Solvothermal synthesis,photoluminescence and photocatalytic properties of pencil-like ZnO microrods

Pencil-like ZnO microrods was synthesized via a simple solvothermal process in an aqueous solution of ethylenediamine and ethanolamine. The as-prepared ZnO was characterized by X-ray powder diffraction, field-emission scanning electron microscopy, room temperature photoluminescence spectra and UV–vis absorption spectra. The results indicated that ZnO microrods had the length in the range of 1.3–25 μm. The photocatalytic activity was studied by degradation of methylene blue (MB) aqueous solution, which showed that the as-prepared ZnO microrods possessed a high photocatalytic activity. The formation mechanism of the pencil-like ZnO was also investigated based on the experimental results.     

Hierarchical ZnO microrods: synthesis,structure, optical and photocatalytic properties

Hierarchical ZnO microrods have been prepared by cetyltrimethylammonium bromide (CTAB)-assisted hydrothermal process at low temperature. Sheetlike or fluffy ZnO nanostructures have been developed in a large density on the surface of the microrods. The ZnO cores grow preferentially along [001]; the nanosheets are single crystalline and grow in two dimensions along the [001] and [120] directions. The formation of hierarchical structures has been attributed to the presence of CTAB in the solution, which facilitates the secondary nucleation and growth. The nanosheet-covered hierarchical microrods have been analyzed by Raman and photoluminescence spectroscopy, and they exhibit a blue emission at 465 nm and a strong orange emission at 640 nm. Photocatalytic activities of the products have been examined, and the nanosheet-covered hierarchical microrods display the best activity in photodegradation of phenol due to their unique surface features and high surface area.     

Structural and optical properties of ZnO and Al-doped ZnO microrods obtained by spray pyrolysis method using different solvents

ZnO and Al-doped ZnO microrods were obtained by spray pyrolysis method using different solvents such as methanol and propanol. The effect of the type of solvent in the starting solution on the structural, morphological and optical properties of the samples was investigated. X-ray diffraction patterns showed that the undoped and Al-doped ZnO microrods exhibited hexagonal crystal structure with a preferred orientation along (0 0 2) direction. Surface morphology of the samples obtained by scanning electron microscopy revealed that undoped and Al-doped ZnO microrods grew as quasi-aligned hexagonal shaped microrods with diameters varying between 0.7 and 1.3 μm irrespective of solvents used. Optical studies indicated that microrods had a low transmittance (≅30%) and the band gap increased from 3.24 to 3.26 eV upon Al doping. Photoluminescence measurements indicated the existence of two emission bands in the spectra: one sharp ultraviolet luminescence at ∼383 nm and one broad visible emission ranging from 420 to 580 nm.     

Photoluminescence and field emission properties of Sn-doped ZnO microrods

Sn-doped ZnO (SZO) microrods have been fabricated by a thermal evaporation method. Effect of Sn dopant on the microstructure, morphological and composition of as-prepared SZO microrods have been investigated by X-ray diffraction (XRD), Raman, scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) spectroscopy. The influence of the doping concentration on the morphological of the microrods has been investigated. Photoluminescence (PL) of these SZO microrods exhibits a weak ultraviolet (UV) emission peak at around 382 nm and the strong green emission peak at around 525 nm at room temperature. Field emission measurements demonstrate that the SZO possess good performance with a turn-on field of ∼1.94 V/μm and a threshold field of ∼3.23 V/μm, which have promising application as a competitive cathode material in FE microelectronic devices.     

Structural, optical and magnetic properties of Cr doped ZnO microrods prepared by spray pyrolysis method

A series of Cr-doped ZnO micro-rod arrays were fabricated by a spray pyrolysis method. X-ray diffraction patterns of the samples showed that the undoped and Cr-doped ZnO microrods exhibit hexagonal crystal structure. Surface morphology analysis of the samples has revealed that pure ZnO sample has a hexagonal microrod morphology. From X-ray photoelectron spectroscopy studies, the Cr 2p3/2 binding energy is found to be 577.3 eV indicating that the electron binding energy of the Cr in ZnO is almost the same as the binding energy of Cr³⁺ states in Cr₂O₃. The optical band gap E_g decreases slightly from 3.26 to 3.15 eV with the increase of actual Cr molar fraction from x = 0.00 to 0.046 in ZnO. Photoluminescence studies at 10 K show that the incorporation of chromium leads to a relative increase of deep level band intensity. It was also observed that Cr doped samples clearly showed ferromagnetic behavior; however, 2.5 at.% Cr doped ZnO showed remnant magnetization higher than that of 1.1 at.% and 4.6 at.% Cr doped samples, while 4.6 at.% Cr doped ZnO samples had a coercive field higher than the other dopings.     

Synthesis and optical properties of phosphorus-doped ZnO nanocombs

Phosphorus-doped ZnO nanocombs with double-sided symmetry were prepared by a modified thermal-evaporation process using phosphorus pentoxide as the dopant source. Scanning electron microscopy and transmission electron microscopy reveal that the single-crystal teeth in the doped nanocombs grow along [0002] direction and that the formation of the tapered tip should be related to the lattice strain caused by the incorporation of phosphorous. Raman spectra further reveal the influence of phosphorus doping on the lattice dynamics of ZnO, and display the amphoteric nature of phosphorus dopant. The p-type doping is confirmed by the temperature-dependent photoluminescence spectra, and the acceptor binding energy is estimated to be about 165 meV.     

Synthesis and optical properties of ultralong ZnO microbushes

Ultralong ZnO microbushes have been synthesized using a simple thermal evaporation and condensation method by Cu catalysts. The lengths of the ZnO microbushes range from several millimeters to more than one centimeter and the diameters of the branches’ teeth are about 300 nm. The growth mechanism of the ultralong microbushes and the catalytic behavior of the copper are discussed. Room-temperature photoluminescence spectra of the ultralong ZnO microbushes showed a UV emission band at about 388 nm and wide green emissions at around 525 nm. It may be very attractive for commercial applications such as electrical devices, microelectromechanical systems and sensors.     

Shuttle-like ZnO nano/microrods: Facile synthesis, optical characterization and high formaldehyde sensing properties

Shuttle-like ZnO nano/microrods were successfully synthesized via a low temperature (80 °C), “green” (without any organic solvent or surfactant) and simple hydrothermal process in the solution of zinc chloride and ammonia water. X-ray diffraction and Raman spectroscopy indicated that the ZnO nano/microrods are a well-crystallized hexagonal wurtzite structure. Yet photoluminescence analysis showed that abundant intrinsic defects (52.97% electron donor defects and 45.49% electron acceptor defects) exist on the surface of ZnO crystals. Gas sensors based on the shuttle-like ZnO nano/microrods exhibited high sensitivity, rapid response-recovery and good selectivity to formaldehyde in the range of 10-1000 ppm at an optimum operating temperature of 400 °C. Through applying linear fitting to the plot of sensitivity versus formaldehyde concentration in logarithmic forms, the chemisorbed oxygen species on the ZnO surface were found to be O²⁻ (highly active among O₂, O₂⁻ and O⁻ species). Notably, formaldehyde can be easily distinguished from acetaldehyde with a selectivity of about 3. The high formaldehyde sensitivity is mainly attributed to the synergistic effect of abundant electron donor defects (52.97%) and highly active oxidants (surface adsorbed O²⁻ species) co-existed on the surfaces of ZnO.     

Synthesis and optical properties of N-In codoped ZnO nanobelts

N-In codoped ZnO nanobelts were successfully synthesized via high-temperature chemical vapor deposition for the first time, using the mixture of In/ZnO as a precursor. The EDX spectrum showed that In was introduced into ZnO nanobelts. In order to better understand the optical properties of N-In codoped ZnO nanobelts, the Raman and low-temperature PL spectra of the undoped, In-doped and N-In codoped ZnO nanostructures were measured. By contrasting, N is incorporated into the nanobelts. The temperature dependent photoluminescence (PL) spectra were investigated. Their PL spectra in the temperature from 9 K to room temperature were dominated by an A^oX emission of excitons bound to 2No-In_Zn acceptor complexes. The dissociation energy of the acceptor complexes is estimated to be 89-112 meV.     

Luminescence anisotropy of ZnO microrods

The local features of light emission from ZnO microrods were studied: it is revealed that ZnO luminescence spectra are significantly influenced by the crystal morphology. It is shown that the near and edge ultraviolet emission occurs primarily from the top (0001) planes of ZnO microrods; while the defect related visible emission was found to occur dominantly from the side facets. The room temperature cathodoluminescence analysis revealed that visible emission consists of a few overlapping peaks, arising due to recombination on common points and surface defects (Zn_i, V_o, V_o⁰/V_o^?*_, V_o^** and surface defects.). While at low temperature, only the luminescence due to neutral donor bound exciton (D⁰X) emission is observed. The data obtained suggest that the light emission spectra of ZnO material of diverse morphology cannot be directly compared, although some common spectral features are present.     

Synthesis, characterization and optical properties of multipod ZnO whiskers

Multipod ZnO whiskers were synthesized successfully by two steps: pulsed laser deposition (PLD) and thermal evaporation process. First, a thin layer of Zn films were deposited on Si(1 1 1) substrates by PLD. Then the whiskers grew on Zn-coated Si(1 1 1) substrate by the simple thermal evaporation oxidation of the metallic zinc powder at 900 °C in the air without any catalysts or additives. The pre-deposited Zn films by PLD on the substrate can promote the growth of ZnO multipod whiskers effectively. The as-synthesized ZnO whiskers were characterized by using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and high-resolution transmission electron microscopy (HRTEM). The results revealed that the whiskers are highly crystalline with the wurtzite hexagonal structure. Room temperature photoluminescence (PL) spectrum of the whiskers shows a UV emission peak at ∼393 nm and a broad green emission peak at ∼517 nm, which was assigned to the near band-edge emission and the deep-level emission, respectively.     

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 optical properties of flower-like ZnO nanorods by thermal evaporation method

Flower-like ZnO nanorods have been synthesized by heating a mixture of ZnO/graphite powders using the thermal evaporation and vapor transport on Si (1 0 0) substrates without any catalyst. The structures, morphologies and optical properties of the products were characterized in detail by using X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), photoluminescence (PL) and Raman spectroscopy. The synthesized products consisted of large quantities of flower-like ZnO nanostructures in the form of uniform nanorods. The flower-like ZnO nanorods had high purity and well crystallized wurtzite structure, whose high crystalline quality was proved by Raman spectroscopy. The as-synthesized flower-like ZnO nanorods showed a strong ultraviolet emission at 386 nm and a weak and broad yellow-green emission in visible spectrum in its room temperature photoluminescence (PL) spectrum. In addition, the growth mechanism of the flower-like ZnO nanorods was discussed based on the reaction conditions.     

Synthesis and optical properties of ZnO nanorods on indium tin oxide substrate

ZnO nanorods with uniform diameter and length have been synthesized on an indium-tin oxide (ITO) substrate by using a simple thermal evaporation method which is suitable to larger scale production and without any catalyst or additives. The samples were characterized with X-ray diffraction (XRD), scanning electron microscopy (SEM), ultraviolet-vis (UV-vis) absorption spectrum, photoluminescence (PL) spectrum and Raman spectrum. The single-phase ZnO nanorods grow well-oriented along the c-axis of its wurtzite structure on ITO substrate. The ZnO nanorods shows sharp and strong UV emission located at 380 nm without notable visible light emission in the PL spectrum, which suggests the good crystallinity of the nanorods, which was also testified by their Raman spectrum. The photodegradation of methylene orange (MO) in aqueous solution reveals that the well-arranged c-axis growth of ZnO nanorods possess evidently improved photocatalytic performance and these properties enable the ZnO nanorods potential application in UV laser.     

Photoluminescence characterization of vertically aligned ZnO microrods

A detailed optical characterization of vertically aligned ZnO microrods (μRs) grown using a Ni-based catalyst was carried out by excitation-power- and temperature-dependent photoluminescence (PL) measurements. Low-temperature PL spectra of ZnO μRs are dominated by near-band-edge (NBE) emission consisted of a series of sharp lines typical for the bulk ZnO. Starting from the higher energy free exciton (FX) emission feature, the majority of them can be explained by radiative recombination of excitons bound to neutral donors (D⁰X), defect bound exciton (DBX), two-electron satellites emission, free-to-bound, i.e. free electrons to the neutral acceptors (eA⁰) transition, as well as their longitudinal-optical phonon replicas. An additional excitonic line located in between the FX and D⁰X lines, denoted as the surface excitons (SX) for ZnO μRs is observed. The intensity of the SX line is found to be smaller than that of the nanosized counterpart and has been attributed to the surface–volume ratio effects. The excitation-power-dependent results of FX line at low and high power regimes show quite close values corresponding to, respectively, p=2 and p=1 limits of the theoretical power law expression I～L^p and larger deviations for the D⁰X, SX and DBX lines. The temperature-dependent measurements confirmed the presence of eA⁰ line showing kT/2 influence to the position of eA⁰ emission line in comparison with FX. FX emissions persist up to 300 K and together with the dominant eA⁰ emission govern the line shape of the NBE emission range, while D⁰X and SX lines are quenched completely at 150 K.     

制备一维可控形貌的ZnO微米棒

用化学溶液法以醋酸锌和六亚甲基四胺为原料在玻璃衬底上生长出不同形貌的亚微米和微米ZnO棒。探讨了反应液的酸碱度和反应液浓度对生成的ZnO棒形貌的影响，并分析了其生长机制。通过控制一定的酸碱度和溶液浓度，可以得到规则的六角ZnO棒状阵列。这种规则的六角棒沿着[002]方向生长。测量了样品的XRD，扫描电镜像(SEM)，并对其发光性能进行了测量分析。其中规则六角ZnO棒的光致发光光谱中有一很强的峰值650nm红色宽谱带和一峰值约387nm的激子发光峰。激子发光峰加宽，实际上是自由激子的发光峰(380nm)和Zni的发光峰(430nm)的叠加。而红色发光峰可能是Vo2+中的电子和价带中的空穴辐射复合所致。     

Synthesis and optical spectroscopy of ZnO nanowires

Single crystal ZnO nanowires with lengths and diameters ranging from 2 to 30 μm and 100 to 300 nm, respectively, have been grown by the vapor transport method on SiO₂/Si substrates using Au as catalyst. Their Raman and emission properties under different excitation wavelengths have been studied at the nanoscale. Whereas Raman measurements on nanowires corroborate the well-known ZnO phonon characteristics, their photoluminescence spectra exhibit a very broad emission band, mainly in the visible region from 450 to 800 nm, which corresponds to different defect-related recombination processes. Spectrally resolved scanning near-field optical microscopy, SNOM, of single ZnO nanowires have also been performed for a direct imaging of the photoluminescence emission with high spatial resolution below 100 nm, establishing a relationship with the simultaneously acquired topography.     

Co掺杂的ZnO室温铁磁半导体材料制备与磁性和光学特性研究

采用溶胶-凝胶法制备出具有室温铁磁性的Co掺杂的ZnO稀磁半导体材料. 通过对样品的结构、磁性和发光特性的研究发现,样品具有室温铁磁性,并发现其铁磁性源于磁性离子对ZnO中Zn离子的取代. 对不同温度制备的样品的磁性以及其发光特性的变化研究发现,样品的铁磁性与样品中锌间隙位（Zn_i）缺陷的密度有关. 关键词： ZnO 稀磁半导体 铁磁性     

Characterization and optical property of ZnO nano-, submicro- and microrods synthesized by hydrothermal method on a large-scale

In the present paper, well-dispersed ZnO nano-, submicro- and microrods with hexagonal structure were synthesized by a simple low temperature hydrothermal process from zinc nitrate hexahydrate without using any additional surfactant, organic solvent or catalytic agent. The phase and structural analysis were carried out by X-ray diffraction (XRD), the morphological analysis was carried out by field emission scanning electron microscopy (FESEM) and the optical property was characterized by room-temperature photoluminescence (PL) spectroscopy. The results revealed the high crystal quality of ZnO powder with hexagonal (wurtzite-type) crystal structure and the formation of well-dispersed ZnO nano-, submicro- and microrods with diameters of about 50, 200 and 500 nm, and lengths of 300 nm, 1 μm and 2 μm, respectively, on a large-scale just using the different temperatures. Room-temperature PL spectrum from the ZnO nanorods reveals a strong UV emission peak at about 360 nm and no green emission band at ∼530 nm. The strong UV photoluminescence indicates the good crystallization quality of the ZnO nanorods. Room-temperature PL spectra from the ZnO submicro- and microrods reveal a weak UV emission peak at ∼400 nm and a very strong visible green emission at 530 nm, that is ascribed to the transition between V_oZn_i and valence band.     

Synthesis of Pr-doped ZnO nanoparticles: Their structural,optical, and photocatalytic properties

Undoped and praseodymium-doped zinc oxide(Pr-doped ZnO)(with 2.0-mol%–6.0-mol% Pr) nanoparticles as sunlight-driven photocatalysts are synthesized by means of co-precipitation with nitrates followed by thermal annealing.The structure, morphology, and chemical bonding of the photocatalysts are studied by x-ray diffraction(XRD), scanning electron microscopy(SEM) with energy dispersive x-ray emission spectroscopy(EDS), x-ray photoelectron spectroscopy(XPS), and Fourier transform infrared spectroscopy(FTIR), respectively. The optical properties are studied by photoluminescence(PL) and UV-vis diffuse reflectance spectroscopy(UV-vis DRS). We find that Pr doping does not change the crystallinity of ZnO; but it reduces the bandgap slightly, and restrains the recombination of the photogenerated electron–hole pairs. The photocatalytic performance of the photocatalysts is investigated by the photodegradation reaction of 10-mg/L rhodamine B(RhB) solution under simulated sunlight irradiation, showing a degradation rate of 93.75% in ZnO doped with6.0-mol% Pr.