过渡金属(Mn2+、Ni2+、Fe3+、Cu2+)掺杂ZnO基稀磁半导体的制备及性质

利用溶液腐蚀法制备了Mn2+、Ni2+、Fe3+、Cu2+离子掺杂的ZnO基稀磁半导体。XRD表明掺杂后的ZnO仍然保持单一的纤锌矿结构,没有任何杂质相产生。由紫外-可见光反射谱可知掺杂后吸收边发生了红移。掺杂前ZnO的带隙为3.20eV,对样品分别掺入Mn、Ni、Fe和Cu后的带隙分别为3.19eV、3.15eV、3.08eV和3.17eV。掺杂后样品的室温PL谱除了紫外发射峰外,对于Mn掺杂的样品还在蓝光区域出现了2个分别位于424nm和443nm的发射峰,Fe掺杂的样品出现了一个位于468nm的微弱发射峰,Cu掺杂的样品出现了位于469nm及535nm的很宽的发射峰。室温磁滞回线显示掺杂后样品有明显的铁磁性,掺入Mn、Ni、Fe和Cu样品的剩余磁化强度(Ms)分别为0.3902×10-3emu/cm3、0.454emu/cm3、0.372emu/cm3和0.962×10-3emu/cm3,矫顽力分别为47Oe、115.92Oe、99.33Oe和23Oe。经分析室温铁磁性来源于缺陷调制的Mn2+-Mn2+长程铁磁交换相互作用。     

A facile one step synthesis of SnO<Subscript>2</Subscript>/CuO and CuO/SnO<Subscript>2</Subscript> nanocomposites: photocatalytic application

Here novel photocatalysts, SnO₂/CuO and CuO/SnO₂ nanocomposites were successfully synthesized by chemical method at room temperature. X-ray Diffraction (XRD), transmission electron microscopy (TEM), Fourier transform Infrared (FT-IR), UV–Visible (UV–Vis) and photoluminescence (PL) spectroscopy were utilized for characterization of the nanocomposites. The photocatalytic activity of the nanocomposites was investigated. The hybrid nanocomposites exhibited high photocatalytic activity as evident from the degradation of methylene blue (MB) dye. The result revealed substantial degradation of the MB dye (92 and 69.5% degradation of SnO₂/CuO and CuO/SnO₂, respectively) under visible light illumination with short period of 30 min. Their large conduction band potential difference and the inner electrostatic field formed in the p–n heterojunction provide a strong driving force for the photogenerated electrons to move from Cu₂O to SnO₂ under visible light illumination. The excellent photodegradation of methylene blue suggested that the heterostructured SnO₂/CuO nanocomposite possessed higher charge separation and photodegradation abilities than CuO/SnO₂ nanocomposite under visible light irradiation.     

Synthesis,characterisation and antimicrobial activity of manganese- and iron-doped zinc oxide nanoparticles

The present work reports study on antimicrobial activity of pure and doped ZnO nanocomposites. Polyvinyl pyrrolidone capped Mn- and Fe-doped ZnO nanocomposites were synthesised using simple chemical co-precipitation technique. The synthesised materials were characterised using transmission electron microscope (TEM), X-ray powder diffraction (XRD), energy dispersive X-ray fluorescence (EDXRF), Fourier transform infrared (FTIR) spectroscopy and ultraviolet (UV) visible spectroscopy. The XRD and TEM studies reveal that the synthesised ZnO nanocrystals have a hexagonal wurtzite structure with average crystalline size ～7–14 nm. EDXRF and FTIR study confirmed the doping and the incorporation of impurity in ZnO nanostructure. The antimicrobial activities of nanoparticles (NPs) were studied against fungi, gram-positive and gram-negative bacteria using the standard disc diffusion method. The photocatalytic activities of prepared NPs were evaluated by degradation of methylene blue dye in aqueous solution under UV light irradiation. Experimental results demonstrated that ZnO NPs doped with 10% of Mn and Fe ions showed maximum antimicrobial and photodegradation efficiency in contrast with that of the 1% loading. The enhancement in antimicrobial effect and photocatalytic degradation is attributed to the generation of reactive oxygen species due to the synergistic effects of Mn and Fe loading.     

Enhanced photocatalytic activity of Fe-doped ZnO nanoparticles synthesized via a two-step sol–gel method

A series of Zn_1–x Fe _x O (x = 0, 1, 2, 3, 4 %) powders via a two-step sol–gel method in open system were successfully fabricated. Influence of Fe doping concentration on the structure, morphology, optical properties and photo catalysis properties were investigated by means of X-ray diffraction, scanning electron microscopy, UV–Vis spectrophotometer and photochemical reaction instrument. The results showed that the ZnO powders were hexagonal wurtzite structures and their crystalline sizes and particle diameters decreased with the increase of Fe doping concentration. An increase of visible light absorption value and a decrease in band gap from 3.219 to 3.167 eV were found with the increase of Fe doping concentration, which enable the sample harvest more photons to excite the electron from the valence. Enhanced visible light induced photocatalytic activity has been found in Fe doped ZnO and the ultraviolet light induced photocatalytic properties of the Fe-doped ZnO have been improved greatly compared with undoped ZnO and commercially available TiO₂ (P25). The photocatalytic activities were not significantly affected by the particle size, and the best Fe doping concentration is 1 %.     

Synthesis and Physical Properties of Mn Doped ZnO Dilute Magnetic Semiconductor Nanostructures

Mn doped ZnO nanostructures have been prepared using low temperature simple, quick, and versatile synthesis approach. The structural, microstructural, and vibrational investigations reveal that as prepared nanostructures with low Mn doping concentration have single hexagonal phase and are grown along the preferred c-axis. The X-rays photoelectron spectroscopy demonstrates that the Mn ions are in mixed oxidation states for high doping concentration of Mn, while are in 2+ oxidation state for low concentration into ZnO lattice. The photoluminescence spectrum (PL) exhibits a significant red-shift of 22 nm in the optical band gap of doped ZnO and shows the improved luminescence properties, which makes it potential for its use in the photocatalyst, optoelectronics and solar cell nanodevices. Furthermore, the magnetic measurement of Mn doped ZnO nanostructures exhibits the ferromagnetism at room temperature.     

Chemical,morphological, structural,optical, and magnetic properties of Zn<Subscript>1−x</Subscript>Nd<Subscript>x</Subscript>O nanoparticles

In the present investigation, we made an endeavor to fabricate the ZnO nanoparticles and achieved the tunable properties with Nd doping. The Nd-doped ZnO nanoparticles were characterized via X-ray diffraction (XRD), Raman, and X-ray photoelectron spectroscopy (XPS) studies that confirmed the successful doping of Nd ions in the ZnO crystal lattice without amending its hexagonal phase. The particle morphology revealed nearly spherical particles with uniform size distribution. The band gap of these samples was determined using diffuse-reflectance spectra (DRS) and was found to vary from 3.17 to 3.21 eV with increasing Nd concentration. A broad and intense emission band at 1083 nm for Nd doped ZnO nanoparticles is observed and is assigned to corresponding emission transition ⁴F_3/2?→?⁴I_11/2 of Nd³⁺ ions. Furthermore, the magnetic studies indicate that the Nd doping altered the magnetic behavior of nanocrystalline ZnO particles from diamagnetic to ferromagnetic at 300 K and that the magnetization of these samples decreased with increasing Nd concentration. The tunable optical band gap as well as room-temperature ferromagnetism of these samples may find applications in both optoelectronics and spintronics.     

Construction of hierarchical TiO<Subscript>2</Subscript> nanorod array/graphene/ZnO nanocomposites for high-performance photocatalysis

The photocatalytic performance of heterostructure photocatalysts is limited in practical use due to the charge accumulation at the interface and its low efficiency in utilizing solar energy during photocatalytic process. In this work, a ternary hierarchical TiO₂ nanorod arrays/graphene/ZnO nanocomposite is prepared by using graphene sheets as bridge between TiO₂ nanorod arrays (NRAs) and ZnO nanoparticles (NPs) via a facile combination of spin-coating and chemical vapor deposition techniques. The experimental study reveals that the graphene sheets provide a barrier-free access to transport photo-excited electrons from rutile TiO₂ NRAs and ZnO NPs. In addition, there generates an interface scattering effect of visible light as the graphene sheets provide appreciable nucleation sites for ZnO NPs. This synergistic effect in the ternary nanocomposite gives rise to a largely enhanced photocurrent density and visible light-driven photocatalytic activity, which is 2.6 times higher than that of regular TiO₂ NRAs/ZnO NPs heterostructure. It is expected that this hierarchical nanocomposite will be a promising candidate for applications in environmental remediation and energy fields.     

Enhanced optical properties of heterostructured ZnO/CeO2 nanocomposite fabricated by one-pot hydrothermal method: Fluorescence and ultraviolet absorption and visible light transparency

Many researchers investigated the properties of either discrete metal oxide CeO₂ or ZnO materials. However, less attention has been paid to the various nanostructure and performances of CeO₂ and ZnO nanocomposite up to now. In this paper, a facile and low cost one-pot hydrothermal synthesis method has been adopted to obtained directly precursors of CeCO₃OH and Zn₅(CO₃)₂(OH)₆ with different Ce atom molar ratios to Zn, which are transformed into their corresponding metal oxide to form the ZnO/CeO₂ heterostructure nanocomposites (HSNCs) by pyrolysis. The heterostructure is composed of ZnO and CeO₂ monocrystals, simultaneously, CeO₂ monocrystals are well dispersed on the surface of ZnO monocrystal for cosmetics. Bing dependent on the analysis results of XRD and TEM for the obtained precursors before and after pyrolysis, the formation mechanism of HSNCs was proposed. To the best of our knowledge, the paper first reported heterostructured ZnO/CeO₂ nanocomposite grown in one-pot mixed aqueous solution of cerium nitrate, zinc acetate and urea without other extra surfactant. Additionally, the influence of various Ce/Zn molar ratios on the heterostructure, fluorescence emission and UV–visible absorption properties of HSNCs was investigated in detail. ZnO/CeO₂ HSNCs display higher fluorescence emission with the increasing Ce/Zn molar ratio. Meanwhile, the larger Ce/Zn molar ratio of ZnO/CeO₂ HSNCs, the stronger transparency in the visible light region and the weaker UV absorption. The results are due to the fact that the band gap of ZnO/CeO₂ HSNCs will decrease from 3.25 to 3.08 eV when Ce/Zn atom molar ratio is increased from 0 to 0.08. By the comprehensive analysis on the optical performances of HSNCs with the different Ce/Zn atom molar ratios, ZnO/CeO₂-0.04 HSNCs could become UV absorber materials and transparent material in the visible region. ZnO/CeO₂-0.04 HSNCs with the UV-filtering and Vis-transparent properties is appropriate for personal-care cosmetics.     

Effect of Fe doping concentration on optical and magnetic properties of ZnO nanorods

Herein, a facile low temperature, aqueous solution-based chemical method has been demonstrated for large-scale fabrication of Fe doped ZnO nanorods (ZnO:Fe) with a series percentage of Fe dopant. Interestingly, the SEM results reveal a uniform well dispersed synthesis of ZnO:Fe nanorods throughout the substrate. The x-ray diffraction result suggests that Fe substitutes Zn in the ZnO matrix and rules out the formation of any secondary phase. Selected area electron diffraction investigation verifies the single crystal, hexagonal wurtzite structure of the ZnO:Fe nanorods. Energy dispersive spectroscopy data confirm Fe doping of the ZnO nanorods with a concentration ranging from 0.9 to 2.2 at.%. The photoluminescence spectrum reveals a continuous suppression of defect related broad-band emission (I(D)/I(UV) = 1-0.11) by increasing the concentration of the dopant ion, which produces the quenching of surface defects present in the nanostructures. An enhancement in ferromagnetism (M = 0.15 × 10?2-0.24 × 10?1 emu g?1 at 2000 Oe) is found in doped ZnO nanorods.     

Synthesis of AgBr/ZnO nanocomposite with visible light-driven photocatalytic activity

AgBr/ZnO nanocomposite was synthesized via chemical precipitation from pure ZnO nanowires, AgNO₃, and NaBr. Inductively coupled plasma optical emission spectroscopy, X-ray diffraction, and high resolution transmission electron microscopy results confirmed the forming of AgBr/ZnO nanocomposite. High resolution transmission electron microscopy results of the as-synthesized AgBr/ZnO nanocomposite revealed that AgBr nanoparticles were attached to the surface of ZnO nanowires. UV-vis diffuse reflectance spectra of both pure ZnO and AgBr/ZnO nanocomposite displayed a band gap edge at about 350-380 nm. However, compared with pure ZnO, an additional broad tail from approximately 400 nm to 700 nm appeared in the UV-vis diffuse reflectance spectrum of AgBr/ZnO nanocomposite. The photocatalytic studies indicated that the as-synthesized AgBr/ZnO nanocomposite was a kind of promising photocatalyst in remediation of water polluted by some chemically stable azo dyes under visible light.     

Structural and magnetic properties of Mn-doped ZnO nanorod arrays grown via a simple hydrothermal reaction

High density Mn-doped ZnO nanorod arrays were vertically grown on ITO substrate via hydrothermal reaction at relatively low temperature of 95 °C. The microstructure and magnetism of the arrays have been examined. Field emission scanning electron microscopy shows that the nanorods of 100 nm diameter and 1 μm length grow along the [001] direction. X-ray photoemission spectroscopy demonstrates that Mn is successfully doped into the nanorods. Meanwhile, all the Mn-doped ZnO nanorod arrays are ferromagnetic at room temperature. It is also found that the value of the saturation magnetization (M_s) of the ZnO nanorod arrays firstly increases with increasing the Mn concentration and then decreases. The higher M_s value is 0.11emu/g, which is obtained in the 5 at.% Mn-doped ZnO nanorod arrays. The ferromagnetism comes from the ferromagnetic interaction between the Mn ions, which partly replace Zn ions.     

Local structure and photocatalytic property of sol–gel synthesized ZnO doped with transition metal oxides

ZnO nanoparticles doped with up to 5 at% of Co and Mn were prepared using a co-precipitation method. The location of dopant ions and the effect of doping on the photocatalytic activity were investigated. The crystal structure of nanoparticles and local atomic arrangements around dopant ions were analyzed by X-ray absorption spectroscopy. The results showed that the Co ions substituted the Zn ions in the ZnO wurtzite phase structure and induced lattice shrinkage, while Mn ions were not completely incorporated in the crystal lattice. The photocatalytic activity under simulated sunlight was characterized by the decomposition of Rhodamine B dye molecules. It was revealed that Co-doping strongly reduced the photocatalytic activity but Mn-doping showed a weaker effect on the reduction of the photoactivity.     

Synthesis and properties of Fe/Fe3O4 nanocomposites coated with ZnS

Multifunctional Fe/Fe₃O₄@ZnS nanocomposites were synthesized by hydrothermal method, with Fe/Fe₃O₄ doped Co ion as the magnetic core and ZnS as the luminescent shell. The morphology, structure, luminescent and magnetic properties of the nanocomposites were investigated by XRD, FESEM, photoluminescence PL and VSM. The maximum emission peak and special saturation magnetization Ms of the nanocomposites are at 467 nm and 78.6 emu/g, respectively. For the nanocomposites, it is shown that there are both better magnetic behavior and fluorescence properties.     

A comparison between ZnO films doped with 3d and 4f magnetic ions

We present electrical and magnetic properties of ZnO films doped with 3d (Mn) and 4f (Gd or Nd) magnetic ions grown on a-plane Al₂O₃ substrates. Both for films doped with 3d magnetic ions and for films doped with 4f magnetic ions, Hall investigations revealed that the carrier concentration decreases and the resistivity increases with increasing the oxygen partial pressure during the pulsed laser deposition growth, probably because the formation of oxygen vacancies is hindered. Measurements of magnetic properties revealed ferromagnetism above room temperature with magnetic moments up to 0.2 μ_B/Mn ion in insulating ZnO:Mn films co-doped with 0.1% P and up to 0.3 μ_B/Gd ion in n-conducting ZnO:Gd films co-doped with 0.2% Al.     

Influence of Fe dopant concentration and annealing temperature on the structural and optical properties of ZnO thin films deposited by sol–gel method

Nanostructured Fe doped ZnO thin films were deposited onto glass substrates by sol–gel spin coating method. Influence of Fe doping concentration and annealing temperature on the structural, compositional, morphological and optical properties were investigated using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), UV–Vis spectroscopy and photoluminescence (PL) measurements. XRD analysis showed that all the films prepared in this work possessed a hexagonal wurtzite structure and were preferentially oriented along the c-axis. Pure ZnO thin films possessed extensive strain, whereas Fe doped films possessed compressive strain. In the doped films, least value of stress and strain was observed in the 0.5 at.% Fe doped thin film, annealed at 873 K. Average crystallite size was not significantly affected by Fe doping, but it increased from 15.57 to 17.79 nm with increase in annealing temperature from 673 to 873 K. Fe ions are present in +3 oxidation state as revealed by XPS analysis of the 0.5 at.% Fe doped film. Surface morphology is greatly affected by changes in Fe doping concentration and annealing temperature which is evident in the SEM images. The increase in optical band gap from 3.21 to 3.25 eV, with increase in dopant concentration was attributed to Moss–Burstein shift. But increase in annealing temperature from 673 to 873 K caused a decrease in band gap from 3.22 to 3.20 eV. PL spectra showed emissions due to excitonic combinations in the UV region and defect related emissions in the visible region in all the investigated films.     

Influence of oxygen vacancies on the structural,dielectric, and magnetic properties of (Mn,Co) co-doped ZnO nanostructures

We analysed the variation and effect of oxygen vacancies on the structural, dielectric and magnetic properties in case of Mn (4%) and Co (1, 2 and 4%) co-doped ZnO nanoparticles (NPs), synthesized by chemical precipitation route and annealed at 750 °C for 2 h. From the XRD, the calculated average crystallite size increased from15.30?±?0.73 nm to 16.71?±?012 nm, when Co content is increased from 1 to 4%. Enhancement of dopants (Mn, Co) introduced more and more oxygen vacancies to ZnO lattice confirmed from EDX and XPS. The high-temperature annealing leads to reduction of the dielectric properties due to enhancement in grain growth (large grain volume and lesser number of grain boundaries) with the incorporation of Co and Mn ions into the ZnO lattice. The electrical conductivity of the Mn doped and (Mn, Co) co-doped ZnO samples were enhanced due to increase in the volume of conducting grains and charge density (liberation of trapped charge carriers in oxygen vacancies and free charge carriers at higher frequencies). The Mn-doped and (Mn, Co) co-doped ZnO NPs show ferromagnetic (FM) behaviour. The saturation and remnant magnetizations (M_s and M_r) elevates from (0.235 to 1.489)?×?10^?2 and (0.12 to 0.27)?×?10^?2 emu/g while Coercivity (H_c) reduced from 97 to 36 Oe with enhancement in the concentration of dopants in ZnO matrix. Oxygen vacancies were found to be the main reason for room-temperature ferromagnetism (RTFM) in the doped and co-doped ZnO NPs. The results show that the enhanced dielectric and magnetic properties of Mn doped and (Mn, Co) co-doped ZnO is strongly correlated with the concentration of oxygen vacancies. The observed enhanced RTFM, dielectric properties and electrical conductivity makes TM doped ZnO nanoparticles suitable for spintronics, microelectronics and optoelectronics based applications.     

Magnetic and optical properties of polycarbonate/Fe nanocomposites

The magnetic and optical properties of polycarbonate (PC)/Fe nanocomposite films prepared by a solution blended process and the role of Fe additives are investigated. The saturation magnetization of the PC/Fe nanocomposites depends on the weight of Fe nanoparticles. Meanwhile, an increase of photoluminescence (PL) intensity with decreasing Fe additives is interpreted. The optical band gap corresponds to the increase of PL elements. The transmittance of the films increases with reduced Fe, and the PL peak energy of PC/Fe composites is also correlated to the weight ratio.     

Cu掺杂ZnO纳米粒子的光学性能及铁磁性

利用溶胶凝胶法制备了纳米结构的Cu掺杂ZnO基稀磁半导体,通过X射线衍射分析表明,样品为纯相ZnO纤锌矿结构,磁性测量表明样品在室温下呈室温铁磁性,铁磁性来源为氧化锌晶格中的缺陷与Cu2+离子之间的交换作用。室温光致发光(PL)谱观察到紫外带边和可见光区两个发射峰,且随着Cu掺杂量增加,紫外峰淬灭,可见峰发射增强。     

High quality ZnO/CuO nanocomposites synthesized by microwave assisted reaction

Highly crystalline zinc oxide (ZnO) and ZnO/CuO nanocomposite powders have been synthesized by a facile microwave irradiation method. The resulting powders were characterized in terms of structural, optical and morphological properties by X-ray diffraction (XRD), room temperature photoluminescence (PL) spectroscopy and scanning electron microscopy (SEM), respectively. XRD patterns revealed the formation of ZnO/CuO nanocomposites with good crystalline quality. SEM images displayed the formation of hexagonal ZnO and flower shaped agglomeration of ZnO/CuO nano-flakes with uniform production. The strong UV emission peak observed at around 380 nm show enhanced intensity for ZnO/CuO nanocomposite. Compared to ZnO nanoparticles, ZnO/CuO composites exhibit good transparency with sharp absorbance edges. The simplicity of synthesis route coupled with better optical and PL emission properties propose the microwave synthesized ZnO/CuO nanocomposite powders a promising material for optoelectronic devices.     

Strong room temperature ferromagnetism in chemically precipitated ZnO:Co2+:Bi3+ nanocrystals for DMS applications

Well crystalline Co-Bi co-doped ZnO nanostructures with various concentration of Bi were synthesized by simple chemical precipitation technique using metal nitrate precursors. The structural and magnetic properties of the samples calcined at 300 °C for 6 h has been studied comprehensively. X-ray diffraction patterns of the pure and Co-with Bi doped samples have shown the well crystalline diffraction peaks corresponds to the characteristic wurtzite ZnO crystal structure. Aggregated nano particles have emerged with flower like morphology and it can be seen from the scanning electron microscopy and transmission electron microscopy. The average particle diameter was estimated and found to be 25–35 nm. Tunable optical band gap related to an additional electron state created by dopant was observed from the UV–Visible spectra. Typical PL emission in the UV, visible and continuous deep level emission further demonstrates that the potential application of the material in optoelectronics. Excellent ferromagnetic features of the material at room temperature reveal the additional carrier induced exchange interaction could enhance the ferromagnetism in co-doped ZnO nanostructure. The addition of Bi at 3⁺ states can act as donor within the semiconductor which provides the additional electron charge carrier that could involve directly to the exchange interaction effectively at certain limit and enhances the ferromagnetism. At higher doping concentration the formation of diamagnetic Bi₂O₃ secondary phase have contributed to change the ferromagnetic behaviour of the sample. From this study it is suggested that this kind of combined ferromagnetism and excellent optical tunability of the Bi co-doped ZnO:Co system will be the potential material for future magneto-opto-electronic devices.