Effect of excitation and detection angles on photoluminescence spectrum from ZnO nanorod array

The angular dependent photoluminescence from ZnO nanorod array was investigated. Variations in the excitation and detection angles provided to reveal a blue shift and then splitting of a near-band edge emission into two bands. It is suggested that the observed phenomenon is caused by an inhomogeneous distribution of the emission along the nanorod length. The spatially resolved cathodoluminescence measurements confirmed that indeed the emission along the length of the nanorod is inhomogeneous and the top and bottom parts of the nanorod exhibit different emission spectra.     

Characterization of optoelectronic properties of the ZnO nanorod array using surface photovoltage technique

Well-aligned ZnO nanorod array, synthesized by wet chemical bath deposition (CBD) method on conductive indium-in-oxide (ITO) substrate, was characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and photoluminescence (PL) spectroscopy. Surface photovoltage (SPV) technique based on a scanning Kelvin Probe system was employed to investigate the optoelectronic behavior of ZnO nanorod array. The surface photovoltage and its time-resolved evolution process are used to determine the energy level structure of the ZnO nanorod array.     

Controllable growth of well-aligned ZnO nanorod arrays by low-temperature wet chemical bath deposition method

Well-aligned ZnO nanorod arrays were synthesized by low-temperature wet chemical bath deposition (CBD) method on Si substrate under different conditions. Results illustrated that dense ZnO nanorods with hexagonal wurtzite structure were vertically well-aligned and uniformly distributed on the substrate. The effects of precursor concentration, growth temperature and time on nanorods morphology were investigated systematically. The mechanism for the effect of preparation parameters was elucidated based on the chemical process of CBD and basic nucleation theory. It is demonstrated that the controllable growth of well-aligned ZnO nanorods can be realized by readily adjusting the preparation parameters. Strong near-band edge ultraviolet (UV) emission were observed in room temperature photoluminescence (PL) spectra for the samples prepared under optimized parameters, yet the usually observed defect related deep level emissions were nearly undetectable, indicating high optical quality ZnO nanorod arrays could be achieved via this easy process chemical approach at low temperature.     

两步法制备超疏水性ZnO纳米棒薄膜

采用两步法制备了超疏水性ZnO纳米棒薄膜,在用磁控溅射在普通玻璃衬底上生长一层ZnO籽晶层基础上,利用液相法制备了空间取向高度一致的ZnO纳米棒阵列,经修饰后由亲水性转变为超疏水性.用扫描电子显微镜观察了纳米棒的表面结构,用接触角测量仪测出水滴在ZnO纳米棒薄膜表面的接触角为151°±05°,滚动角为7°.用Cassie模型对ZnO纳米棒薄膜的超疏水性进行了验证. 关键词： ZnO纳米棒 超疏水 两步法     

Synthesis and optical characterization of vertically grown ZnO nanowires in high crystallinity through vapor-liquid-solid growth mechanism

The gas-phase growth and optical characteristics of 1-dimensional ZnO nanostructure have been investigated. The ZnO nanowires (NWs) were grown vertically on Au coated silicon substrates by vapor-liquid-solid (VLS) growth mechanism using chemical vapor deposition (CVD). The ZnO NWs were grown in the crystal direction of [0 0 0 1]. The ZnO NWs exhibit the uniform size of less than 100 nm in diameter and up to 5 μm in length. Photoluminescence (PL) spectrum of ZnO NWs shows the strong band-edge emission at ∼380 nm (∼3.27 eV) without significant deep-level defect emission. The exciton lifetime of ZnO NWs was measured to be approximately 150 ± 10 ps.     

Nanostructured solar cell based on solution processed Cu2ZnSnS4 nanoparticles and vertically aligned ZnO nanorod array

Cu₂ZnSnS₄ (CZTS) has attracted intensive interest for application in photovoltaic technology due to its excellent semiconductor properties. We report a nanostructured CZTS solar cell which was fabricated by infiltrating of CZTS nanoparticles into CdS coated ZnO nanorod arrays. The well aligned ZnO nanorods facilitate the efficient infiltration of CZTS nanoparticles. A hole transport layer was deposited to facilitate the transport of holes. The nanostructured CZTS solar cell demonstrated a remarkably high short‐circuit current density (11.0 mA/cm²). As a result, a power conversion efficiency of 2.8% was obtained. (© 2014 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

热蒸发法制备ZnO纳米棒阵列

氩气氛常压下，利用热蒸发法，在无催化剂、无ZnO预沉积层的硅衬底上制备了取向良好，排列整齐的ZnO纳米棒阵列．在距Zn源不同位置的Si衬底上得到了不同形貌的样品．硅衬底置于锌源正上方是得到取向一致的ZnO纳米阵列的一个关键性条件．用场发射扫描电子显微镜、X射线粉末衍射表征样品表面形貌、晶体结构．进一步研究了样品的生长机制和荧光性质．     

Photovoltaic properties of the copper-phthalocyanine and ZnO nanorod array system affected by ethanol

Well-aligned ZnO nanorod array, fabricated on conductive indium-tin-oxide (ITO) substrate by wet chemical bath deposition (CBD) method, was characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD). Surface photovoltage (SPV) technique was employed to study the photovoltaic properties of the copper-phthalocyanine (CuPc) and ZnO nanorod array system affected by ethanol. Prior to ethanol adsorption, two pronounced SPV response bands were exhibited for this system in the range 300-410 and 540-760 nm, respectively. Post-adsorption measurements reveal that the SPV intensity of the former band is enhanced, while that of the latter band is suppressed if ethanol was used to modify CuPc surface. Moreover, both of the SPV intensity of two response bands is enhanced if ethanol was used to modify ZnO and CuPc interface. Mechanisms of these phenomena were suggested.     

Well-aligned ZnO rod arrays grown on glass substrate from aqueous solution

Well-aligned ZnO rod arrays have been successfully synthesized on glass substrate from the aqueous solution of Zn(NO₃)₂·6H₂O and C₆H₁₂N₄ (HMT). Some critical issues such as seed layers, concentration and reaction time were investigated. The results show that ZnO seed layers were pre-requisite for the aligned growth of ZnO rod arrays. The length of rods is tunable in a range from 2 μm to 3 μm by varying the solution concentration and reaction time. X-ray diffraction results demonstrate that ZnO rods are wurtzite crystal structures preferentially orienting in the direction of the c-axis. Microstructure observation by scanning electron microscope confirms that ZnO rods grew up perpendicular to the substrate. Room-temperature photoluminescence (PL) spectrum of rod arrays shows a strong emission band at about 396 nm.     

Synthesis of submicron rhombic ZnO rods via ZnOHF intermediate using electrodeposition route

ZnOHF submicron rods with the rhombus-like shape were successfully prepared by a low-temperature aqueous electrodeposition route. By further adjusting the experimental parameters including the electrolyte concentration, temperature, the electrodeposition potential, and the duration, the morphologies of ZnOHF films can further be controlled; accordingly, ZnO films with different morphologies were also obtained by calcining ZnOHF intermediate at 400 °C for 2 h. Based on the experimental results, a plausible mechanism for the conversion from ZnOHF to ZnO crystals was proposed. The surface morphology and microstructure of the products were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and transmission electron microscopy (TEM), and the optical property of the samples was investigated by room-temperature photoluminescence (PL) spectra as well. The PL spectra confirmed that ZnOHF and ZnO exhibited emission band centered at 413 nm and 382 nm in UV region, respectively.     

Synthesis and characterization of Mn-doped ZnO column arrays

Mn-doped ZnO column arrays were successfully synthesized by conventional sol-gel process. Effect of Mn/Zn atomic ratio and reaction time were investigated, and the morphology, tropism and optical properties of Mn-doped ZnO column arrays were characterized by SEM, XRD and photoluminescence (PL) spectroscopy. The result shows that a Mn/Zn atomic ratio of 0.1 and growth time of 12 h are the optimal condition for the preparation of densely distributed ZnO column arrays. XRD analysis shows that Mn-doped ZnO column arrays are highly c-axis oriented. As for Mn-doped ZnO column arrays, obvious increase of photoluminescence intensity is observed at the wavelength of ∼395 nm and ∼413 nm, compared to pure ZnO column arrays.     

Growth of ZnO nanorods by aqueous solution method with electrodeposited ZnO seed layers

ZnO nanorod arrays on ZnO-coated seed layers were fabricated by aqueous solution method using zinc nitrate and hexamethylenetetramine at low temperature. The seed layers were coated on ITO substrates by electrochemical deposition technique, and their textures were dominated by controlling the deposition parameters, such as deposition potential and electrolyte concentration. The effects of the electrodeposited seed layers and the growing parameters on the structures and properties of ZnO nanorod arrays were primarily discussed. The orientation and morphology of both the seed layer and successive nanorods were analyzed by using X-ray diffraction (XRD), SEM and TEM. The results show that the seed layer deposited at −700 mV has evenly distributed crystallites and (0 0 2) preferred orientation; the density of resultant nanorods is high and ZnO nanorods stand completely perpendicular onto substrates. Meanwhile, the size of nanorods quite also depends on the growth solution, and the higher concentration of growth solution primary leads to a large diameter of the ZnO nanorods.     

Photoluminescence of ZnO nanostructures grown by the aqueous chemical growth technique

Zinc oxide nanostructured films were grown by the aqueous chemical growth technique using equimolar aqueous solutions of zinc nitrate and hexamethylenetetramine as precursors. Silicon(100) and glass substrates were placed in Pyrex glass bottles with polypropylene autoclavable screw caps containing the precursors described above, and heated at 95 C for several hours. X-ray diffraction 2θ/θ scans showed that the only crystallographic phase present was the hexagonal wurtzite structure. Scanning electron microscopy showed the formation of flowerlike ZnO nanostructures, consisting of hexagonal nanorods with a diameter of a few hundred nanometers. The photoluminescence spectra of the ZnO nanostructures were recorded at 18–295 K using a cw He–Cd laser (325 nm) and a pulsed laser (266 nm). The ZnO nanostructures exhibit an ultraviolet emission band centered at 3.192 eV in the vicinity of the band edge, which is attributed to the well-known excitonic transition in ZnO.     

Fabrication and characterization of Mg-doped pencil-shaped ZnO microprisms

Two types of novel Mg-doped pencil-shaped ZnO microprisms had been successfully synthesized on Mg(NO₃)₂-coated Si (1 1 1) substrates by thermal chemical vapor deposition method. The as-prepared ZnO prisms were characterized with X-ray diffraction (XRD), scanning electron microscopy (SEM), field-emission transmission electron microscope (FETEM), selected area electron diffraction (SAED), and photoluminescence (PL) spectroscopy. The straight microprisms are made up of hexagonal pyramids tips and hexagonal prisms bodies. Both of the structures are perfect single crystal and have grown along the [0 0 0 1] direction preferentially. Photoluminescence reveals a red-shift at around 387 nm which is induced by Mg doping and a green light emission peak at around 511 nm. The pencil-shaped ZnO microstructure can provide an improvement in novel ultraviolet light-emitting devices. In addition, the growth mechanism of the special ZnO microprisms is discussed briefly.     

Unusual electrical properties of hydrothermally grown ZnO

Bulk ZnO of high structural and optical quality can be grown by the hydrothermal method. An X-ray rocking-curve linewidth of 18 arcsec has been measured for the (002) reflection, and a photoluminescence linewidth of 0.3 meV has been found for one of the donor–bound exciton lines. However, the electrical properties are unusual in that shallow donors are not dominant, as is the case for vapor-phase-grown and melt-grown bulk crystals. This situation can be greatly modified by annealing in forming gas (5% H₂ in N₂) at , with bulk shallow donors then becoming completely dominant for , and near-surface donors at lower temperatures. As T_A is varied from 100–650 C, both the mobility and carrier concentration vary in nonmonotonic fashion, due to changes in the relative strengths of the bulk and surface components of conduction.     

Synthesis and characterization of ZnO nano/microfibers thin films by catalyst free solution route

Zinc oxide (ZnO) nano/microfibrous thin films were successfully synthesized by a catalyst free solution route on glass and Si substrates. X-ray diffraction study revealed the formation of ZnO nanofibers of hexagonal crystalline structure. The texture coefficient of different planes varied with annealing temperature and that of the (0 0 2) plane was the highest for films annealed at temperature 873 K. Scanning electron micrograph showed the well formation of ZnO nano/microfibers with an average diameter 500 nm and having an average aspect ratio 150. UV–Vis–NIR spectroscopic study for the films deposited on glass substrates showed the high transmittance in the visible and near-infrared region. It was also observed that the band gap energy decreased as the films were annealed at higher temperature. The band gap energies of nanostructured ZnO thin films were determined to be in the range 3.03–3.61 eV. The photoluminescence study showed an UV emission peak at 397 nm, a visible blue–green emission peak at 468 nm and a green emission peak at 495 nm. Field emission properties of nanofiber ZnO thin film showed considerably low turn-on field around 1.4 V/μm. The emission current was as high as 70 μA at the field of 3.6 V/μm.     

Rapid synthesis and luminescence of the Eu, Er codoped ZnO quantum-dot chain via chemical precipitation method

ZnO quantum-dot chains codoped with Eu³⁺ and Er³⁺ were synthesized by the chemical precipitation method and the codoping effects on the structures, morphologies and optical properties of the powders were briefly investigated. The X-ray diffraction (XRD) and energy dispersive spectroscopy (EDS) results indicated the Eu³⁺ and Er³⁺ were incorporated into the crystal lattice of ZnO host. Transmission electron microscope (TEM) measurements showed the sizes of the ZnO quantum dots decreased with the increase of Eu³⁺ and Er³⁺ doping concentration, and the quantum-dot chains were formed by codoping with Eu³⁺ and Er³⁺. The green emissions in the photoluminescence spectra were attributed to 4f-4f of Er³⁺ inner shell ²H_11/2 → ⁴I_15/2 and ⁴S_3/2 → ⁴I_15/2 transitions, and the characteristic red emissions of Eu³⁺ ions were attributed to the ⁵D₀ → ⁷F₁ and ⁵D₀ → ⁷F₂ transitions, respectively. Moreover, the red emission of the Eu³⁺ ions gradually decreased with the Er³⁺ ions doping concentration increased, which may be due to the different energy storage centers in the powders.     

Photoluminescence behavior of ZnO nanorods produced by eclipse PLD from a Zn metal target

In this work, arrays of one-dimensional ZnO nanostructures were deposited on c-axis sapphire by standard and eclipse pulsed laser deposition (EPLD) using a metallic Zn target. One reference sample was grown by standard PLD and nine were grown by EPLD using a 16 by 16 mm² square shadow mask. Three shadow mask positions were used, with three depositions at varying oxygen pressures for each mask position. The oxygen partial pressure was between 100 and 200 mTorr for all growth procedures with a substrate temperature of 600 C.SEM reveals that arrays of nanorods are formed when growing by standard PLD. When grown by EPLD the rods tend to clump together with ordering on the micron scale. Low temperature photoluminescence was carried out as a function of position over several of the samples with 1 or 2 mm spacing. In general, it was found that the luminescence intensity is maximum in the center of the samples and falls off toward the edges while the shape stays roughly the same. Free exciton emission was resolved in most samples along with several other emission peaks from donor-bound excitons. The integrated PL intensity for all the EPLD samples is an order of magnitude higher than for the standard PLD sample. Linewidths are significantly reduced as well. Hence, the EPLD grown samples have superior optical quality and this growth technique shows promise for growth of high quality ZnO nanostructures.     

Effect of the annealing environment on the optical properties of ZnO/GaAs grown by MOCVD

The optical properties of ZnO grown on (1 0 0) GaAs substrate using metalorganic chemical vapor deposition are investigated by photoluminescence (PL) spectroscopy. Postgrowth annealing in nitrogen and oxygen was performed for different times and temperatures in order to incorporate As from the substrate into the ZnO thin films. The PL spectra of the samples annealed in different ambients reveal that the effect of As diffusion into the ZnO thin films is more pronounced when the annealing is performed in oxygen at 550 °C. The 11 K PL spectra show the appearance of a transition at ∼3.35 eV after annealing in oxygen at 550 °C for 1 h. A further increase in the annealing temperature leads to the disappearance of this line, while for annealing times longer than 2 h at 550 °C, it is no longer prominent. The increase in intensity of this new transition is also accompanied by the enhancement of radiative centers related to structural defects, such as the stacking fault-related transition at 3.31 eV and the Y-line. Temperature dependent PL illustrates the excitonic nature of the new transition at ∼3.35 eV, which is therefore assigned to (A⁰, X) transition, where the acceptor is possibly the 2V_Zn-As_Zn complex, with an activation energy E_A in the range of 160-240 meV. Furthermore, the enhancement of the radiative centers related to structural defects is regarded as evidence that As atoms tend to segregate in the vicinity of structural defects to relieve local strain.