Controlling the size of ZnO quantum dots using the dressed photon–phonon-assisted sol–gel method

We developed a sol–gel method using the dressed photon–phonon (DPP) process. DPPs are selectively exited in nanoscale structures at photon energies that are lower than the bandgap energy, which allows one to increase the growth rate of smaller ZnO quantum dots (QDs). Thus, we obtained a smaller size variance of ZnO QDs. The growth rate was proportional to the power of the light used for DPP excitation. The results were confirmed using a rate equation that accounted for the concentration of the sol–gel solution.     

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.     

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.     

The structural and optical properties of ZnO bulk and nanocrystals under high pressure

The elastic properties of high-quality ZnO crystals and nanopowder of grain size of about 65 nm are studied for both wurtzite (low pressure) and rock-salt high pressure phases. The measured values of bulk moduli for wurtzite and rock-salt phases of bulk ZnO crystals are equal to 156±13 and 187±20 GPa, respectively, and considerably larger for ZnO nanocrystals. The phase transition begins at a pressure of about 9 GPa and it is completed at a pressure of about 13.8 GPa for bulk crystals, whereas the values of pressure at which the phase transition occurs are lower for nanocrystals. A carefull Rietveld analysis of the obtained data does not exhibit the presence of any intermediate phases between low pressure wurtzite and high pressure rock-salt phases of ZnO. The phase transition is accompanied by a strong decrease in the near-band-gap photoluminescence intensity. In addition, the pressure coefficient of the near-band-gap luminescence in ZnO nanocrystals exhibits strong deviation from the linearity observed in bulk crystals. An analysis of the results shows that defects present in the nanopowdered sample are responsible for the observed effects.     

哑铃状氧化锌纳米晶的合成及光谱研究

在较低温度范围内,采用醋酸锌和氨水,均相沉淀法合成了哑铃状ZnO纳米晶,利用X射线粉末衍射（XRD）、扫描电镜（SEM）、透射电镜（TEM）、紫外-可见（UV-Vis）光谱及荧光光谱对其形貌和光学性质进行了表征,并对其生长机理进行了研究。     

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.     

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。     

热氧化法制备ZnO纳米晶体、纳米线

以高纯Zn块为源材料,通过热氧化法制备了纳米ZnO薄膜。在950℃的温度和一定的压力条件下,通过改变生长时间,分别制备了ZnO纳米晶体、纳米纤维和纳米线。应用扫描电镜观察发现,在恒温生长条件下,纳米ZnO具有定向生长的趋势。随生长时间的延长,纳米晶体定向生长为纳米纤维,最后生长为超长的纳米线。     

纳米ZnO在高压下的性质与结构研究

 在金刚石压砧上测量了20 nm的ZnO和体相粉末ZnO的电阻-压力关系。研究结果表明，20 nm的ZnO在7.9 GPa 压力时出现了相变，而体相粉末ZnO在5 GPa 时有相变发生。虽然粒径小的相变压力大于粒径大的，但与以前关于体相粉末ZnO所报道的文献结果有所不同。文中对此作了解释，并对纳米ZnO在压力下的畴破裂进行了研究。     

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。     

ZnO filled opal arrays: Photo and cathodoluminescence studies

The photo and cathodoluminescence of zinc oxide (ZnO) filled opal arrays, as well as ZnO nanocrystals prepared by a chemical deposition method were investigated. The photoluminescence (PL) from the arrays was studied using angular resolution. The PL spectra of the filled opal exhibited a dip corresponding to the array’s photonic band gap. ZnO nanocrystals embedded in the opal matrix demonstrated quenched excitonic emission while the opal matrix showed enhanced emission. This effect is explained by an energy transfer from ZnO nanocrystals to the opal matrix.     

High-temperature-mixing hydrothermal synthesis of ZnO nanocrystals with wide growth window

High-quality and controllable growth of nanocrystals (NCs) have been attracting great attention. Here, a high-temperature-mixing hydrothermal (HTMH) method was designed to synthesize ZnO NCs with high crystallinity and narrow size distribution in a wide growth window. Compared with conventional hydrothermal (CH) growth, zinc source and alkali precursors were intentionally separated in temperature-rising stage and permitted to mix at the starting of heat preservation stage of HTMH growth. Highly crystalline ZnO NCs with uniform spherical morphology can be formed at alkali concentration and temperature windows as wide as 0.1–0.5 M and 160–200 °C, respectively. However, the products via CH method have much larger changes in not only morphology but also size. These results demonstrated that the high-temperature-mixing reaction greatly facilitates nucleation but depresses grain growth. Considering the simplicity and reproducibility, such HTMH method could have wide potentials for the fabrication of various functional nanocrystals.     

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.     

In situ preparation and fluorescence quenching properties of polythiophene/ZnO nanocrystals hybrids through atom-transfer radical polymerization and hydrolysis

In this paper, a new approach for in situ preparing nanocomposites of conjugated polymers (CPs) and semiconductor nanocrystals was developed. Polythiophene grafted poly(zinc methacrylate) (PTh-g-PZMA) copolymer was synthesized by atom-transfer radical polymerization (ATRP) of zinc methacrylate (ZMA) initiated from the macroinitiator poly(2,5-(3-(bromoisopropyl-carbonyl-oxymethylene) thiophene)) (PTh-Br) with pendant initiator groups. Subsequently, the polythiophene grafted poly(methacrylate)/ZnO (PTh-g-PMA/ZnO) hybrid heterojunction nanocomposites were successfully prepared by in situ hydrolysis of PTh-g-PZMA casting films in alkaline aqueous solution. The structures of PTh-Br, PTh-g-PZMA and PTh-g-PMA/ZnO were confirmed by the proton nuclear magnetic resonance (¹H NMR) spectra, Fourier transform infrared (FTIR) spectra and X-ray photoelectron spectroscopy (XPS). The morphologies of PTh-g-PMA/ZnO films prepared for different hydrolysis time were observed in the cross-sections by scanning electron microscope (SEM). The SEM images revealed that ZnO nanocrystals were uniformly dispersed in polymers without any aggregation and the appearances of ZnO nanocrystals changed from nanoparticles to nanorods with the hydrolysis treatment time increasing. The optical properties of these nanocomposites were studied by ultraviolet-visible (UV-vis) absorption and fluorescence spectroscopy. UV-vis absorption spectroscopy showed that the adsorption band of PTh-g-PMA/ZnO hybrids was broader than that of PTh-Br, implying that the existence of ZnO nanocrystals increased the optical absorption region of hybrids. The photoluminescence (PL) spectra of the hybrids showed that fluorescence quenching occurred in PTh-g-PMA/ZnO blends and a maximum of 85% of the fluorescence intensity quenched in the PTh-g-PMA/ZnO obtained from treatment in NaOH aqueous solution for 2 h, which revealed the existence of photo-induced charge transfer between the polythiophene chains and ZnO. These results indicated that the hybrid heterojunction nanocomposites could be promising candidates for photovoltaic applications.     

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.     

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.     

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.     

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.     

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.     

氧化锌纳米晶体的光谱分析

采用沉淀法并通过控制前驱体的煅烧温度来制备粒径不同的氧化锌(ZnO)纳米晶体,对粒子的透射电镜照片进行分析,结果表明,制备出的纳米粒子分散性好、形貌一致、粒径分布集中。样品的X射线衍射光谱分析表明,随着前驱体煅烧温度增加,晶体粒径增大、结晶度提高;样品的紫外-可见吸收光谱的峰位随粒径减小而发生蓝移,这一实验结果表明ZnO纳米晶体呈现出较明显的量子限域效应;红外吸收光谱测量结果表明,用沉淀法制备的ZnO纳米晶体的表面会吸附一小部分残余的离子,对红外吸收光谱中的ZnO特征振动峰随粒径减小发生宽化和红移的现象进行了理论分析;光致发光光谱测量结果表明,ZnO纳米晶体在紫外区(360 nm)存在一较弱的发光峰,而在可见区(468 nm)存在一较强的发光峰,与理论计算结果进行比较后,认为锌空位点缺陷是导致ZnO纳米晶体可见区发光的主要原因。