Sanjaya Brahma

Self-assembled ZnO nanoparticles on ZnO microsheet: ultrafast synthesis and tunable photoluminescence properties

We report on the tunable photoluminescence characteristics of porous ZnO microsheets fabricated within 1-5 min of microwave irradiation in the presence of a capping agent such as citric acid, and mixture of citric acid with polyvinylpyrrolidone (PVP). The UV emission intensity reduces to 60% and visible emission increases tenfold when the molar concentration of citric acid is doubled. Further diminution of the intensity of UV emission (25%) is observed when PVP is mixed with citric acid. The addition of nitrogen donor ligands to the parent precursor leads to a red shift in the visible luminescence. The deep level emission covers the entire visible spectrum and gives an impression of white light emission from these ZnO samples. The detailed luminescence mechanism of our ZnO samples is described with the help of a band diagram constructed by using the theoretical models that describe the formation energy of the defect energy levels within the energy band structure. Oxygen vacancies play the key role in the variation of the green luminescence in the ZnO microsheets. Our research findings provide an insight that it is possible to retain the microstructure and simultaneously introduce defects into ZnO. The growth of the ZnO microsheets may be due to the self assembly of the fine sheets formed during the initial stage of nucleation.

Effect of substrates and surfactants over the evolution of crystallographic texture of nanostructured ZnO thin films deposited through microwave irradiation

We report the crystallographic texture of ZnO thin films comprising nanorods grown by a microwave irradiation assisted method. Different substrates were used, namely Si, Ge, metal coated Si, PMMA coated Si and ITO coated glass, to examine the respective development of crystallographic texture. The films were characterized by Xray diffraction and scanning electron microscopy, while the texture analysis was done by Xray pole figure analysis using the Schultz reflection method. The ZnO film deposited on Si and Ge showed a mixed texture. On all the other substrates, c axis oriented ZnO films were obtained.

Enhancement in the structure quality of ZnO nanorods by diluted Co dopants: Analyses via optical second harmonic generation

We report a systematic study about the effect of cobalt concentration in the growth solution over the crystallization, growth, and optical properties of hydrothermally synthesized Zn1−xCoxO [0 ≤ x ≤ 0.40, x is the weight (wt.) % of Co in the growth solution] nanorods. Dilute Co concentration of 1 wt. % in the growth solution enhances the bulk crystal quality of ZnO nanorods, and high wt. % leads to distortion in the ZnO lattice that depresses the crystallization, growth as well as the surface structure quality of ZnO. Although, Co concentration in the growth solution varies from 1 to 40 wt. %, the real doping concentration is limited to 0.28 at. % that is due to the low growth temperature of 80 °C. The enhancement in the crystal quality of ZnO nanorods at dilute Co concentration in the solution is due to the strain relaxation that is significantly higher for ZnO nanorods prepared without, and with high wt. % of Co in the growth solution. Second harmonic generation is used to investigate the net dipole dis...

Surfactant-mediated Synthesis of Functional Metal Oxide Nanostructures via Microwave Irradiation-assisted Chemical Synthesis

Nanostructured materials have attracted considerable interest in recent years due to their properties which differ strongly from their bulk phase and potential applications in nanoscale electronic and optoelectronic devices. Metal oxide nanostructures can be synthesized by variety of different synthesis techniques developed in recent years such as thermal decomposition, sol-gel technique, chemical coprecipitation, hydrothermal process, solvothermal process, spray pyrolysis, polyol process etc. All the above processes go through a tedious synthesis procedure followed by prolonged heat treatment at elevated temperature and are time consuming. In the present work we describe a rapid microwave irradiation-assisted chemical synthesis technique for the growth of nanoparticles, nanorods, and nanotubes of a variety of metal oxides in the presence of an appropriate surfactant, without the use of any templates The method is simple, inexpensive, and helps one to prepare nanostructures in a very simple way, and in a very short time, measured in minutes. The synthesis procedure employs high quality metalorganic complexes (typically -diketonates) featuring a direct metal-to-oxygen bond in its molecular structure. The complex is dissolved in a suitable solvent, often with a surfactant added, and the solution then subjected to microwave irradiation in a domestic microwave oven operating at 2.45 GHz frequency with power varying from 160-800 W, from a few seconds to a few minutes, leading to the formation of corresponding metal oxides. This method has been used successfully to synthesize nanostructures of a variety of binary and ternary metal oxides such as ZnO, CdO, Fe2O3, CuO, Ga2O3, Gd2O3, ZnFe2O4, etc. There is an observed variation in the morphology of the nanostructures with the change of different parameters such as microwave power, irradiation time, appropriate solvent, surfactant type and concentration. Cationic, anionic, nonionic and polymeric surfactants have been used to generate a variety of nanostructures. Even so, to remove the surfactant, there is either no need of heat treatment or a very brief exposure to heat suffices, to yield highly pure and crystalline oxide materials as prepared. By adducting the metal complexes, the shape of the nanostructures can be controlled further. In this manner, very well formed, single-crystalline, hexagonal nanorods and nanotubes of ZnO have been formed. Adducting the zinc complex leads to the formation of tapered ZnO nanorods with a very fine tip, suitable for electron emission applications. Particle size and their monodispersity can be controlled by a suitable choice of a precursor complex, the surfactant, and its concentration. The resulting metal oxide nanostructures have been characterized by X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, FTIR spectroscopy, photoluminescence, and electron emission measurements.

Crystal Orientation Dynamics of Collective Zn dots before Preferential Nucleation

The island nucleation in the context of heterogeneous thin film growth is often complicated by the growth kinetics involved in the subsequent thermodynamics. We show how the evolution of sputtered Zn island nucleation on Si(111) by magnetron sputtering in a large area can be completely understood as a model system by combining reflective second harmonic generation (RSHG), a 2D pole figure with synchrotron X-ray diffraction. Zn dots are then oxidized on the surfaces when exposed to the atmosphere as Zn/ZnO dots. Derived from the RSHG patterns of Zn dots at different growth times, the Zn dots grow following a unique transition from kinetic to thermodynamic control. Under kinetic-favoring growth, tiny Zn dots prefer arranging themselves with a tilted c-axis to the Si(111) substrate toward any of the sixfold in-plane Si<110> directions. Upon growth, the Zn dots subsequently evolve themselves to a metastable state with a smaller tilting angle toward selective <110> directions. As the Zn dots grow over a critical size, they become most thermodynamically stable with the c-axis vertical to the Si(111) substrate. For a system with large lattice mismatch, small volume dots take kinetic pathways with insignificant deviations in energy barriers.

Surfactant Free, Non-aqueous Method, for the Deposition of ZnO Nanoparticle Thin Films on Si(100) Substrate with Tunable Ultraviolet (UV) Emission

We report, strong ultraviolet (UV) emission from ZnO nanoparticle thin film obtained by a green synthesis, where the film is formed by the microwave irradiation of the alcohol solution of the precursor. The deposition is carried out in non-aqueous medium without the use of any surfactant, and the film formation is quick (5 min). The film is uniform comprising of mono-disperse nanoparticles having a narrow size distribution (15-22 nm), and that cover over an entire area (625 mm(2)) of the substrate. The growth rate is comparatively high (30-70 nm/min). It is possible to tune the morphology of the films and the UV emission by varying the process parameters. The growth mechanism is discussed precisely and schematic of the growth process is provided.

Bis(acetyl-acetonato-κO,O')(pyridine-κN)zinc(II).

In the title compound, [Zn(C5H7O2)2(C5H5N)], the metal atom has square-pyramidal coordination geometry with the basal plane defined by the four O atoms of the chelating acetylacetonate ligands and with the axial position occupied by the pyridine N atom. The crystal packing is characterized by a C—H⋯O hydrogen-bonded ribbon structure approximately parallel to [10].

Flower-like ZnO nanorod arrays grown on HF-etched Si (111): constraining relation between ZnO seed layer and Si (111)

We demonstrate the formation of self-assembled homogenous flower-like ZnO nanorods over a ZnO seed layer deposited on a HF-etched Si (111) substrate. The typical flower-like morphology of ZnO nanorod arrays is ascribed to the formation of the island-like seed layer which is deposited by the drop method followed by annealing at 300 °C. The island-like ZnO seed layer consists of larger ZnO grains, and is built by constraining of the Si (111) surface due to pattern matching. Pattern matching of Si with ZnO determines the shape and size of the seed layer and this controls the final morphology of ZnO nanorods to be either flower like or vertically aligned. The high quality of the island-like ZnO seed layer enhances the diameter and length of ZnO nanorods. Besides, while the amorphous layer formed during the annealing process would influence the strained ZnO grain, that subsequent amorphous layer will not block the constraining between the ZnO grain and the substrate.

Shape Transformation of ZnO Nanorods/Nanotubes at Low Temperature

We report the shape transformation of ZnO nanorods/nanotubes at temperatures (similar to 700 degrees C) much lower than the bulk melting temperature (1975 degrees C). With increasing annealing temperature, not only does shape transformation take place but the luminescence characteristics of ZnO are also modified. It is proposed that the observed shape transformation is due to surface diffusion, contradicting the previously reported notion of melting and its link to luminescence. Luminescence in the green-to-red region is observed when excited with a blue laser, indicating the conversion of blue to white light.