(Zn)减弱了体系的磁性,但与V_(Zn)的位置无关. V_O的出现会使体系带隙变宽,且电导率显著低于无缺陷ZnO:Mn体系,但是其导电性会随着V_O与Mn的距离变远而增强.同时,V_O的出现不会影响体系原来的磁性.     

Oxygen vacancy induced ferromagnetism in rutile TiO2–x

First‐principles LDA + U calculations have been performed to study the effects of oxygen vacancies (V_O) on the electronic structure and magnetism in undoped rutile TiO_2–x . Instead of treated as an adjustive parameter, the value of U was determined by constrained‐density‐functional calculations. The calculated electronic structure reveals that the valence electrons released by V_O would occupy mainly the neighboring Ti:3d orbital which then becomes spin‐polarized due to intra‐atomic exchange interaction, thereby giving rise to the half‐metallic ferromagnetism. The magnetization induced by V_O in rutile TiO_2–x is almost proportional to the V_O concentration (x) for x > 0.0625, and becomes 0 for x ≤ 0.0417. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Dopant concentration dependent magnetism of Cu-doped TiO2 nanocrystals

Journal of Nanoparticle Research - Mannosylation is a method commonly used to deliver nanomaterials to specific organs and tissues via cellular macrophage uptake. In this work, for the first time,...     

与掺杂浓度相关的ZnS∶Mn纳米粒子的发光性质

采用溶胶法制备了Mn掺杂的ZnS纳米粒子,探讨了掺杂离子浓度对ZnS∶Mn纳米粒子的晶体结构和发光性质的影响。通过X射线衍射（XRD）对样品的结构进行了表征,结果表明：所制备的ZnS∶Mn纳米粒子为立方闪锌矿结构,其在Mn离子的掺杂浓度达到6%时不发生分相,但随着掺杂浓度的增加,纳米粒子的平均粒径会减小。光致发光光谱和荧光光谱的结果表明：通过改变掺杂离子的浓度可实现对ZnS∶Mn纳米粒子590 nm附近荧光发射波长的调节。此外,研究了温度对纳米粒子形貌和发光性质的影响。高分辨透射电子显微镜（HRTEM）观察发现,经过50℃陈化1 h后的ZnS∶Mn样品的平均粒径增大约为20 nm,且加热陈化有利于ZnS∶Mn纳米粒子中Mn2＋在590 nm处产生荧光。     

Nitrogen vacancy effects on the ferromagnetism of Mn doped GaN films

The amorphous gallium nitride thin films doped with Mn were deposited by Laser assisted Molecular Beam Epitaxy (LMBE). After annealing at different NH₃ flow rates, the high-quality GaMnN crystalline films with different concentration of nitrogen vacancies (V _N) were obtained, which were confirmed by the X-ray diffraction spectroscopy and Raman measurements. The magnetic behaviors of these films were also obtained to investigate the effects of nitrogen vacancies. It indicates that V _N play a significant role in the origin of ferromagnetism. The stronger room-temperature ferromagnetism is given with the higher V _N concentration when it is not beyond a critical concentration. Moreover, from our M(T) curves and Raman analysis, the films present high resistivity. The magnetism of films with high resistivity varies with concentration of nitrogen vacancies, which can be explained by the bound magnetic polarons (BMP) theory.     

First-principles study on electronic,magnetic properties and optical absorption of vanadium doped rutile TiO2

The electronic, magnetic properties and optical absorption of vanadium (V) doped rutile TiO₂ have been studied by the generalized gradient approximation GGA and GGA+U (Hubbard coefficient) approach respectively. On the one hand, we consider the influence of vanadium with different doping concentration on the electronic structure. On the other hand, we study double V atoms doped TiO₂, mainly study four V-doped TiO₂ configurations, and find the magnetic ground states are ferromagnetic state. For the TiO₂@V-V1, TiO₂@V-V3 and TiO₂@V-V4 configurations without O ion as bridge between V-V atoms, there will have a metastable state of antiferromagnetic configurations, while, for the TiO₂@V-V2 configurations with an O ion as bridge between V-V atoms, due to the existence of superexchange between V-O-V, there will only exist the ground state of ferromagnetic state and there are no other metastable configurations. Furthermore, the optical properties of V-doped TiO₂ are calculated. The results show that the V-doped TiO₂ has strong infrared light absorption and visible light absorption.     

Oxygen vacancy model for chemochromic effects in LiNbO3 doped with Mn,Fe or Cu

Chemically induced changes in the optical absorption spectra of Mn, Fe or Cu in LiNbO₃ are interpreted by oxygen vacancy association during reduction. Relations to the photorefractive effect are discussed.     

Titanium atoms dimerization phenomenon and magnetic properties of titanium-antisite (TiO) and chromium doped rutile TiO2, ab-initio calculation

The ab-initio calculations based on the Korringa Kohn Rostoker approximation approach combined with coherent potential approximation (KKR-CPA), were used to study the magnetic properties of the titanium anti-site (Ti_O) and chromium (Cr) doped TiO₂. In the considered systems, we used different concentrations for Ti_O defect and Cr doping. In TiO_2(0.98)(Ti_O)_0.02, the obtained results indicate that Ti_O is a donor having half-metal behavior. Ti_O[3d] band is located at the Fermi level, although isn’t 100% polarized, the ferromagnetic (FM) state is verified as being more stable than disordered local moment (DLM) state. For Ti_0.98Cr_0.02O₂ the Cr doping introduced new states which give the material half-metallic feature. The majority spin of Cr impurities are located at the Fermi level and the conduction electrons around the Fermi level are 100% spin polarized. This indicates the stability of (FM) state. Moreover, in Ti_0.98Cr_0.02O_2(0.98)(Ti_O)_0.02, the top of the valence band is shifted to lower energy compared to pure TiO₂, and the n-type of TiO₂ is verified. The majority spin of Cr[3d] are located at 0.025 Ry close to the Fermi level. The predicted Curie temperatures (Tc) were calculated using the mean field approximation (MFA) and we predicted that Ti_O defect in Cr doped TiO₂ makes Tc higher. This kind of defect makes the material useful for spinotronics's applications and devices.     

基于第一性原理研究Y掺杂锐钛矿TiO2的磁光性质

基于第一性原理计算,建立了未掺杂和三种Y掺杂量的锐钛矿TiO2模型。对各个模型的形成能、磁性、电子结构及吸收光谱进行了计算。结果表明：掺入锐钛矿晶格的不同Y原子之间没有团簇趋势;Y掺杂量越大,实现掺杂所需的能量越高;Y掺杂的锐钛矿体系具有铁磁性,因而晶格中的自旋能级分裂效应能降低锐钛矿的带隙宽度,但当Y掺杂量升高时,这种影响显著减弱;随着Y掺杂量增加,弱束缚的O-2p态电子浓度增加,导致价带顶的O-2p态跨越费米能级,使得带隙值减小,进而提高了改性锐钛矿TiO2对可见光的吸收系数。     

Oxygen vacancy control of electrical,optical, and magnetic properties of Fe0.05Ti0.95O2 epitaxial films

High-quality Fe-doped TiO₂ films are epitaxially grown on MgF₂ substrates by pulsed laser deposition. The x-ray diffraction and Raman spectra prove that they are of pure rutile phase. High-resolution transmission electron microscopy (TEM) further demonstrates that the epitaxial relationship between rutile-phased TiO₂ and MgF₂ substrates is 110 TiO₂₂. The room temperature ferromagnetism is detected by alternative gradient magnetometer. By increasing the ambient oxygen pressure, magnetization shows that it decreases monotonically while absorption edge shows a red shift. The transport property measurement demonstrates a strong correlation between magnetization and carrier concentration. The influence of ambient oxygen pressure on magnetization can be well explained by a modified bound magnetization polarization model.     

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.     

Magnetic properties of Mn doped BN compound

Electronic and magnetic properties of diluted B_1−xMn_xN alloys are calculated by means of the full potential linearized augmented plane wave (FP-LAPW) method and the generalized gradient approximation (GGA). A half-metallic state is predicted for a composition of 6.25%. The spin majority being metallic and minority being semiconducting. We found a total magnetic moment of 2 μ_B (Bohr-magnetons) per supercell, in agreement with the half-metallic behaviour. The main contribution of the cell magnetic moment is localized at the transition metal site Mn, with a local moment of 1.24 μ_B.     

Influence of Mn ions concentration on optical and magnetic properties of Mn-doped ZnS nanowires

The optical and magnetic properties of ZnS:Mn²⁺ nanowires are tuned by Mn²⁺ concentration. The magnetic variation is ascribed to the competition between antiferromagnetic and ferromagnetic exchange interactions.

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