Synthesis and optical properties of Co-doped ZnO nanofibers prepared by electrospinning

In this work, Co-doped ZnO nanofibers have been fabricated successfully by an electrospinning technique. The as-prepared nanofibers are characterized by themogravimetric analysis (TG), scanning electron microscopy (SEM), transmission electron microscopy (TEM), powder X-ray diffraction (XRD), Raman spectra and photoluminescence spectroscopy (PL). Results have showed that a wurtzite ZnO nanofibers were obtained and the PL spectrum showed a red-shift by 10 nm due to narrowing of the ZnO band gap (∼3.29 eV) as a result of Co doping. Meanwhile, Raman scattering spectra exhibited an unusual peak at 540 cm⁻¹.     

Synthesis and characterization of ZnO:Co<Superscript>2+</Superscript> nanoparticles

This work investigates cobalt doped ZnO nanoparticles prepared by using wet chemical methods. The nanoparticles have a typical size of 3–8 nm. The electronic structure as well as the optical and magnetic properties of Co²⁺ have been characterized. X-ray diffraction spectra of the powder show wurtzite ZnO with no secondary Co phases. In the energy range below the bandgap, the optical absorption spectra show the internal d–d transitions related to Co²⁺ incorporated on the Zn lattice site in ZnO. Low temperature photoluminescence measurements confirm these results. Based on the analysis of the g-valuesfor bulk ZnO:Co., electron paramagnetic resonance measurements coincide with the simulation of Co-doped ZnO powder. Thus far, no evidence for ferromagnetism has been obtained. PACS 61.46.Df; 76.30.Fc; 78.67.Bf     

Raman spectroscopy of Cu doping in Zn1−xCoxO diluted magnetic semiconductor

The room‐temperature ferromagnetism and the Raman spectroscopy of the Cu‐doped Zn_1−xCo_xO powders prepared by the sol–gel method are reported. The x‐ray diffraction (XRD) data confirmed that the wurtzite structure of ZnO is maintained for ZnO doped with Co below 10 at%. The magnetization–field curves measured at room temperature demonstrated that all Co‐doped ZnO powders were paramagnetic. Ferromagnetic ordering is observed for the samples doped with Cu in Zn_0.98Co_0.02O and strongly depends on the concentration of Cu. The relative strength of the second‐order LO peak to the first‐order one in the Raman spectra, which is related to the carrier concentration, of the Cu‐doped Zn_0.98Co_0.02O powder is strongly correlated with the saturation magnetic moment of the system. This seems to be in favor of the Ruderman‐Kittel‐Kasuya‐Yosida (RKKY) or double exchange mechanism of the ferromagnetism in this system. Copyright © 2009 John Wiley & Sons, Ltd.     

Growth,electronic and magnetic properties of doped ZnO epitaxial and nanocrystalline films

We have used oxygen plasma assisted metal organic chemical vapor deposition along with wet chemical synthesis and spin coating to prepare Co_xZn_1-xO and Mn_xZn_1-xO epitaxial and nanoparticle films. Co(II) and Mn(II) substitute for Zn(II) in the wurtzite lattice in materials synthesized by both methods. Room-temperature ferromagnetism in epitaxial Co:ZnO films can be reversibly activated by diffusing in Zn, which occupies interstitial sites and makes the material n-type. O-capped Co:ZnO nanoparticles, which are paramagnetic as grown, become ferromagnetic upon being spin coated in air at elevated temperature. Likewise, spin-coated N-capped Mn:ZnO nanoparticle films also exhibit room-temperature ferromagnetism. However, the inverse systems, N-capped Co:ZnO and O-capped Mn:ZnO, are entirely paramagnetic when spin coated into films in the same way. Analysis of optical absorption spectra reveals that the resonances Co(I)↔Co(II)+e^- _CB and Mn(III)↔Mn(II)+h⁺ _VB are energetically favorable, consistent with strong hybridization of Co (Mn) with the conduction (valence) band of ZnO. In contrast, the resonances Mn(I)↔Mn(II)+e^- _CB and Co(III)↔Co(II)+h⁺ _VB are not energetically favorable. These results strongly suggest that the observed ferromagnetism in Co:ZnO (Mn:ZnO) is mediated by electrons (holes). PACS 75.50.Pp     

Studies of the physical properties of Co, Cu codoped ZnO powders

Zn_0.95−xCo_0.05Cu_xO powders have been synthesized by the sol-gel method and the structural, magnetic and electrical properties of the powders have been investigated. X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) indicate that the Co ions do not change the ZnO wurtzite structure. Magnetic measurements indicate that Co doping can induce room temperature (RT) ferromagnetism and the addition of Cu to the powders further increases the magnetic moment per Co ion. The effects of the introduction of Cu as an acceptor dopant in the host matrix are further studied using resistance measurements. It is demonstrated experimentally that acceptor doping plays an important role in realizing dominant ferromagnetic ordering in Co doped ZnO powders.     

衬底温度对ZnO薄膜的结构和光学特性的影响

利用等离子体辅助分子束外延(P-MBE)设备在蓝宝石衬底上通过改变生长温度,制备了不同的ZnO样品.研究了衬底温度对ZnO的结构、光学和电学性质的影响.样品的晶体结构利用X射线衍射谱进行表征.X射线衍射谱表明,所有的ZnO样品都是(002)取向的六角纤锌矿结构.随着生长温度的升高,X射线的(002)衍射峰的半峰全宽逐渐...     

Effects of doping concentration on properties of Mn-doped ZnO thin films

This paper reports that the radio frequency magnetron sputtering is used to fabricate ZnO and Mn-doped ZnO thin films on glass substrates at 500~°C. The Mn-doped ZnO thin films present wurtzite structure of ZnO and have a smoother surface, better conductivity but no ferromagnetism. The x-ray photoelectron spectroscopy results show that the binding energy of Mn_2p3 / 2 increases with increasing Mn content slightly, and the state of Mn in the Mn-doped ZnO thin films is divalent. The chemisorbed oxygen in the Mn-doped ZnO thin films increases with increasing Mn doping concentration. The photoluminescence spectra of ZnO and Mn-doped ZnO thin films have a similar ultraviolet emission. The yellow green emissions of 4~wt.% and 10~wt.% Mn-doped thin films are quenched, whereas the yellow green emission occurs because of abundant oxygen vacancies in the Mn-doped ZnO thin films after 20~wt.% Mn doping. Compared with pure ZnO thin film, the bandgap of the Mn-doped ZnO thin films increases with increasing Mn content.     

退火氛围对掺杂ZnO薄膜磁性的影响

采用直流磁控反应共溅法制备了非磁性元素Al和磁性元素Co掺杂的ZnO薄膜, 样品原位真空退火后再空气退火处理. 利用X射线衍射仪(XRD) 和物理性能测量仪(PPMS) 对薄膜的结构和磁性进行了表征. XRD和PPMS结果表明, 不同的退火氛围对掺杂薄膜的结构和磁性有着很大的影响. 真空退火的Al掺杂ZnO薄膜没有观察到铁磁性, 而空气退火的样品却显示出明显的室温铁磁性, 铁磁性的来源与空气退火后导致Al和ZnO基体间电荷转移增强有关. 而对于Co掺杂ZnO薄膜, 真空退火后再空气退火, 室温铁磁性明显减弱. 其磁性变化与Co离子和ZnO基体间电荷转移导致磁性增强和间隙Co原子被氧化导致磁性减弱有关.     

Effect of Al doping on microstructure and optical band gap of ZnO thin film synthesized by successive ion layer adsorption and reaction

Thin films of pure and aluminum-doped zinc oxide (AZO) were deposited on glass substrates from ammonium zincate bath following a chemical dipping technique called successive ion layer adsorption and reaction (SILAR). Characterization techniques such as X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy-dispersive X-rays (EDX) were used to investigate the effect of Al doping on the microstructure of AZO films. Particle size analysis using X-ray line broadening shows marginally increasing trend with increasing Al impurity. The average particle size for pure ZnO is 22.75 nm. It increases to 24.26 nm for 1% AZO film and 25.13 nm for 2% AZO film. Incorporation of Al was confirmed from elemental analysis using EDX. SEM micrograph shows that pure ZnO particles are spherical shaped. However, AZO films show particles with off-spherical shape with compact interconnected grains. The value of band gap for pure ZnO is 3.229 eV and it increases to 3.29 eV for 1% AZO indicating a blue-shift for 1% AZO film. However, for 2% AZO film, a decrease in band gap compared to pure ZnO is observed indicating a red-shift of fundamental absorption edge. Electrical resistance shows an initial decrease with increasing Al content. With further enhancement of Al incorporation, the resistance increases.     

Synthesis and characterization of undoped and tin-doped ZnO nanostructures

In this paper, undoped and tin-doped ZnO nanostructures were grown onto non-conductive substrates by a simple solution method. Structural, morphological, optical and electrical properties of the structures were investigated with respect to tin concentration. From XRD studies, all the ZnO nanostructures were found as hexagonal wurtzite type structures growing preponderantly oriented with c-axis normal to the substrate. An increase in tin content resulted in a decrease in grain size, whereas the dislocation density increases. SEM observations indicated that all the structures were textured throughout the substrates without any cracks or pores. The influence of incorporation of tin on surface morphology of the samples was clearly seen. Average diameter of the nanostructures decreased with increasing tin content. Absorption spectra of the structures revealed that the band gap of the films increases with increasing tin concentration. It is found that the tin-doped samples have higher average transmittance than the undoped one. The 1?% tin-doped sample exhibited ??80?% average transparency, which was the best transparency among the doped samples. Electrical measurements showed that resistivity of the structures increased with increasing dopant concentration. This increasing was attributed due to a decrease in carrier concentration caused by carrier traps at the grain boundaries.     

Room-temperature anomalous Hall effect and magnetroresistance in (Ga, Co)-codoped ZnO diluted magnetic semiconductor films

This paper reports that the(Ga,Co)-codoped ZnO thin films have been grown by inductively coupled plasma enhanced physical vapour deposition.Room-temperature ferromagnetism is observed for the as-grown thin films.The x-ray absorption fine structure characterization reveals that Co 2+ and Ga 3+ ions substitute for Zn 2+ ions in the ZnO lattice and exclude the possibility of extrinsic ferromagnetism origin.The ferromagnetic(Ga,Co)-codoped ZnO thin films exhibit carrier concentration dependent anomalous Hall effect and positive magnetoresistance at room temperature.The mechanism of anomalous Hall effect and magneto-transport in ferromagnetic ZnO-based diluted magnetic semiconductors is discussed.     

Electrical and optical spectroscopy on ZnO:Co thin films

Magnetic oxide semiconductors, for example the highly transparent and intrinsically n-type conducting zinc oxide doped with the 3d transition metal Co (ZnO:Co), are promising for the emerging field of spintronics [1]. We investigated n-conducting ZnO:Co thin films with a Co content of nominal 0.02, 0.20, or 2.00 at. %. The substitution of Co cations in the tetrahedral sites of wurtzite ZnO with Zn was confirmed at low temperature by the 1.877 eV photoluminescence between crystal field split d-levels of Co²⁺ (d⁷) ions. Based on theoretical studies, it is predicted that the formation of electron levels with zinc interstitials (I_Zn) or hole levels with zinc vacancies (V_Zn) is necessary to induce ferromagnetism, whereas the formation of electron levels with oxygen vacancies (V_O) is detrimental for ferromagnetism in ZnO:Co [2]. Cobalt generates a hole level in ZnO [3]. We investigated the generation of electron levels in n-conducting ZnO:Co in dependence on the Co content by means of deep level transient spectroscopy (DLTS). However, because of the ambiguous categorization of deep defects in n-conducting ZnO (V_O, I_Zn), an optimization of defect-related ferromagnetism in ZnO:Co is not possible at the moment. PACS 78.30.Fs; 91.60.Ed; 91.60.Mk     

Microstructure and optical properties of ZnO nanoparticles prepared by a simple method

In this investigation, ZnO nanoparticles were prepared by a simple and rapid method. This method is based on the short time solid state milling and calcinations of zinc acetate and citric acid powders. The samples were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared (FTIR) spectroscopy, photoluminescence and UV-vis spectroscopy. It was shown that the calcination temperature significantly affected the particle size and optical properties of the synthesized ZnO nanoparticles. Calculation based on the XRD data shows that the average sizes of ZnO particles are in agreement with those from TEM images and the size of the particles increases on increasing the calcination temperature. Also the band gap of samples decreased from 3.29 to 3.23 eV on increasing the calcination temperature from 350 to 600 °C. Photoluminescence analyses show that many defects such as interstitial zinc, zinc vacancy and oxygen vacancy are responsible for the observed optical properties.     

Effect of defects on room-temperature ferromagnetism in Co and Na co-doped ZnO

The role of defects in the room temperature ferromagnetism of the Co–ZnO based diluted magnetic semiconductor (DMS) was investigated by co-doping the DMS with Na. The structure characterizations indicate that both Na and Co ions enter into the ZnO lattice without the formation of secondary phase. The oxygen vacancy of ZnCoNaO increased while the carrier concentration decreased compared with that of ZnCoO, leading to the enhancement of the ferromagnetic property in the ZnCoNaO. The observed ferromagnetism introduced by Na ions is attributed to the exchange interaction via the electron trapped oxygen vacancies coupled with the magnetic Co ions.     

Structural and optical properties of Co-doped ZnO nanocrystallites prepared by a one-step solution route

Zinc oxide (ZnO) nanocrystallites with different Co-doping levels were successfully synthesized by a simple one-step solution route at low temperature (95 °C) in this study. The structure and morphology of the samples thus obtained were characterized by XRD, EDS, XPS and FESEM. Results show that cobalt ions, in the oxidation state of Co²⁺, replace Zn²⁺ ions in the ZnO lattice without changing its wurtzite structure. The dopant content varies from 0.59% to 5.39%, based on Co-doping levels. The pure ZnO particles exhibit well-defined 3D flower-like morphology with an average size of 550 nm, while the particles obtained after Co-doping are mostly cauliflower-like nanoclusters with an average size of 120 nm. Both the flower-like pure ZnO and the cauliflower-like Co:ZnO nanoclusters are composed of densely arrayed nanorods. The optical properties of the ZnO nanocrystallites following Co-doping were also investigated by UV–Visible absorption and Photoluminescence spectra. Our results indicate that Co-doping can change the energy-band structure and effectively adjust the luminescence properties of ZnO nanocrystallites.     

Effect of iron doping concentration on magnetic properties of ZnO nanoparticles

The ZnO:Fe nanoparticles of mean size 3-10 nm were synthesized at room temperature by simple co-precipitation method. The crystallite structure, morphology and size estimation were performed by X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM). The wurtzite structure of ZnO gradually degrades with the increasing Fe doping concentration. The magnetic behavior of the nanoparticles of ZnO with varying Fe doping concentration was investigated using a vibrating sample magnetometer (VSM). Initially these nanoparticles showed strong ferromagnetic behavior, however at higher doping percentage of Fe, the ferromagnetic behavior was suppressed and paramagnetic nature was observed. The enhanced antiferromagnetic interaction between neighboring Fe-Fe ions suppressed the ferromagnetism at higher doping concentrations of Fe. Room-temperature Mössbauer spectroscopy investigation showed Fe³⁺ nature of the iron atom in ZnO matrix.     

Effects of temperature-induced stress on the structural,electrical, and optical properties of ZnO:Ga thin films grown on Si substrates

Crystalline ZnO:Ga thin films with highly preferential c-axis oriented crystals were prepared on Si(001) substrates at different temperatures using the reactive magnetron sputtering technique. Effects of temperature-induced stress in ZnO:Ga films were investigated using X-ray diffraction (XRD), atomic force microscopy (AFM), electrical transport, and spectroscopic ellipsometry measurements. XRD results showed that the films were highly c-axis (out-of-plane) oriented and crystallinity improved with growth temperature. The residual compressive stress in films grown at low temperature relaxes with substrate temperature and becomes tensile stress with further increases in growth temperature. Resistivity of the films decreases with increasing stress, while the carrier concentration and mobility increase as the stress increases. The mechanism of the stress-dependent bandgap of ZnO:Ga films grown at different temperatures is suggested in the present work.     

过渡金属与F共掺杂ZnO薄膜结构及磁、光特性

采用溶胶-凝胶法在玻璃衬底上制备了过渡金属元素与F共掺杂Zn_0.98-xTM_xF_0.02O (TM_x=Cu_0.02, Ni_0.01, Mn_0.05, Fe_0.02, Co_0.05)薄膜, 进而利用X射线衍射仪、扫描电子显微镜、紫外-可见透过谱、光致发光及振动样品磁强计等研究了薄膜的表面形貌、微结构、禁带宽度及光致发光(PL)和室温磁学特性. 研究表明: 掺杂离子都以替位的方式进入了ZnO晶格, 掺杂不会破坏ZnO的纤锌矿结构. 其中Zn_0.93Co_0.05F_0.02O薄膜样品的颗粒尺寸最大, 薄膜的结晶度最好且c轴择优取向明显; Zn_0.93Mn_0.05F_0.02O薄膜样品的颗粒尺寸最小, 薄膜结晶度最差且无明显的c轴择优取; Cu, Ni, Fe与F共掺杂样品的颗粒尺寸大小几乎相同. TM掺杂样品均表现出很高的透过率, 同时掺杂后的薄膜样品的禁带宽度都有不同程度的红移. PL谱观察到Zn_0.98-xTM_xF_0.02O薄膜的发射峰主要由较强的紫外发射峰和较弱的蓝光发射峰组成. Zn_0.93Mn_0.05F_0.02O薄膜样品的紫外发光峰最弱, 蓝光发射最强, 饱和磁化强度最大; 与之相反的是Zn_0.96Cu_0.02F_0.02O薄膜, 其紫外发光峰最强, 蓝光发射最弱, 饱和磁化强度最小. 结合微结构和光学性质对Zn_0.98-xTM_xF_0.02O薄膜的磁学性质进行了讨论.     

Enhanced ferromagnetism in nano-sized Zn0.95Mn0.05O grains

The present work reports ferromagnetism by doping magnetic Mn atoms in the diamagnetic ZnO matrix and the ferromagnetism has been extended up to 640 K in nano-grained Zn_0.95Mn_0.05O samples. The bulk and nano-grained samples were stabilized in hexagonal crystal structure with space group p63mc. The grain size and lattice strain of the samples were estimated from room temperature XRD spectrum. Surface morphology of the samples was examined at room temperature using SEM picture and EDX spectrum. The ferromagnetism of the bulk material shows enhancement in nano-grained samples, which was mainly due to the solution of Mn atoms into the lattice sites of ZnO by mechanical milling. The enhancement of magnetic moment and ferromagnetic ordering temperature with reduction in grain size has been understood in terms of the core-shell structure and existing theoretical models. The present work also demonstrated the role of surface spin disorder on the enhancement of ferromagnetism in Zn_0.95Mn_0.05O nanograins.     

Room-temperature ferromagnetism in EDTA capped Cr-doped ZnS nanoparticles

Cr-doped ZnS nanoparticles with Cr concentrations of 0.5, 1, 2 and 3 atm.% were successfully synthesized by the chemical co-precipitation method using ethylenediaminetetraacetic acid (EDTA) as the capping agent. The structural, optical and magnetic properties of the prepared samples were studied. Energy dispersive spectroscopy (EDS) measurements showed the presence of Cr in the Cr-doped ZnS. No mixed phase was observed from X-ray diffraction (XRD) studies and all the peaks were indexed to the cubic phase of ZnS. The average diameter of the particles was in the range of 6–10 nm, and it was confirmed by TEM studies. The magnetic behavior of the nanoparticles for different chromium concentrations was investigated by magnetism measurements using a vibrating sample magnetometer (VSM). The nanoparticles with lower Cr concentration exhibited strong ferromagnetism, where as in samples of higher Cr concentrations the ferromagnetism suppressed. The electron paramagnetic resonance (EPR) spectra of the nanocrystals showed the resonance of electron centers with a g-value of 1.989. The signal intensity and linewidth of the EPR signal increased with increasing Cr content. FTIR studies indicated that the nanoparticles were sterically stabilized by EDTA.