Optical studies of ZnO nanocrystals doped with Eu3+ ions

Synthetic ZnO nanocrystals have been intentionally doped with Eu³⁺ ions. Structural analysis performed on the nanocrystals showed wurtzite-ZnO as the only phase present in the samples. Photoluminescence in emission and excitation modes allows the assignment of the intra-4f⁶ transitions for the Eu³⁺ ions. From the analysis of the optical data we are able to demonstrate that multiple Eu-related optical centres are present in the studied samples. Oxygen vacancies are likely candidates to be responsible for the ion accommodation in the ZnO lattice and from the photoluminescence excitation data we tentatively assign a trap level at ∼200 meV below the conduction band to this intrinsic defect. PACS 78.66.Hf; 78.67.-n; 82.80.Yc     

Surface-enhanced Raman spectroscopy of semiconductor nanostructures

We review our recent results concerning surface-enhanced Raman scattering (SERS) by confined optical and surface optical phonons in semiconductor nanostructures including CdS, CuS, GaN, and ZnO nanocrystals, GaN and ZnO nanorods, and AlN nanowires. Enhancement of Raman scattering by confined optical phonons as well as appearance of new Raman modes with the frequencies different from those in ZnO bulk attributed to surface optical modes is observed in a series of nanostructures having different morphology located in the vicinity of metal nanoclusters (Ag, Au, and Pt). Assignment of surface optical modes is based on calculations performed in the frame of the dielectric continuum model. It is established that SERS by phonons has a resonant character. A maximal enhancement by optical phonons as high as 730 is achieved for CdS nanocrystals in double resonant conditions at the coincidence of laser energy with that of electronic transitions in semiconductor nanocrystals and localized surface plasmon resonance in metal nanoclusters. Even a higher enhancement is observed for SERS by surface optical modes in ZnO nanocrystals (above 10⁴). Surface enhanced Raman scattering is used for studying phonon spectrum in nanocrystal ensembles with an ultra-low areal density on metal plasmonic nanostructures.     

In-situ neutron scattering study of crystallization in a Zr-based bulk metallic glass

In this paper, we report the structure, optical, and gas-sensing properties of Co-doped ZnO nanocrystals prepared by a simple solvothermal route. The red-shift of the band-gap edge is attributed to a merging of donor and conduction bands due to Co doping. Photoluminescence (PL) spectra were used to study the dependence of doping on the deep-level emission, which show obvious enhanced blue-green emission after Co doping. Gas sensors were prepared and tested for the detection of C₂H₅OH in air. It is found that the Co-doped nanocrystals have a significantly better sensing performance than pure ZnO, which is comparable to the Au-functionalized ZnO sensors. We provide a possible explanation in terms of the sensing mechanism of the surface reaction process.     

Room-temperature growth of high-quality ZnO nanocrystals using a dressed-photon-assisted near-field process

Single-crystalline ZnO nanocrystals were fabricated by room-temperature photo-chemical vapor deposition (PCVD). We further enhanced the growth of high-quality single-crystalline ZnO nanocrystals using dressed photons and phonons (DPPs). This resulted in greater position control and the growth of high-quality ZnO nanocrystals. The ZnO nanocrystals produced with DPPs had excellent cathodoluminescence characteristics, indicating that the near-field PCVD process could be a promising technique for nanophotonic integrated circuit production.     

Excimer laser accelerated hydrothermal synthesis of ZnO nanocrystals & their electrical properties

The synthesis of ZnO nanocrystals is reported using a hydrothermal chemical growth technique combined with 248 nm nanosecond excimer laser heating at fluences in the range 0-390 mJ cm⁻². The effect of laser heating in controlling the morphology of the nanocrystals is investigated using optical spectroscopy and electron microscopy characterization. Laser heating is shown to allow control of the crystal morphology from nanoparticles to nanorods as well as to modify the size distributions. The results indicate that not only does the laser accelerate the growth of nanocrystals, but can also produce crystals with a narrow size distribution possibly via photothermal size selection. An initial study of electrical conduction properties of ZnO nanocrystal thin films is also discussed.     

Optical nanolaser on the heavy hole transition in semiconductor nanocrystals: Theory

We discuss the energy spectrum of electron–hole pairs in a quasi-zero-dimensional system consisting of spherical semiconductor nanocrystals placed in transparent dielectric matrices. We study theoretically the prospect of using hole transitions between equidistant series of quantum levels observed in nanocrystals for designing an optical nanolaser.     

Effect of solution concentrations on crystal structure,surface topographies and photoluminescence properties of ZnO thin films

Zinc oxide thin films were deposited on silicon substrates via hydrothermal method. Microstructures, surface topographies and optical properties of ZnO thin films were systematically investigated by X-ray diffraction, atomic force microscopy and fluorescence spectrophotometer. The mean grain size and surface roughness of the thin films decrease first and then increase with increasing the concentration of zinc nitrate hexahydrate. The photoluminescence spectra of ZnO thin films, excited by the 240, 320, 360, 380 and 400 nm excitation wavelength, were investigated in detail. Based on our analysis, it can be noted that mechanisms of the ultraviolet, violet and blue emissions are attributed to the transitions from the localized levels below the conduction band, zinc vacancy, interstitial zinc and extended interstitial zinc levels to the valance band, respectively. Blue–violet emissions of ZnO have great potential in light emitting and biological fluorescence labeling applications.     

Position-controlled and catalyst-free growth of ZnO nanocrystals by nanoparticle-assisted pulsed laser deposition

We have synthesized ZnO nanocrystals, such as nanowires, nanorods, and nanosheets, using a nanoparticle-assisted pulsed laser deposition (NAPLD) method. Recently, we achieved position-controlled growth of the ZnO nanocrystals by means of a ZnO buffer layer and laser irradiation without any catalyst. The periodic structure was formed on the ZnO buffer layer by multi-beam interference patterning, and then vertically aligned ZnO nanowalls, corresponding to the patterning, were grown on the buffer layer. It was found that the periodic ZnO nanowalls grew along the c-axis direction by X-ray diffraction measurement. The well-aligned ZnO nanowalls are expected to be utilized as building blocks for field emitters and UV LEDs. The proposed technique can be used as one of the effective methods to control the growth position of the ZnO nanocrystals because various structures can be easily fabricated by a laser writing and a spatial light modulator.     

液晶-氧化锌纳米复合材料的可调发光

采用超声波分散技术,选用氧化锌纳米晶体和液晶（N-（4-methoxybenzylidene）-4-ethoxybenzenamine）,制成液晶质量分数分别为10%、20%、30%、40%、50%、60%、70%、80%的液晶-氧化锌纳米复合材料。通过X射线衍射仪、透射电子显微镜、光致发光光谱仪对样品进行表征。实验结果表明：当液晶MB₂BA在氧化锌纳米晶体的质量分数从0增加到80%时,氧化锌纳米复合材料的PL光谱峰值最终移到了418 nm的蓝光区域。随着氧化锌纳米晶体中液晶分子的增加,氧化锌纳米晶体的表面缺陷减少、其深层发光明显削弱,氧化锌纳米晶体的光致发光可以由最初的黄绿色转变为蓝色。因此,可以在氧化锌纳米晶体中通过添加适量的液晶MB₂BA来实现蓝光发射。     

Density-controlled growth of ZnO nanorods using ZnO nanocrystals-embedded polymer composite

This work focuses on novel synthesis of ZnO nanorods for their potential applications to optoelectronic and electronic nanodevices. The growth density of ZnO nanorods was modulated through controlling of the density of ZnO nanocrystals dispersed on Si substrate. For this, ZnO nanocrystals synthesized via a polyol process were blended with a polymer matrix. ZnO nanocrystals-embedded polymer composite film was generated by spin-coating the mixed solution. Subsequent heat treatment of composite film removed a polymer matrix and left ZnO nanocrystals on the substrate, serving as seeds for the following ZnO nanorod growth. The density of grown ZnO nanorods was well controllable, depending on the density of dispersed ZnO nanocrystals on the substrate, which was varied by the concentration of ZnO nanocrystal-polymer solution.     

Photoluminescence properties of bare and ZnO infilled artificial opal

Photoluminescence of bare and ZnO infilled artificial opals was investigated. A presence of a photonic band gap results in distortion of the photoluminescence spectra of both the bare and ZnO infilled opal nanocomposite. Filling of the opal with ZnO resulted in a shift of the Bragg diffraction peak from 430 to 460 nm. The emission from ZnO infilled opal contains no UV photoluminescence from ZnO nanocrystals, while the ZnO nanocrystals deposited on substrate by the same method exhibit strong excitonic UV emission. Although a high temperature treatment in ambient air results in an increase in the photoluminescence intensity of the ZnO nanocrystals, the quenched behavior of the excitonic emission from ZnO nanocrystals embedded in the opal matrix remains. A domination of the artificial opal matrix intrinsic emission in the photoluminescence spectra from the untreated as well as heat treated ZnO filled opal nanocomposites is observed.     

Nanosecond dynamics of the near-infrared photoluminescence of Er-doped SiO2 sensitized with Si nanocrystals

We report on an observation of a fast 1.5 microm photoluminescence band from Er3+ ions embedded in an SiO2 matrix doped with Si nanocrystals, which appears and decays within the first microsecond after the laser excitation pulse. We argue that the fast excitation and quenching are facilitated by Auger processes related to transitions of confined electrons or holes between the space-quantized levels of Si nanocrystals dispersed in SiO2. We show that a great part--about 50%--of all Er dopants is involved in these fast processes and contributes to the submicrosecond emission.     

La、Ce掺杂ZnO纳米晶的发光特性

共沉淀法制备了稀土镧、铈掺杂的ZnO半导体纳米晶。X射线衍射(XRD)结果表明:掺杂的ZnO纳米晶为六方纤锌矿结构,随掺杂浓度增加ZnO粒径减小。对铈掺杂纳米ZnO,以波长380nm激发,在443nm处出现了半峰宽较窄的强的蓝光发射峰;镧掺杂ZnO纳米晶则为从418~610nm的多峰宽带发射。     

Structural and optical properties of cobalt doped ZnO nanocrystals

Zn_1−xCo_xO nanocrystals with nominal Co doping concentrations of x = 0–0.1 were synthesized through a simple solution route followed by a calcining process. The doping effects on the structural, morphological and optical properties were investigated by means of X-ray diffraction, scanning electron microscopy, transmission electron microscopy, Raman, absorption and luminescence spectroscopy. The results indicated that a small amount of Co ions were incorporated into ZnO lattice structure, whereas the secondary phase of Co₃O₄ was segregated and precipitated at high Co doping concentrations, the solid solubility of Co ions in ZnO nanocrystals could be lower than 0.05. The spectra related to transitions within the tetrahedral Co²⁺ ions in the ZnO host crystal were observed in absorption and luminescence spectra.     

Luminescence of ZnO nanocrystals capped with an organic dye

ZnO nanocrystals capped with an organic dye Rhodamine 6G (Rh6G) were investigated by photoluminescence (PL) and cathodoluminescence (CL) techniques. PL and CL spectra showed a remarkable decrease in visible emission intensity after ZnO nanocrystals were capped with Rh6G, indicating that dangling bonds and defect states existing at the surface of ZnO nanocrystals were significantly passivated. Rh6G on the ZnO surface exhibited a monomer-like emission, and the intensity and the position of the emission were dependent on the dye concentration.     

Controllable synthesis and shape-dependent photocatalytic activity of ZnO nanorods with a cone and different aspect ratios and of short-and-fat ZnO microrods by varying the reaction temperature and time

ZnO nanorods with a cone and different aspect ratios and short-and-fat ZnO microrods were synthesized via a hydrothermal reaction of Zn with Zn(CH₃COO)₂ and H₂O. The control over these ZnO nanocrystals with a wurtzite structure and different shapes was achieved by adjusting only the reaction temperature and time. A possible kinetic mechanism was proposed to account for the growth of these ZnO nanocrystals with different shapes. Photocatalytic activities of ZnO nanocrystals with distinctive shapes in the degradation of methyl orange were investigated. The results indicate that the photocatalytic ability of the ZnO nanorods with a cone and different aspect ratios is stronger than that of the short-and-fat microrods.     

Synthesis and characterisation: Zinc oxide–sulfide nanocomposites

A novel synthesis method is presented for the preparation of nanosized-semiconductor zinc oxide–sulphide (ZnO/ZnS) core–shell nanocomposites, both formed sequentially from a single-source solid precursor. ZnO nanocrystals were synthesized by a simple co-precipitation method and ZnO/ZnS core–shell nanocomposites were successfully fabricated by sulfidation of ZnO nanocrystals via a facile chemical synthesis at room temperature. The as-obtained samples were characterized by X-ray diffraction and transmission electron microscopy. The results showed that the pure ZnO nanocrystals were hexagonal wurtzite crystal structures and the ZnS nanoparticles were sphalerite structure with the size of about 10 nm grown on the surface of the ZnO nanocrystals. Optical properties measured reveal that ZnO/ZnS core–shell nanocomposites have integrated the photoluminescent effect of ZnO and ZnS. Based on the results of the experiments, a possible formation mechanism of ZnO/ZnS core–shell nanocomposites was also suggested. This treatment is suggested to improve various properties of optoelectronically valuable ZnO/ZnS nanocomposites. These nanosized semiconductor nanocomposites can form a new class of luminescent materials for various applications.     

Electron-phonon interaction in non-polar quantum dots induced by the amorphous polar environment

We propose a Fröhlich-type electron-phonon interaction mechanism for carriers confined in a non-polar quantum dot surrounded by an amorphous polar environment. Carrier transitions under this mechanism are due to their interaction with the oscillating electric field induced by the local vibrations in the surrounding amorphous medium. We estimate the corresponding energy relaxation rate for electrons in Si nanocrystals embedded in a SiO₂ matrix as an example. When the nanocrystal diameter is larger than 4 nm then the gaps between the electron energy levels of size quantization are narrow enough to allow for transitions accompanied by emission of a single local phonon having the energy about 140 meV. In such Si/SiO₂ nanocrystals the relaxation time is in nanosecond range.     

Photoluminescence from ZnO-SiO2 opals with different sphere diameters and thicknesses

We systematically investigated the photoluminescence (PL) and transmittance characteristics of ZnO-SiO₂ opals with varied positions of the stop-band and film thicknesses. An improved ultraviolet (UV) luminescence was observed from ZnO-SiO₂ composites over pure ZnO nanocrystals under 325 nm He-Cd laser excitation at room temperature. The UV PL of ZnO nanocrystals in SiO₂ opals with stop-bands center of 410 nm is sensitive to the thickness of opal films, and the UV PL intensity increases with the film thickness increasing. The PL spectra of ZnO nanocrystals in SiO₂ opals with stop-bands center of 570 nm show a suppression of the weak visible band. The experimental results are discussed based on the scattering and/or absorbance in opal crystals.     

Band alignment and charge transport characteristics of TPP/ZnO hybrid for photovoltaic cell potential

Growth of ZnO nanocrystals has been carried out by a two-electrode electrochemical cell arrangement. The nanocrystals serve as substrates onto which tetraphenylporphyrin (TPP) is evaporated under integrated UHV conditions for the development of TPP/ZnO hybrid specimen. The quality of the hybrid specimen is investigated by XPS measurement. Direct interaction between the valence electrons of the adsorbed TPP molecules and ZnO electronic levels is revealed by Ultraviolet Photoemission Spectroscopy (UPS). Absorption spectroscopic studies are used to examine the ground state electronic structure and polarization dependence (excitation to π* and σ* vacant orbitals) of the hybrid specimen. The studies further show efficient charge transfer from donor (TPP) to proximate acceptor (ZnO). Thus, porphyrin molecules act as an active layer for generation of electron and as an enhancement for subsequent sudden transfer of the charge to the ZnO at a timescale faster than that of core hole.