Studies of luminescence properties of ZnO and ZnO:Zn nanorods prepared by solution growth technique

Pyramidal ZnO nanorods with hexagonal structure having c-axis preferred orientation are grown over large area silica substrates by a simple aqueous solution growth technique. The as-grown nanorods were studied using XRD, SEM and UV-vis photoluminescence (PL) spectroscopy for their structural, morphological and optical properties, respectively. Further, the samples have also been annealed under different atmospheric conditions (air, O₂, N₂ and Zn) to study the defect formation in nanorods. The PL spectra of the as-grown nanorods show narrow-band excitonic emission at 3.03 eV and a broad-band deep-level emission (DLE) related to the defect centers at 2.24 eV. After some mild air annealing at 200 °C, fine structures with peaks having energy separation of ∼100 meV were observed in the DLE band and the same have been attributed to the longitudinal optical (LO) phonon-assisted transitions. However, the annealing of the samples under mild reducing atmospheres of N₂ or zinc at 550 °C resulted in significant modifications in the DLE band wherein high intensity green emission with two closely spaced peaks with maxima at 2.5 and 2.7 eV were observed which have been attributed to the V_O and Zn_i defect centers, respectively. The V-I characteristic of the ZnO:Zn nanorods shows enhancement in n-type conductivity compared to other samples. The studies thus suggest that the green emitting ZnO:Zn nanorods can be used as low voltage field emission display (FED) phosphors with nanometer scale resolution.     

The structural and magnetic properties of Co-doped titanate nanotubes synthesized under hydrothermal conditions

Co-doped titanate nanotubes were prepared from hydrothermal treatment on Co-doped anatase TiO₂ powders in a concentrated NaOH aqueous solution and characterized by a variety of techniques. We mainly investigated the structural and magnetic properties of these nanotubes. It was found that the obtained nanotubes might possibly be constructed from H₂Ti₃O₇, their undoped counterpart. The result from Raman spectra showed that Ti–OH bonds existed in the tubular structure. The electron paramagnetic resonance and X-ray photoelectron spectroscopy studies clearly showed that the Co was incorporated into the titanate lattice as Co²⁺ and substituted for Ti cations sites. Also, from the photoluminescence measurement, the presence of oxygen vacancies was detected in the nanotubes. The vibrating sample magnetometer measurement revealed a clear paramagnetic behavior with weakly ferromagnetic ordering at room temperature. The results suggested that ferromagnetism of the nanotubes was related to the oxygen vacancies and could be suppressed by their quantum size. PACS 81.07.De; 75.75.+a; 75.50.Pp     

Ag-doped ZnO nanorods synthesized by two-step method

A two-step method is adopted to synthesize Ag-doped ZnO nanorods.A ZnO seed layer is first prepared on a glass substrate by thermal decomposition of zinc acetate.Ag-doped ZnO nanorods are then assembled on the ZnO seed layer using the hydrothermal method.The influences of the molar percentage of Ag ions to Zn ions(RAg/Zn) on the structural and optical properties of the ZnO nanorods obtained are carefully studied using X-ray diffractometry,scanning electron microscopy and spectrophotometry.Results indicate that Ag ions enter into the crystal lattice through the substitution of Zn ions.The<002>c-axis-preferred orientation of the ZnO nanorods decreases as RAg/Zn increases.At RAg/Zn >1.0%,ZnO nanorods lose their c-axis-preferred orientation and generate Ag precipitates from the ZnO crystal lattice.The average transmissivity in the visible region first increases and then decreases as R Ag/Zn increases.The absorption edge is first blue shifted and then red shifted.The influence of Ag doping on the average head face,and axial dimensions of the ZnO nanorods may be optimized to improve the average transmissivity at RAg/Zn <1.0%.     

Selective growth of ZnO nanorods in aqueous solution

ZnO nanorod arrays find applications in solar energy conversion, light emission and other promising areas. One approach to generate ZnO nanorods is the cost efficient aqueous chemical growth (ACG). Usually the ACG process is based on a nucleation step followed by growth of ZnO nanorods in aqueous solution at temperatures below 95 C.We report on the fabrication of homogeneous, large scale arrays of nanorods on various substrate materials (Si, glass, polymer) by ACG. PL-measurements show surprisingly good optical quality although the rods were grown at low temperature.Even though we have developed patterning of these arrays with photolithographic techniques, a bottom up approach for lateral patterning is important concerning further applications especially for mass-production. The substrates with patterned metal layers were employed to realize selective growth of nanorods. The experiments were carried out on Ti-, Ag- and Pt-patterned substrates. Selective growth on metal structured glass substrates was developed and is described.     

Study of the magnetic and structural properties of Mn-, Fe-, and Co-doped ZnO powder

A study of the magnetic and structural properties of Zn_1−xM_xO powder (where x=0 or 0.01, and M=Mn, Fe or Co) produced by the proteic sol–gel process was undertaken. The sample crystal structure was analyzed by XRD and magnetic measurements were carried out in a SQUID magnetometer. Of the XRD analysis, all samples had hexagonal wurtzite crystal structure with P63mc space group, and no secondary phase was observed. It is observed of the M(H) measures at 2 K, that the Co- and Mn-doped ZnO displayed saturation magnetizations (M_s) of approximately 2 and 3.2 emu/g, respectively, and no remanence (M_r) was observed, indicating a superparamagnetic behavior in these samples. However, the Fe-doped sample showed a ferromagnetic behavior with M_s∼0.34 emu/g, M_r∼0.05 emu/g, and coercivity (H_c)∼1090 Oe. Already at room temperature, the M(H) measurements reveal a purely paramagnetic behavior for Mn- and Fe-doped ZnO, indicating that the Curie temperature (T_c) is below 300 K. However, a weak superparamagnetic behavior was observed in the Co-doped sample, indicating that T_c>300 K.     

A study on morphology control and optical properties of ZnO nanorods synthesized by microwave heating

In this study, we present morphology control investigations on zinc oxide (ZnO) nanorods synthesized by microwave heating of a mixture of zinc nitrate hexahydrate and hexamethylenetetramine (HMTA) precursors in deionized water (DI water). To study the morphology and structural variations of the obtained ZnO nanorods in different molar ratio of zinc nitrate hexahydrate to HMTA, X-ray diffraction (XRD), scanning electron microscopy (SEM) images, Raman scattering, and photoluminescence (PL) spectroscopy were measured. XRD and SEM images are utilized to examine the crystalline quality as well as the morphological properties of the ZnO nanorods. It is found that morphology control can be achieved by simply adjusting the reactant concentrations and the molar ratio of zinc nitrate hexahydrate to HMTA. Raman scattering and PL spectroscopy measurements were demonstrated to study the size- and shape-dependent optical response of the ZnO nanorods. The Raman scattering result shows that the intensity of LO mode at around 576 cm^?1 decreases with the increase in the molar ratio of zinc nitrate hexahydrate to HMTA, indicating the reduction of defect concentrations in the synthesized ZnO nanorods. Room temperature PL spectrum of the synthesized ZnO nanorods reveals an ultraviolet (UV) emission peak and a broad visible emission. An enhancement of UV emission appears in the PL spectra as the molar ratio of zinc nitrate hexahydrate to HMTA increases, indicating that the defect concentration of the synthesized ZnO nanorods can be reduced by increasing the molar ratio.     

Structural, electronic, and magnetic properties of Co-doped ZnO

Density functional theory based calculations have been carried out to study structural, electronic, and magnetic properties of Zn1-xCoxO (x = 0, 0.25, 0.50, 0.75) in the zinc-blende phase, and the generalized gradient approximation proposed by Wu and Cohen has been used. Our calculated lattice constants decrease while the bulk moduli increase with the increase of Co 2+ concentration. The calculated spin polarized band structures show the metallic behavior of Co-doped ZnO for both the up and the down spin cases with various doping concentrations. Moreover, the electron population is found to shift from the Zn-O bond to the Co-O bond with the increase of Co 2+ concentration. The total magnetic moment, the interstitial magnetic moment, the valence and the conduction band edge spin splitting energies, and the exchange constants decrease, while the local magnetic moments of Zn, Co, O, the exchange spin splitting energies, and crystal field splitting energies increase with the increase of dopant concentration.     

Optical and magnetic properties of laser-deposited Co-doped ZnO thin films

We report the optical and magnetic properties of laser-deposited Zn_1−xCo_xO (x=0.06-0.3) thin films with no intentional electrical carrier doping. The analysis of the high-temperature magnetization data provides an unambiguous evidence that antiferromagnetic superexchange interaction is the dominant mechanism of the exchange coupling between Co ions in Zn_1−xCo_xO alloy, yielding the value of the effective exchange integral J₁/k_B to be about −27 K. The low-temperature magnetization data reveals a spin glass transition in Zn_1−xCo_xO alloy for the Co content x>0.15, giving the value of the spin freezing temperature T_f to be ∼8 and ∼12 K for x=0.2 and 0.25, respectively. Optical spectra analysis shows a linear increase of the band gap E_g with the increase of the Co content following E_g=3.231+1.144x eV.     

Doping dependent room-temperature ferromagnetism and structural properties of dilute magnetic semiconductor ZnO:Cu nanorods

Copper doped ZnO nanoparticles were synthesized by the chemical technique based on the hydrothermal method. The crystallite structure, morphology and size were determined by X-ray diffraction (XRD), high resolution transmission electron microscopy (HRTEM) and scanning electron microscopy (SEM) for different doping percentages of Cu²⁺ (1-10%). TEM/SEM images showed formation of uniform nanorods, the aspect ratio of which varied with doping percentage of Cu²⁺. The wurtzite structure of ZnO gradually degrades with the increasing Cu²⁺ doping concentration and an additional CuO associated diffraction peak was observed above 8% of Cu²⁺ doping. The change in magnetic behavior of the nanoparticles of ZnO with varying Cu²⁺ doping concentrations was investigated using a vibrating sample magnetometer (VSM). Initially these nanoparticles showed strong room-temperature ferromagnetic behavior, however at higher doping percentage of copper the ferromagnetic behavior was suppressed and paramagnetic nature was enhanced.     

Optical properties of ZnO nanorods realised by aqueous chemical growth

Photoluminescence investigations of ZnO nanorods realised by an advanced two-step aqueous chemical growth process have been carried out revealing well-resolved near-band-edge emission accompanied by phonon replicas. The optical properties of nanorods with different lengths and diameters are quite similar indicating a good control of the growth process without influencing the optical properties even on plastic substrate. The near-band-edge emission has a very broad line-width of 10 meV. Annealing in Ar atmosphere reduces the deep-level emission with a corresponding increase of the near-band-edge emission.     

Effect of Fe-doping on the structural,morphological and optical properties of ZnO nanoparticles synthesized by solution combustion process

The effect of Fe-doping on the structural, morphological and optical properties of ZnO nanoparticles synthesized by simple solution combustion process are reported. The powder XRD pattern indicates that the Fe-doped ZnO samples exhibit primary and secondary phases. The primary phase indicates the hexagonal wurtzite structure with the average crystalline size of around 25–50 nm and the secondary phase is associated with the face centered cubic structure of magnetite iron oxide. The elemental composition of pure and Fe-doped samples are evaluvated by EDX. The results of FE-SEM and HR-TEM cleary show that particles morphology have changed with respect to the incorporation of doping agent and particles are in aggregating nature. The vibrational properties of the synthesized ZnO nanoparticles are investigated by Raman scattering technique and it exhibits that the influence of Fe-doping significantly modify the lattice vibrational characteristics in ZnO sites. The optical properties of the Fe-doped ZnO nanoparticles are carried out by UV–vis absorption and PL spectra. The results of PL spectra show the near-band edge related emission as well as strong blue emissions in the Fe-doped ZnO nanoparticles.     

Magnetic behavior of nanocrystalline powders of Co-doped ZnO diluted magnetic semiconductors synthesized by polymerizable precursor method

This paper reports the first synthesis of nanocrystalline powders of Co-doped ZnO (i.e. Zn_0.9Co_0.1O) diluted magnetic semiconductor by a polymerizable precursor method using nitrate salts of Zn and Co and a mixed solution of citric acid and ethylene glycol as a chelating agent and reaction medium, respectively. The polymeric precursors were characterized by TG-DTA to determine the thermal decomposition and crystallization temperature which was found to be at 723 K. The precursors were calcined at different temperatures of 773, 873, 973, and 1073 K for 1 h to obtain nanocrystalline powders. The morphology and crystalline size of the calcined particles were evaluated by SEM, TEM and Scherrer's equation. The average particle sizes calcined at 773, 873, 973, and 1073 K for 1 h were, respectively, 20, 60, 80, 150 nm, obtained from TEM. The XRD and Fourier transmission infrared (FT-IR) results indicated that the synthesized Zn_0.9Co_0.1O powders have the pure wurtzite structure without any significant change in the structure affected by Co substitution. Optical absorption measurements showed absorption bands indicating the presence of Co²⁺ in substitution of Zn²⁺. Room temperature magnetization results revealed a ferromagnetic behavior for the Zn_0.9Co_0.1O powders. Although the specific magnetization seemed to change with the particle size but there was no clear dependency since the largest magnetization was observed in the powders calcined at 873 K (60 nm). Instead, the specific magnetization appeared to show a trend of dependency on the lattice constant c of the wurtzite unit cell.     

Effects of growth duration on the structural and optical properties of ZnO nanorods grown on seed-layer ZnO/polyethylene terephthalate substrates

Well-aligned single crystalline zinc oxide (ZnO) nanorods were successfully grown, by hydrothermal synthesis at a low temperature, on flexible polyethylene terephthalate (PET) substrates with a seed layer. Photoluminescence (PL), field-emission scanning electron microscopy (FE-SEM), X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM) measurements were used to analyze the optical and structural properties of ZnO nanorods grown for various durations from 0.5 h to 10 h. Regular and well-aligned ZnO nanorods with diameters ranging from 62 nm to 127 nm and lengths from 0.3 μm to 1.65 μm were formed after almost 5 h of growth. The growth rate of ZnO grown on PET substrates is lower than that grown on Si (1 0 0) substrates. Enlarged TEM images show that the tips of the ZnO nanorods grown for 6 h have a round shape, whereas the tips grown for 10 h are sharpened. The crystal properties of ZnO nanorods can be tuned by using the growth duration as a growth condition. The XRD and PL results indicate that the structural and optical properties of the ZnO nanorods are most improved after 5 h and 6 h of growth, respectively.     

The growth mechanism of ZnO single-crystal nanorods synthesized by polymer complexing with zinc salts

The growth mechanism of single-crystal ZnO nanorods synthesized by the method of polymer complexing with zinc salts is investigated. The annealing temperature is controlled at about the decomposition temperature of dihydrate zinc acetate (Zn(O₂CCH₃)₂·2H₂O) of 573 K. By changing the annealing time, the ZnO nanostructures can be modified from nanoparticles to nanorods. As a result, the formation of single-crystal ZnO nanorods can be observed. Through investigating the Fourier transform infrared spectra of (a) polyvinyl pyrrolidone (PVP), (b) Zn(O₂CCH₃)₂·2H₂O and (c) the mixture of PVP and Zn(O₂CCH₃)₂(H₂O)₂, the interaction between PVP and Zn(O₂CCH₃)₂·2H₂O can be observed. PVP plays an important role in the growth of the single-crystal ZnO nanorods. We analyze the growth process of ZnO nanorods by observing their TEM images at different moments. Consequently, our results indicate that the single-crystal ZnO nanorods were formed by self-assembling the ZnO nanoparticles. PACS 61.46.Hk; 61.46.Df; 78.30.-j; 81.07.-b; 81.16.Be     

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.     

Effects of temperature and atmosphere on the magnetic properties of Co-doped ZnO rods

Co-doped ZnO (Zn_0.95Co_0.05O) rods are fabricated by co-precipitation method at different temperatures and atmospheres. X-ray diffraction, Energy dispersive X-ray spectroscopy and Raman results indicate that the samples were crystalline with wurtzite structure and no metallic Co or other secondary phases were found. Raman results indicate that the Co-doped ZnO powders annealed at different temperatures have different oxygen vacancy concentrations. The oxygen vacancies play an important role in the magnetic origin for diluted magnetic semiconductors. At low oxygen vacancy concentration, room temperature ferromagnetism is presented in Co-doped ZnO rods, and the ferromagnetism increases with the increment of oxygen vacancy concentration. But at very high oxygen vacancy concentration, large paramagnetic or antiferromagnetic effects are observed in Co-doped ZnO rods due to the ferromagnetic-antiferromagnetic competition. In addition, the sample annealed in Ar gas has better magnetic properties than that annealed in air, which indicates that O₂ plays an important role. Therefore, the ferromagnetism is affected by the amounts of structural defects, which depend sensitively on atmosphere and annealing temperature.     

Effect of oxygen vacancy defect on the magnetic properties of Co-doped ZnO

The influence of oxygen vacancy on the magnetism of Co-doped ZnO has been investigated by the first-principles calculations.It is suggested that oxygen vacancy and its location play crucial roles on the magnetic properties of Co-doped ZnO.The exchange coupling mechanism should account for the magnetism in Co-doped ZnO with oxygen vacancy and the oxygen vacancy is likely to be close to the Co atom.The oxygen vacancy (doping electrons) might be available for carrier mediation but is localized with a certain length and can strengthen the ferromagnetic exchange interaction between Co atoms.     

Influence of Mn doping on structural and optical properties of ZnO nano thin films synthesized by sol–gel technique

Undoped and Mn-doped ZnO samples with different percentages of Mn content (1, 5 and 10?at%) were synthesized by a dip-coating sol?Cgel method. We have studied the structural, chemical and optical properties of the samples by using X-ray diffraction (XRD), scanning electron microscopy (SEM) and UV-visible spectroscopy. The XRD spectra show that all the samples are hexagonal wurtzite structures. We note that doping favors c-axis orientation along (002) planes. Up to 5?at% of Mn doping level, the c-axis lattice parameter shifts towards higher values with the increase of manganese content in the films. The expansion of the lattice constant of ZnO?CMn indicates that Mn is really doped into the ZnO. The SEM investigations of all samples revealed that the crystallites are of nanometer size. The surface quality of the ZnO?CMn film increases with Mn doping but no significant change of the grain size is observed from SEM images. The transmittance spectra show that the transparency of all the samples is greater than 85?%. We note, also, that a small doping (1?%) lowered the refractive index while the thickness of the layers and the gap increase. However, on raising the proportion of Mn beyond 5?%, practically the same values of index and gap as pure ZnO are found.     

Difference in magnetic properties between Co-doped ZnO powder and thin film

This paper reports that the Zn掺钴;氧化锌粉末;氧化锌薄膜;磁性差异;晶体取向ZnO, Co-doped, crystalline orientation, magnetismProject supported by the Shanghai Nanotechnology Promotion Center (Grant No~0452nm071).2006-09-152006-11-29This paper reports that the Zn0.95Co0.05O polycrystalline powder and thin film were prepared by sol-gel technique under the similar preparation conditions. The former does not show typical ferromagnetic behaviour, while the latter exhibits obvious ferromagnetic properties at 5 K and room temperature. The UV-vis spectra and x-ray absorption spectra show that Co2＋ ions are homogeneously incorporated into ZnO lattice without forming secondary phases.The distinct difference between film and powder sample is the c-axis （002） preferential orientation indicated by the x-ray diffraction pattern and field emission scanning electron microscopy measurement, which may be the reason why Zn0.95Co0.05O film shows ferromagnetic behaviour.     

氧空位对钴掺杂氧化锌半导体磁性能的影响

从实验和理论上阐述了氧空位对Co掺杂ZnO半导体磁性能的影响.采用磁控溅射法在不同的氧分压下制备了Zn_095Co_005O薄膜,研究了氧分压对薄膜磁性能的影响.实验结果表明,高真空条件下制备的Zn_095Co_005O薄膜具有室温铁磁性,提高氧分压后制备的薄膜铁磁性逐渐消失.第一性原理计算表明,在Co掺杂ZnO体系中引入氧空位有利于降低铁磁态的能量,铁磁态的稳定性与氧空位和Co之间的距离密切相关. 关键词： Co掺杂ZnO 稀磁半导体 第一性原理计算 氧空位缺陷