Photoluminescence properties of various CVD-grown ZnO nanostructures

We have studied systematically room-temperature photoluminescence (PL) properties of many nanostructured ZnO samples grown by chemical vapour deposition (CVD). Their PL spectra consist of two emissions peaked in the ultraviolet (UV) and green regions. The relative intensity of these emissions depends on the excitation energy density, size and morphology of ZnO nanostructures. Based on the excitation-density dependence of the integrated intensity ratio of UV-to-green emission, we could classify PL spectra of ZnO nanostructures into three groups characteristic of size and morphology. Our study also reveals that with increasing excitation density, the UV-peak position shifts slightly towards longer wavelengths while the green emission around 514-520 nm is almost unchanged. This green-luminescence emission is dominant when the nanostructure sizes range from 20 to 200 nm, which is related to a large surface-to-volume ratio.     

Microstructures and optical properties of Cu-doped ZnO films prepared by radio frequency reactive magnetron sputtering

Pure and Cu-doped ZnO (ZnO:Cu) thin films were deposited on glass substrates using radio frequency (RF) reactive magnetron sputtering. The effect of substrate temperature on the crystallization behavior and optical properties of the ZnO:Cu films have been studied. The crystal structures, surface morphology and optical properties of the films were systematically investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM) and a fluorescence spectrophotometer, respectively. The results indicated that ZnO films showed a stronger preferred orientation toward the c-axis and a more uniform grain size after Cu-doping. As for ZnO:Cu films, the full width at half maxima (FWHM) of (0 0 2) diffraction peaks decreased first and then increased, reaching a minimum of about 0.42° at 350 °C and the compressive stress of ZnO:Cu decreased gradually with the increase of substrate temperature. The photoluminescence (PL) spectra measured at room temperature revealed two blue and two green emissions. Intense blue-green luminescence was obtained from the sample deposited at higher substrate temperature. Finally, we discussed the influence of annealing temperature on the structural and optical properties of ZnO:Cu films. The quality of ZnO:Cu film was markedly improved and the intensity of blue peak (∼485 nm) and green peak (∼527 nm) increased noticeably after annealing. The origin of these emissions was discussed.     

Room temperature Ge and ZnO embedded inside porous silicon using conventional methods for photonic application

In this paper we reported room temperature synthesis of embedded porous Si (PS) based structures using simple and low cost techniques of electrochemical etching and thermal evaporation. PS was prepared by anodization of Si wafer in ethanoic hydrofluoric acid (HF). The Ge and ZnO layers were deposited onto the PS by conventional thermal evaporation. Three samples prepared namely PS, Ge/PS and ZnO/Ge/PS. Structural analyses, SEM revealed that the structures contained 500–700 nm circular-pores and EDX suggested the presence of Ge and ZnO inside the pores. Photoluminescence (PL) spectra of the three samples revealed emissions peak at 380, 520 and 639 nm, respectively, with ZnO/Ge/PS displaying a high UV emission peak accompanied by low and broad green to red emission peaks. The Ge/PS sample shows emission peaks from green to red and the PS sample reveals a broad peak in the red region. These characteristics demonstrate the potential of the PS-based structures to emit light at a broader spectrum for prospective applications in optoelectronic devices.     

Yellowish-white photoluminescence from ZnO nanoparticles doped with Al and Li

ZnO nanoparticles codoped with Al and Li were chemically synthesized with a low temperature drying process. They are crystalline and can be made as small as 5 nm. Intense yellowish white photoluminescence was observed from smaller ZnO nanoparticles with a higher concentration of Al and Li. The photoluminescence peak consists of yellow and green emission bands. Both peak intensities increase with increasing the Al and Li concentrations and with decreasing the size of ZnO nanoparticles. The green and yellow emission bands were attributed to donor–acceptor-pair recombination involving Zn vacancies and lithium as the acceptor state, respectively, and the donor responsible for both emissions to oxygen vacancies. Both enhanced emissions by codoping may be explained by an increase in the number of electrons occupying the deep donor level on account of doping with Al. Although the yellowish white emission decays with time, passivation of the crystallite surface with poly(p-phenylene vinylene) suppresses the degradation. The observed high-intensity and stable yellowish white emission makes PPV-passivated ZnO nanoparticles, codoped with Al and Li, more attractive as a candidate for “white” phosphor.     

热蒸发法Zn／ZnO叶状微米结构自组装生长及其发光特性

采用热蒸发法在ZnO缓冲层覆盖着Si衬底上合成了2D叶状的Zn晶枝结构,Zn的晶枝长度约为几十微米,厚度约为200nm,随后Zn晶枝在O2的气氛下热处理,在晶枝表面获得纤细、均匀的ZnO纳米线。晶枝按照无催化、自组装、汽相生长模式生长,晶枝最快生长方向是沿着载气气流的方向释放凝固潜热,XRD分析结果结果显示了Zn纳米线具有六角纤锌矿结构,Zn/ZnO的发光谱显示,在380nm处有一弱的UV近带边发射和中心在505nm处的强绿光发射,绿光发射归因于施主/受主对之间的辐射跃迁。     

硫掺杂ZnO纳米线的电化学制备及发光特性

"采用电场辅助电化学沉积法,利用阳极氧化铝模板模板制备了高度择优取向的硫掺杂ZnO单晶纳米线．X射线衍射仪、隧道电子显微镜、选取电子衍射对所得样品的结构、形貌分析表明,所得纳米线是沿(101)择优取向的六方纤锌矿结构单晶纳米线,长约几十微米、平均直径约70 nm. X射线光电子能谱对化学组成的分析进一步证实掺杂硫原子的存在．用荧光光谱仪(PL)对S掺杂前后的ZnO纳米线进行光学特性测量发现,S掺杂较大地改变了ZnO纳米线的发光性质．在PL谱中,除了有典型的ZnO纳米线在378、392 nm处的强紫外发光峰     

ZnO纳米带外延树枝状锯齿形缺口结构的制备及其发光特性

应用气固生长方式在没有催化剂的情况下合成出一种新奇的ZnO纳米结构．通过透射电子显微镜分析，发现这种ZnO纳米带外延晶枝直径约20 nm，在[0001]方向有着良好的外延生长取向．提出了一个模型来解释这种树枝状锯齿结构的生长．室温下光致发光测量表明这种ZnO纳米结构在382、491 nm处有一个紫外发光峰和绿光发光峰．     

Growth of ZnO Nanostructures on Porous Silicon and Oxidized Porous Silicon Substrates

We have investigated an oxidation of substrate effect on structural morphology of zinc oxide (ZnO) rods. ZnO rods are grown on porous silicon (PS) and on thermally oxidized porous silicon substrates by carbothermal reduction of ZnO powder through chemical vapour transport and condensation. Porous silicon is fabricated by electrochemical etching of silicon in hydrofluoric acid solution. The effects of substrates on morphology and structure of ZnO nanostructures have been studied. The morphology of substrates is studied by atomic force microscopy in contact mode. The texture coefficient of each sample is calculated from X-ray diffraction data that demonstrate random orientation of ZnO rods on oxidized porous silicon substrate. The morphology of structures is investigated by scanning electron microscopy that confirms the surface roughness tends to increase the growth rate of ZnO rods on oxidized PS compared with porous silicon substrate. A green emission has been observed in ZnO structures grown on oxidized PS substrates by photoluminescence measurements.     

Fabrication of three-dimensional ZnO with hierarchical structure via an electrodeposition process

A novel three-dimensional (3D) hierarchical structured ZnO was prepared on TiO₂ nanoparticles film by electrodeposition process from aqueous ZnCl₂ solution. The hierarchical structured ZnO was observed by scanning electron microscopy. The results showed that the deposition time had an obvious effect on the morphology of the ZnO structures. Accordingly, a possible growth mechanism was proposed. Furthermore, the room-temperature optical properties of hierarchical structured ZnO were investigated by photoluminescence spectrum, indicating that a strong green emission peak centered at 542 nm.     

Synthesis and optical properties of pencil-like and shuttle-like ZnO microrods

The pencil-like and shuttle-like ZnO microrods have been fabricated on Si (100) substrates by chemical vapor deposition. Structure characterization results show that the microrods are perfect single crystals with the wurtzite structure along the [0001] growth direction and have diameters ranging from 100 nm to 2 μm and lengths up to 10 μm. Room-temperature photoluminescence measurements of ZnO microstructures exhibit an intensive ultraviolet peak at 390 nm and a broad peak centered at about 526 nm, which can be attributed to the free exciton emission and the deep level emission, respectively. Cathodoluminescence measurements show the same ultraviolet and green emissions as seen in the photoluminescence results. A possible growth mechanism of ZnO microrods is finally proposed.     

Photoluminescence and absorption in sol-gel-derived ZnO films

Highly c-axis-oriented ZnO films were obtained on corning glass substrate by sol-gel technique. The characteristics of photoluminescence (PL) of ZnO, as well as the exciton absorption in the absorption (UV) spectra are closely related to the post-annealing treatment. The difference between PL peak position and the absorption edge, designated as Stokes shift, is found to decrease with the increase of annealing temperature. The minimum Stokes shift is about 150 meV. The decrease of Stokes shift is attributed to the decrease in carrier concentration in ZnO film with annealing. X-ray diffraction, surface morphology and refractive index results indicate an improvement in crystalline quality with annealing. Annealed films also exhibit a green emission centered at ∼520 nm with activation energy of 0.89 eV. The green emission is attributed to the electron transition from the bottom of the conduction band to the antisite oxygen O_Zn defect levels.     

RF溅射钕掺杂ZnO薄膜的结构与发光特性

通过射频磁控溅射技术在Si(111)衬底上制备了未掺杂ZnO薄膜和Nd掺杂ZnO薄膜。应用XRD分析了ZnO:Nd薄膜的晶格结构,通过AFM观察了ZnO:Nd薄膜的表面形貌。结果表明,Nd掺入了ZnO晶格中,由于Nd原子半径大于Zn原子半径,Nd以替位原子的形式存在于ZnO晶格中。ZnO:Nd薄膜为纳米多晶薄膜,表面形貌粗糙。ZnO:Nd薄膜的室温光致发光谱表明,相同条件下制备的未掺杂ZnO薄膜和Nd掺杂ZnO薄膜都出现了395nm的强紫光带和495nm的弱绿光带。我们认为,紫光发射峰窄而锐且强度远大于绿光峰,源于薄膜中激子复合;绿光峰强度较弱,源于薄膜中的氧空位(VO)及氧反位锌缺陷(OZn)。Nd掺杂没有影响ZnO:Nd薄膜的PL谱的发射峰的峰位。由于Nd3 离子电荷数与Zn2 离子电荷数不相等,为了保持ZnO薄膜的电中性,间隙锌(VZn)可以作为Nd替位补偿性的受主杂质而存在,影响ZnO薄膜的激子浓度。同时,Nd掺入使ZnO的晶格畸变缺陷浓度改变增强,因而发射峰的强度随Nd掺杂浓度不同而变化。     

Morphology-dependent upconversion luminescence of ZnO:Er nanocrystals

Morphology impact on the upconverted luminescence of ZnO:Er³⁺ nanocrystals was studied with controllable morphology of nanorod, prickly sphere-like, column-like, branch rod, prism-like, and grain-like, prepared via the cetyltrimethylammonium bromide (CTAB)-assisted hydrothermal process. The upconversion emission of Er³⁺ with 980 nm excitation demonstrated morphology sensitivity which was related with the local environments of Er³⁺ ions in ZnO and doping efficiency. Under ultraviolet (UV) direct excitation, where exciton and defect emissions of ZnO appeared, morphology sensitivity was discussed in terms of surface-to-volume ratios.     

Synthesis,characterization and photoluminescence of ZnO:Cd rosette-like nanostructures using solution process

Well crystalline undoped and Cd-doped ZnO rosette-like structures were successfully synthesized at low temperature (80 °C) via solution process technique during 30 min. Zinc nitrate, cadmium nitrate, sodium hydroxide and hexamine were used as starting materials. The morphology and microstructure were determined by field emission scanning electron microscopy (FE-SEM), X-ray diffraction (XRD), transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDX) and photoluminescence (PL) spectroscopy. X-ray diffraction indicated that the structure has a single phase with wurtzite structure. FESEM indicated that rosette like structures have been formed. This rosette consists of nanorods with length 210 and 460 nm and diameter 50 and 74 nm for undoped and Cd doped ZnO, respectively. HRTEM showed a decrease in the lattice parameter after the Cd doping. EDX showed that the amount of Cd incorporated into ZnO is 6.4 wt.%. Photoluminescence measurements taken on both doped and undoped samples showed that, in the Cd-doped ZnO nanostructures, the band-edge UV emission is blue shifted and the broad green emission intensity decreased.     

Annealing effect on structure and green emission of ZnO nanopowder by decomposing precursors

ZnO nanopowder is successfully synthesized by annealing the precursors in oxygen gas using the chemical precipitation method. Structural and optical properties of thus synthesized ZnO nanopowder are characterized by scanning electron microscopy (SEM) and photoluminescence (PL). The morphology of ZnO nanopowders evolves from nanorod to cobble as annealing temperature increases from 500 to 1000~\du, while spiral structures are observed in the samples annealed at 900 and 1000~\du. The PL spectra of ZnO nanopowder consist of largely green and yellow emission bands. The green emission from ZnO nanopowder depends strongly on the annealing temperature with a peak intensity at a temperature lower than 800~℃ while the yellow emission is associated with interstitial oxygen \rm O_\i.     

Ultraviolet emissions realized in ZnO via an avalanche multiplication process

Au/MgO/ZnO/MgO/Au structures have been designed and constructed in this study. Under a bias voltage, a carrier avalanche multiplication will occur via an impact ionization process in the MgO layer. The generated holes will be drifted into the ZnO layer, and recombine radiatively with the electrons in the ZnO layer. Thus obvious emissions at around 387 nm coming from the near-band-edge emission of ZnO will be observed. The reported results demonstrate the ultraviolet (UV) emission realized via a carrier multiplication process, and so may provide an alternative route to efficient UV emissions by bypassing the challenging p-type doping issue of ZnO.     

Synthesis and performance of core-shell structured ZnO/In2O3 composites in situ growth

Core-shell structured ZnO/In₂O₃ composites were successfully synthesized via situ growth method. Phase structure, morphology, microstructure and property of the products were investigated by X-ray diffraction (XRD), TG-DTA, field emission scanning electron microscopy (FESEM), energy-dispersive spectrometry (EDS), transmission electron microscope (TEM) and photoluminescence (PL). Results show that the core-shell structures consist of spindle-like ZnO with about 800 nm in length and 200 nm in diameter, and In₂O₃ particles with a diameter of 50 nm coated on the surface of ZnO uniformly. HMTA plays an important role in the formation of core-shell structures and the addition of In₂O₃ has a great effect on PL spectrum. Possible mechanism for the formation of core-shell structures is also proposed in this paper.     

纳米晶ZnO可见发射机制的研究

利用化学沉淀法制备了纳米ZnO粉体,室温下测量了样品的光致发光谱(PL)、X射线衍射谱(XRD),给出了样品的透射电子显微照片(TEM).X射线衍射(XRD)的结果表明:纳米晶ZnO具有六角纤锌矿晶体结构,颗粒呈球形或椭球形.观察到二个荧光发射带,中心波长分别位于398 nm的紫带和510 nm的绿光带.发现随退火温度升高,粒径增大,紫带的峰值减弱、绿带的峰值增强.证实了纳米晶ZnO绿光可见发射带来自氧空位形成的施主和锌空位形成的受主之间的复合.     

Optical characterization of ZnO nanoparticles capped with various surfactants

The presence of surfactants (Hexamine, tetraethylammonium bromide (TEAB), cetyltrimethylammonium bromide (CTAB), tetraoctylammonium bromide (TOAB) and PVP) on the surface of zinc oxide (ZnO) nanoparticles resulted variation in their optical properties. The optical properties of each surfactant-capped zinc oxide nanoparticles were investigated using UV-visible absorption and fluorescence techniques. The particle size of these nanoparticles were calculated from their absorption edge, and found to be in the quantum confinement range. The absorption spectra and fluorescent emission spectra showed a significant blue shift compared to that of the bulk zinc oxide. Large reduction in the intensity of visible emission of zinc oxide/surfactant was observed and these emissions were vanished more quickly, with the decrease in excitation energy, for the smaller nanoparticles. Out of the four surfactants (other than PVP), CTAB-capped zinc oxide has smallest particle size of 2.4 nm, as calculated from the absorption spectrum. Thus the presence of surfactant on the surface of zinc oxide plays a significant role in reducing defect emissions. Furthermore, ZnO/PVP nanoparticles showed no separate UV emission peak; however, the excitonic UV emission and the visible emission at 420 nm overlap to form a single broad band around 420 nm.     

Thickness effect on the evolution of morphology and optical properties of ZnO films

N-Al co-doped ZnO films with various thicknesses were deposited on glass substrates by ultrasonic spray pyrolysis (USP). The crystalline microstructure, morphology, distribution of elements and photoluminescence properties of ZnO films were characterized by X-ray diffraction (XRD), field emission scanning microscopy (FESEM), energy dispersive X-ray spectroscopy (EDS) and photoluminescence (PL) spectroscopy. The XRD and FESEM results show that with the increase of film thickness the grain size increases and the grain shape changes from regular hexagonal sheet-like to wedge-shaped, even pyramidal. The PL spectra illustrate that there is an obvious red-shift for the emission center from ultraviolet to blue region, and the intensities of defects emissions increase with the increase of thickness. In addition, the electrical properties are proved to be strongly affected by film thickness.