p‐type conducting ZnO:P microwires prepared by direct carbothermal growth

Phosphorous‐doped (ZnO:P) and undoped ZnO wires with diameter of several micrometers and length of several hundred micrometers were thermally grown directly on phosphorus pentoxide doped and undoped ZnO:graphite targets, respectively. The cathodoluminescence spectra of single ZnO:P microwires show three typical acceptor‐related emissions which are attributed to (A⁰, X), (e, A⁰), and DAP. Three‐terminal, gate voltage dependent electrical measurements of back‐gate field effect transistors with the microwires as channels indicate reproducibly that undoped ZnO and ZnO:P microwires are n‐type and p‐type conductive, respectively. The p‐type conductivity was found to be stable over more than six months. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Effects of Mn‐doping on surface acoustic wave properties of ZnO films

Surface acoustic wave (SAW) filters based on Mn‐doped ZnO films have been fabricated and effects of Mn‐doping on SAW properties are investigated. It is found that the electromechanical coupling coefficient (K²) of Zn_0.913Mn_0.087O films is 0.73 ± 0.02%, which is 73.8% larger than that of undoped ZnO films (0.42 ± 0.02%). Zn_0.913Mn_0.087O film filters also exhibit a lower absolute value of insertion loss (|IL|) of 16.1 dB and larger bandwidth (BW) of 5.9 MHz compared with that of undoped ZnO film filter. However, Zn_0.952Mn_0.048O film filters exhibit a smaller K² of 0.34 ± 0.02%, larger |IL| of 26.9 dB and smaller BW of 3.5 MHz. It is suggested that the SAW properties can be improved by appropriate Mn‐doping and Mn–ZnO/Si multilayer structure with large d₃₃ is promising for wide‐band and low‐loss SAW applications. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Multiphonon resonant Raman scattering in N‐doped ZnO

Multiphonon resonant Raman scattering in N‐doped ZnO films was studied, and an enhancement of the resonant Raman scattering process as well as longitudinal optical (LO) phonon overtones up to the sixth order were observed at room temperature. The resonant Raman scattering intensity of the 1LO phonon in N‐doped ZnO appears three times as strong as that of undoped ZnO, which mainly arises from the defect‐induced Raman scattering caused by N‐doping. The nature of the 1LO phonon at 578 cm⁻¹ is interpreted as a quasimode with mixed A₁ and E₁ symmetry because of the defects formed in the ZnO lattice. In addition, the previously neglected impurity‐induced two‐LO‐phonon scattering process was clearly observed in N‐doped ZnO. Copyright © 2009 John Wiley & Sons, Ltd.     

ZnO-doped LiNbO<Subscript>3</Subscript> single crystals studied by X-ray and density measurements

Energy Dispersive X-ray Fluorescence Spectroscopy, X-ray diffraction and density measurements were conducted on undoped and ZnO-doped congruent LiNbO₃ single crystals grown by the Czochralski method. Based on the experimental results, an intrinsic defect evolution model was proposed. When ZnO was doped into the congruent LN crystals, the Zn ions replaced first the Li ions and increased the density. Then, the Zn ions simultaneously replaced the Li ions and the antisite Nb_Lis until all Nb_Li ions were replaced, which increased the density further. After that, the Zn ions substituted Nb ions in the Nb-sublattice sites with the reduction of the Li vacancies as self-compensation and thus reduced the density. When the Li vacancies disappeared completely, the Zn ions substituted simultaneously both Li ions in the Li-sublattice sites and Nb ions in the Nb-sublattice sites. The simultaneous substitution might finally lead to the generation of oxygen vacancies and decreased the density further. PACS 61.72.-y; 06.30.Dr; 61.10.-i     

Micro‐Raman investigation of transition‐metal‐doped ZnO nanoparticles

We measured the Raman spectra of ZnO nanoparticles (ZnO‐NPs), as well as transition‐metal‐doped (5% Mn(II), Fe(II) or Co(II)) ZnO nanoparticles, with an average size of 9 nm. A typical Raman peak at 436 cm⁻¹ is observed in the ZnO‐NPs, whereas Zn_1−xMn_xO, Zn_1−xFe_xO and Zn_1−xCo_xO presented characteristic peaks at 661, 665 and 675 cm⁻¹, respectively. These peaks can be related to the formation of Mn₃O₄, Fe₃O₄ and Co₃O₄ species in the doped ZnO‐NPs. Moreover, these samples were analyzed at various laser powers. Here, we observed new vibrational modes (512, 571 and 528 cm⁻¹), which are specific to Mn, Fe and Co dopants, respectively, and ZnO‐NPs did not reveal any additional modes. The new peaks were interpreted either as disorder activated phonon modes or as local vibrations of Mn‐, Fe‐ and Co‐related complexes in ZnO. Copyright © 2007 John Wiley & Sons, Ltd.     

Synthesis of α‐Willemite Nanoparticles by Post‐calcination of Flame‐made Zinc Oxide/Silica Composites

Composite ZnO/SiO₂ nanoparticles were made by flame spray pyrolysis (FSP). Characteristics of the product powder and its crystallization behavior on post‐calcination were evaluated. Polyhedral aggregates of nano‐sized primary particles consisting of ZnO nano‐crystals 1–3 nm in size and amorphous SiO₂ were obtained by FSP. A short residence time in the flame can result in the co‐existence of the ZnO and SiO₂ clusters without substitution or reaction hindering each other's grain growth. There was almost no change in the XRD pattern by calcination at 600 °C for 2 h, suggesting a high thermal stability of the ZnO nano‐crystals in the composite particles. A pure α‐willemite phase was obtained at 900 °C. At this calcination temperature, d_C and d_BET of the powder were 63 and 44 nm, respectively. The nano‐composite structure of the FSP‐made particles can suppress crystalline growth of ZnO during calcination to maintain a high reactivity of ZnO with SiO₂, obtaining pure α‐willemite with high specific surface area at low calcination temperatures.     

Surface‐enhanced Raman scattering of molecules adsorbed on Co‐doped ZnO nanoparticles

Transition‐metal‐doped semiconductor nanoparticles (NPs) have been well studied for their optical and catalytic properties but seldom studied by surface‐enhanced Raman scattering (SERS). In this paper, transition‐metal‐doped semiconductor NPs are investigated for their SERS property. Four groups of Co‐doped (0.5, 1, 3, and 5%) ZnO (Co ZnO) NPs and pure ZnO NPs were synthesized and studied. When 4‐mercaptobenzoic acid was used as probing molecule, significant SERS signals were obtained on all the five samples. Moreover, it is very interesting to observe a relationship between the Co‐doping concentration and enhancement of the SERS signals. SERS intensities first increase with doping concentration (up to 1%), and then decrease with further increase in doping concentration (up to 5%). Charge transfer (CT) is considered to be the main contribution to this phenomenon. Different CT ratios from substrates to molecules seem to induce different intensities of the SERS signals. In our experiments, the crystalline defects of Co ZnO NPs caused by the Co dopant affect the CT ratios. A possible mechanism of CT from the valance band of Co ZnO NPs to the lower unoccupied molecular orbital of the molecules via energy of the surface states is suggested. X‐ray photoelectron spectra, UV vis spectra, and Raman spectra were used to characterize the structure and defects in Co ZnO NPs. Copyright © 2011 John Wiley & Sons, Ltd.     

Microstructure and optical properties of nanocrystalline ZnO and ZnO:(Li or Al) thin films

Zinc oxide thin films (ZnO, ZnO:Li, ZnO:Al) were deposited on glass substrates by a sol-gel technique. Zinc acetate, lithium acetate, and aluminum chloride were used as metal ion sources in the precursor solutions. XRD analysis revealed that Li doped and undoped ZnO films formed single phase zincite structure in contrast to Al:ZnO films which did not fully crystallize at the annealing temperature of 550 °C. Crystallized films had a grain size under 50 nm and showed c-axis grain orientation. All films had a very smooth surface with RMS surface roughness values between 0.23 and 0.35 nm. Surface roughness and optical band tail values increased by Al doping. Compared to undoped ZnO films, Li doping slightly increased the optical band gap of the films.     

Specific features of growth and structure of LiNbO<Subscript>3</Subscript> : Zn crystals near the ZnO concentration threshold of 6.76 mol %

The crystallization conditions and Raman spectra of LiNbO₃ : Zn crystals (0.02–8.91 mol % ZnO in the melt) have been investigated. It has been established that the most favorable conditions for growing optically and compositionally homogeneous heavily doped LiNbO₃ : Zn crystals, which are characterized by a low photorefractive effect, are implemented in the ZnO concentration range of ~4.0–6.76 mol % in the melt. Since the distribution coefficient K _eff decreases significantly with an increase in the ZnO concentration in the melt, one can obtain LiNbO₃ : Zn crystals with significantly different defect structures but identical zinc concentrations. A change in the zinc concentration in crystals has been shown to induce a stepwise change in the sequence order of the main (Li and Nb) and doping (Zn) cations and vacancies and stepwise anisotropic expansion of the oxygen octahedra along the polar axis. The number of kinks in the concentration behavior of the spectral-line widths (five kinks for the lines with frequencies of 630 (A ₁(TO)) and 876 cm^–1 (A ₁(LO))) significantly exceeds the number of thresholds (two) known from the literature.     

Formation and Raman scattering of seed‐like ZnO nanostructure

This work demonstrates seed‐like ZnO nanostructure aggregated with nano‐entities using the colloid chemical method. The formation mechanism and optical properties of the ZnO nanostructure are studied. The X‐ray diffraction spectrum indicates that the ZnO nanostructures are polycrystalline pure wurtzite phase. Multiphonon processes in the nanostructure are identified from the Raman scattering spectra in the spectral range of 300–2000 cm⁻¹. A strong violet photoluminescence band emission was visible in the room temperature photoluminescence spectra. This work determines the quality of such crystals and extends the optical applications of ZnO nanostructures. Copyright © 2009 John Wiley & Sons, Ltd.     

Study of ZnO and Ni-doped ZnO synthesized by atom beam sputtering technique

Zinc oxide (ZnO) and Ni-doped zinc oxide (ZnO:Ni) films are prepared by atom beam sputtering with an intent of growing transparent conducting oxide (TCO) material and understanding its physical properties. The crystalline phases of the films are identified by the grazing angle X-ray diffraction (GAXRD) technique. Thicknesses of the films are measured by ellipsometry. Chemical states of the elements present in the films are investigated by X-ray photoelectron spectroscopy (XPS), which indicates the presence of Ni in the ZnO environment in a divalent state. Average transmission across the ZnO:Ni film was determined to be ∼83% in the visible region, which is less than that (∼90%) of undoped ZnO films. The resistivity measured by van der Pauw technique of the ZnO:Ni film (∼9×10^-3 Ω cm) is two orders of magnitude smaller as compared to its undoped counterpart (1 Ω cm). For ZnO:Ni film an average carrier concentration of ∼1.4×10¹⁹ cm^-3 was observed by Hall measurements. Two important mechanisms reported in the literature viz. influence of d–d transition bands and electron scattering from crystallites/grains are discussed as the possible causes for the increase in conductivity on Ni doping in ZnO. PACS 73.50.Bk; 78.66.Li; 79.60.Dp; 61.05.cp     

Electrical characterization of ZnO,including analysis of surface conductivity

Most current device applications of ZnO are hampered by the lack of control over the electrical conductivity. As-grown ZnO usually exhibits n-type conductivity, and the cause of this residual doping is heavily debated. We have performed temperature-dependent Hall measurements and material characterization by secondary ion mass spectroscopy on nominally undoped bulk ZnO crystals as well as on material doped with potential candidates for p-conductivity in order to explore the cause of the background doping and to study the impact of possible candidates for p-doping of ZnO. Also, this paper gives an overview about surface conductivity of high-resistivity ZnO bulk material and discusses how this property might impact the difficult search for p-type ZnO. We will demonstrate the effect of a surface conducting channel on homoepitaxial MgZnO layers grown by liquid-phase epitaxy. The detectability of such a surface layer on an epi sample indicates the high structural quality and low background doping of the layer. PACS 61.72.Vv; 68.49.Sf; 73.25.+i; 74.62.Dh; 81.15.Lm     

Micropatterned ZnO rod arrays prepared by Au‐catalyzed electroless deposition

Micropatterned ZnO was synthesized by an electroless deposition process using Au stripes as catalytic surfaces. The Au‐patterned electrodes were prepared on SiO₂/Si wafers using photolithography. The site‐selective deposition of patterned ZnO hexagonal rod arrays is confirmed by scanning electron microscopy. The ZnO micropatterned surface revealed a conversion of wettability from hydrophilic to superhydrophobic depending on the deposition reaction param‐ eters. The electrical measurements carried out at room temperature before and after exposure to ammonia vapors of the patterned ZnO arrays show a resistance variation with exposure time. Highly reproducible, easy scalable and low‐cost, photolithography and electroless deposition techniques could provide a facile approach to fabricate functionalized micropatterns, for a wide range of applications. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Geometry‐based analysis of azulene and azulene‐like systems with H‐ or Li‐bonding

B3LYP/6–311+G** optimization was carried out for azulene and its analogs, in which CH? CH? CH fragment was replaced with O···X···O (X = H or Li). π‐electron delocalization in four possible derivatives with H‐bonding and three possible derivatives with Li‐bonding was described by the use of HOMA index. All derivatives with Li‐bonding exhibit high π‐electron delocalization similar to that found for azulene. Among four H‐bonded systems, two exhibit lower π‐electron delocalization (HOMA < 0.39) and higher total electron energy than the other two derivatives. Copyright © 2007 John Wiley & Sons, Ltd.     

Optomechanically Assisted Assembly of Surface‐Functionalized Zeolite‐L‐Based Hybrid Soft Matter

Nanoporous particles are particularly interesting for the assembly of functional nano‐ and microsystems because they provide hierarchical supramolecular organization of a large variety of guest molecules. In this work, arbitrary nanoarchitectures consisting of nanoporous zeolite‐L crystals are assembled by combining holographic optical tweezers (HOT) with polymer brush functionalized particles to overcome the limitations of 1D and restricted self‐assembly of zeolite‐L crystals. Readily prepared and functionalized polymer shells allow for controlled, instant, and highly efficient particle–particle and particle–surface adhesion without the need for an external trigger. In contrast to earlier studies, these assemblies remain permanently stable after release out of the HOT system. This novel strategy can be used to fabricate either motile units or locally grounded 1D, 2D, and 3D microconstructions, which can be further utilized as microtools in microfluidic and nanophotonic applications.     

Growth of epitaxial c ‐plane ZnO film on a ‐plane sapphire by radio frequency reactive magnetron sputtering

In this Letter, we report the successful growth of high quality c ‐plane oriented epitaxial ZnO films on a ‐plane sapphire substrates by using radio frequency reactive magnetron sputtering. The effect of substrate temperature on the structural and optical properties has been investigated. X‐ray diffraction (XRD) studies reveal that the ZnO film is grown epitaxially on a ‐plane sapphire substrate, and the film quality is improv‐ ed as the substrate temperature is increased. Photoluminescence (PL) results manifest that screw dislocations can exert great influence on the optical properties. It is found that the line width of the near‐band‐edge emission of PL decreases linearly with increase in screw density. In addition, a simple and effective method is proposed to assess the defect density in epitaxial ZnO films by performing PL measurement. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Photonic engineering of surface‐emitting terahertz quantum cascade lasers

Various resonators for surface emission are reviewed that have recently been developed to improve radiative‐ and collection‐efficiencies of terahertz quantum cascade lasers (THz QCL). While the fabrication of waveguides for long wavelengths is challenging in terms of molecular beam epitaxy, long wavelengths also provide a wonderful testbed for new photonics structure concepts, since these can be easily produced by conventional optical lithography because of the typically large size of the required features. This led to novel geometries, like one‐ and two‐dimensional non‐periodic photonic crystals, or circular gratings for microdisk‐ and ring‐lasers, which are all implemented by simply patterning the top metal cladding of a metal‐metal waveguide. The modeling of such resonators with the finite element method is also described, highlighting the importance of this tool for the engineering of surface losses and far‐field patterns.     

Enhanced photocatalytic activity of Cu-doped ZnO nanorods

Cu-doped ZnO nanorods with different Cu concentrations were synthesized through the vapor transport method. The synthesized nanorods were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM) and UV–vis spectroscopy. The XRD results revealed that Cu was successfully doped into ZnO lattice. The FE-SEM images showed that the undoped ZnO has needle like morphology whereas Cu-doped ZnO samples have rod like morphology with an average diameter and length of 60–90 nm and 1.5–3 μm respectively. The red shift in band edge absorption peak in UV-vis absorbance spectrum with increasing Cu content also confirm the doping of Cu in ZnO nanorods. The photocatalytic activity of pure and Cu-doped ZnO samples was studied by the photodegradation of resazurin (Rz) dye. Both pure ZnO and the Cu-doped ZnO nanorods effectively removed the Rz in a short time. This photodegradation of Rz followed the pseudo-first-order reaction kinetics. ZnO nanorods with increasing Cu doping exhibit enhanced photocatalytic activity. The pseudo-first-order reaction rate constant for 15 % Cu-doped ZnO is equal to 10.17×10^?2min^?1 about double of that with pure ZnO. The increased photocatalytic activity of Cu-doped ZnO is attributed to intrinsic oxygen vacancies due to high surface to volume ratio in nanorods and extrinsic defect due to Cu doping.     

Structural homogeneity of photorefractive LiNbO<Subscript>3</Subscript> crystals doped with 0.03–4.5 mol % of ZnO

Using the electronic spectroscopy method, the laser-conoscopy method, and the Raman light-scattering method, we have studied the structural homogeneity of LiNbO₃ crystals doped with 0.03–4.5 mol % of ZnO. We have found that, as the laser radiation power is increased to 90 mW, the conoscopic patterns of crystals show additional distortions, which are attributed to the manifestation of the photorefractive effect. For the LiNbO₃ crystal doped with 4.5 mol % of ZnO, in which the photorefractive effect is low, we have revealed a considerable shift (compared to the remaining crystals) of the optical absorption edge toward the shortwavelength range, which indicates a high structural homogeneity of this crystal. We have shown that, in the LiNbO₃ crystal doped by 0.05 mol % ZnO, due to the displacement of Nb_Li and Li□ structural defects by Zn²⁺ cations, the crystal structure is ordered and, simultaneously, the number of defects with localized electrons decreases.     

Harnessing Calcium‐Oxalate‐ (CaOx‐) Nanocrystal‐Induced Prodeath Autophagy for Attenuating Human Renal Proximal Tubular Epithelial Cell Injury

Calcium oxalate (CaOx) stone is the most common type of kidney stone, with a formation process comprising supersaturation, nucleation, growth, aggregation to crystals, and adhesion on renal tubular epithelial cells. CaOx stones generally lead to renal injury; however, the underlying mechanism remains poorly understood. Accumulating evidence suggests that nanosized materials could induce much greater toxicity than bulk materials with the same components. As aggregation to nanocrystals is necessary to form CaOx stones and nanocrystals have been widely reported to elicit either prodeath or prosurvival autophagy, the aim is to address the precise role of autophagy in CaOx‐ nanocrystal‐induced cytotoxicity. Clinical CaOx stones from patients are collected followed by ball milling. As a result, CaOx nanocrystals significantly reduce renal cell viability in a dose‐ and time‐dependent manner. Further study shows that CaOx nanocrystals possess an autophagy‐inducing capacity and autophagic flux is complete. Autophagy abrogation by specific chemical inhibitor wortmannin or chloroquine obviously attenuates cytotoxicity, strongly suggesting that prodeath autophagy contributes to CaOx nanocrystals‐elicited cytotoxicity. Finally, it is revealed that autophagy is an essential signaling pathway participating in apoptosis regulation. Collectively, the findings demonstrate the role of autophagy in CaOx‐nanocrystal‐elicited cytotoxicity, and harnessing autophagy can be helpful to design promising strategies for attenuating kidney injury in nephrolithiasis.