Effect of seed layer on the growth of well-aligned ZnO nanowires

We demonstrate that vertical well-aligned crystalline ZnO nanowire arrays were grown on ZnO/glass substrates by a low-temperature solution method. Different thicknesses of ZnO seed layers on glass substrates were prepared by radio-frequency sputtering. In this work it was found that the morphology of ZnO nanowires strongly depends on the thickness of ZnO seed layers. The average diameter of nanowires is increased from 50 to 130 nm and the nanowire density is decreased from 110 to 60 μm⁻² while the seed layer thickness is varied from 20 to 1000 nm. The improved control of the morphology of ZnO nanowire arrays may lead to an enhanced carrier collection of hybrid polymer photovoltaic devices based on ZnO.     

Hydrothermal fabrication of well-ordered ZnO nanowire arrays on Zn foil: room temperature ultraviolet nanolasers

Well-ordered nanowires of the hexagonal wurtzite ZnO having an average diameter of 80 nm, a typical length of 12 μm, and a mean packing density of 7.5 nanowires μm⁻² have been directly grown on Zn foil in a preferred [0001] direction by a hydrothermal process and employed for room temperature ultraviolet nanolasers. The lasing action of arrayed ZnO nanowires has been observed from 370 to 400 nm with threshold irradiance of 25 kW cm⁻². Photoluminescence decays biexponentially: the fast component is attributed to free-exciton decay, and the slow one is to bound-exciton decay. The amplitude of the fast component increases whereas its lifetime decreases with the increment of threshold irradiance, suggesting that ZnO nanowire arrays undergo a change in the lasing mechanism from exciton–exciton scattering to electron–hole plasma recombination.     

Structural and optical properties of nearly stress-free m-plane ZnO film on (1 0 0) γ-LiAlO2 with a GaN buffer layer by metal-organic chemical vapor deposition

m-plane ZnO film was epitaxially deposited on (1 0 0) γ-LiAlO₂ by metal-organic chemical vapor deposition at 600 °C with a GaN buffer layer. The epitaxial relationships between ZnO and GaN, GaN and (1 0 0) γ-LiAlO₂ were determined by X-ray diffraction Φ-scans. There exhibits very small decrease for the E₂ mode shift (0.3 cm⁻¹) of ZnO in the Raman spectrum, which indicates the epitaxial ZnO film was under a slight tensile stress (5.77 × 10⁷ Pa). Unlike the highly strained a-plane ZnO, temperature dependent photoluminescence spectra show that the free A exiton emission was observed with the temperature ≤138 K.     

An electrical characterization of a hetero-junction nanowire (NW) PN diode (n-GaN NW/p-Si) formed by dielectrophoresis alignment

This is a report on the electrical characterization of gallium nitride (GaN) nanowire (NW) p–n junction diodes. These diodes were formed by assembling n-GaN NWs on p-Si (1 0 0) substrates using alternating current (AC) dielectrophoresis (DEP). The AC DEP was optimized with a bias voltage of 15 V_p−p at a frequency of 1 kHz. The hetero-junction single GaN nanowire p-n diode (n-GaN NW/p-Si) showed well-defined current rectifying behavior with a forward voltage drop of 1.2–2.0 V at a current density of 10–60 A/cm². The GaN nanowire p–n diodes had a high parasite resistance in the range of >470 kΩ. We observed that these high resistances were mostly the result of the metal contacts to the n-GaN NWs. We also found that these parasite resistances were reduced by the formation of an additional capping layer on the top of the n-GaN NW as well as high temperature annealing.     

ZnO nanowire lines and bundles: Template-deformation-guided alignment for patterned field-electron emitters

One-dimensional ZnO materials have been promising for field-emission (FE) application, but how to facially control the alignment of ZnO emitters is still a great challenge especially for patterned display application. Here, we report the fabrication of novel ZnO nanowire (NW) line and bundle arrays for patterned field-electron emitters. The effects of PS template size and heating time on the resulted ZnO nanoarrays were systematically studied. The deformation degree of PS templates was controlled and hence utilized to adjust the alignment of electrochemically deposited ZnO arrays. It was found that the length of NW lines and the density of NW bundles can effectively tuned by the PS template heating time. The optimal FE performance with turn-on electric field as low as of 4.4 V μm⁻¹ and the field-enhancement factor as high as of 1450 were achieved through decreasing the screening effect among the patterned field-electron emitters.     

The luminescence of ZnO ceramics

The luminescence properties of ZnO ceramics with grains 100–5000 nm sintered by different techniques from nanopowders were studied. The luminescence decay times were compared with that obtained for ZnO single crystal. The temperature dependence of non-exponential decay of defect luminescence (2.0–2.6 eV) was measured in wide time, intensity and temperature range. The luminescence decay kinetic at T ≤ 20 K shows the decay close to I(t) ～ t^?1 dependence. At temperature region 50–250 K the decay kinetics is more complicate since the TSL was observed in this temperature region. It is shown that the luminescence properties of NP and ceramics strongly depend on defect distribution on grains surface and the volume/surface ratio determine the luminescence decay in ZnO nanostructures and ceramics.     

Bandgap engineering of GaxZn1–xO nanowire arrays for wavelength‐tunable light‐emitting diodes

Wavelength‐tunable light‐emitting diodes (LEDs) of Ga_xZn_1–xO nanowire arrays are demonstrated by a simple modified chemical vapor deposition heteroepitaxial growth on p‐GaN substrate. As a gallium atom has similar electronegativity and ion radius to a zinc atom, high‐level Ga‐doped Ga_xZn_1–xO nanowire arrays have been fabricated. As the x value gradually increases from 0 to 0.66, the near‐band‐edge emission peak of Ga_xZn_1–xO nanowires shows a significant shift from 378 nm (3.28 eV) to 418 nm (2.96 eV) in room‐temperature photoluminescence (PL) measurement. Importantly, the electroluminescence (EL) emission of Ga_xZn_1–xO nanowire arrays LED continuously shifts with a wider range (∼100 nm), from the ultraviolet (382 nm) to the visible (480 nm) spectral region. The presented work demonstrates the possibility of bandgap engineering of low‐dimensional ZnO nanowires by gallium doping and the potential application for wavelength‐tunable LEDs.     

Photophysical study on daunorubicin by fluorescence spectroscopy

Steady-state fluorescence and time-resolved fluorescence intensity decays of daunorubicin have been studied in polar solvents and in aqueous solution by a time-correlated single-photon counting technique. Daunorubicin, quinizarin, and 2,3-dimethylquinizarin show bi-exponential decay. The decay of daunorubicin becomes tri-exponential in the presence of adenosine 5′ monophosphate. The quenching of the fluorescence of daunorubicin by adenosine 5′ monophosphate exhibits downward deviation from the Stern-Volmer linearity, suggesting the existence of fluorophore in two conformers in the ground state differing only in the extent of hydrogen bonding.     

Aligned growth of ZnO nanowires and lasing in single ZnO nanowire optical cavities

Ordered ZnO nanowire arrays have been fabricated in N₂ background gas by catalyst-free nanoparticle-assisted pulsed-laser deposition. A single ZnO nanowire was collected in an electrode gap by dielectrophoresis. Under the optical pumping above an exciting laser (λ= 355 nm) threshold of ∼ 334 kW/cm², ultraviolet lasing action in a single ZnO nanowire was observed at room temperature, indicating that the as-synthesized nanowires in pure N₂ background gas are of high quality. The crystalline facets of both ends of the nanowire acted to form an optical cavity. Therefore, the mode spacings corresponding to cavity lengths of the respective nanowires were observed in photoluminescence spectra. PACS 78.66.Hf; 81.07.Bc; 78.67.-n; 81.16.Mk     

Multi-photon-pumped stimulated emission from ZnO nanowires: A time-resolved study

In this work, we study temporal evolution of multi-photon-pumped stimulated emission from ZnO nanowires. In addition to second harmonic generation, ultraviolet stimulated emission is observed in ZnO nanowires under femtosecond pulse excitation at 800 nm. Sharp emission peaks appear when excitation flux reaches a threshold of 80 mJ/cm², which can be interpreted as lasing action in self-formed nanowire microcavities. Temporal evolution of the emission captured by Kerr shutter technique shows strong excitation-power dependence. The dynamic trace of stimulated emission exhibits a fast decay with a lifetime about 4.5 ps at intermediate excitation (∼100 mJ/cm²) and a lifetime about 2 ps at high excitation (>160 mJ/cm²). The difference in the lifetime can be attributed to different gain mechanisms related to excitonic interaction and electron-hole plasma, respectively.     

Magnetic domain structure in small diameter magnetic nanowire arrays

Fe_0.3Co_0.7 alloy nanowire arrays were prepared by ac electrodepositing Fe²⁺ and Co²⁺ into a porous anodic aluminum oxide (PAO) template with diameter about 50 nm. The surface of the samples were polished by 100 nm diamond particle then chemical polishing to give a very smooth surface (below ±10 nm/μm²). The morphology properties were characterized by SEM and AFM. The bulk magnetic properties and domain structure of nanowire arrays were investigated by VSM and MFM respectively. We found that such alloy arrays showed strong perpendicular magnetic anisotropy with easy axis parallel to nanowire arrays. Each nanowire was in single domain structure with several opposite single domains surrounding it. Additionally, we investigated the domain structure with a variable external magnetic field applied parallel to the nanowire arrays. The MFM results showed a good agreement with our magnetic hysteresis loop.     

The synthesis of highly oriented GaN nanowire arrays

Highly oriented GaN nanowire arrays have been achieved by the catalytic reaction of gallium with ammonium. The resulting materials were characterized by X-ray diffraction (XRD), field-emission scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), transmission electron microscopy (TEM) and selected-area electron diffraction (SAED). SEM images show that the resulting materials are nanowire arrays with a uniform length of about 10 μm. XRD, EDS, TEM and SAED indicate that the nanowire arrays are single-crystal hexagonal GaN with a wurtzite structure. They have diameters of 10 to 20 nm. Received: 2 October 2002 / Accepted: 7 October 2002 / Published online: 17 December 2002 RID="*" ID="*"Corresponding author. E-mail: wwwangjc@sina.com     

Robust Type-II Band Alignment and Stacking-Controlling Second Harmonic Generation in GaN/ZnO vdW Heterostructure

Most traditional 2D materials have small bandgaps, resulting in low laser damage thresholds and limiting their applications in the ultraviolet region. Recently experimentally synthesized 2D GaN and ZnO can be such candidates due to their wide bandgaps, high charge mobilities, and optical transparency. Here, the van der Waals heterostructure GaN/ZnO is predicted that can exhibit both wide bandgap and strong second harmonic generation (SHG) response by compelling simulations. The results show the heterostructure always exhibits type-II band alignment under all probable stacking configurations. The out-of-plane SHG coefficients are up to 90 pm V⁻¹ at 400 nm, comparable to those of MoS₂ and MoSe₂ and higher than most 3D crystals. Interestingly, the positions are enhanced with localized, symmetric, and stacking-dependent features in the Brillouin zone. This peculiar momentum space behavior is originated from the relative strength of two distinct mechanisms contributing to the second-order nonlinear optical (NLO) response, that is, a purely interband transition part and a mixed interband-intraband contribution. Thus, this study proposes that GaN/ZnO heterostructure may be an efficient and high laser damage thresholds (LDTs) NLO material and an interesting platform for studying NLO optical properties.     

Growth of vertically aligned one-dimensional ZnO nanowire arrays on sol–gel derived ZnO thin films

Vertically aligned one-dimensional ZnO nanowire arrays have been synthesized by a hydrothermal method on sol–gel derived ZnO films. Sol–gel derived ZnO films and corresponding ZnO nanowire arrays have been characterized by X-ray diffraction and field-emission scanning electron microscopy. The effect of sol–gel derived ZnO film surface on the morphology of ZnO nanowire arrays has been investigated. The authors suggest from our investigation that sol–gel derived ZnO films affect the growth of one-dimensional ZnO nanostructures. Not only crystalline ZnO films but also amorphous ones can act as a scaffold for ZnO nucleus. Tilted ZnO micro-rods are grown on ZnO gel films, whereas vertically aligned ZnO nanowire arrays are grown on nanometer-sized ZnO grains. The average diameter of ZnO nanowire arrays are correlated strongly with the grain size of sol–gel derived ZnO films.     

Highly flexible,transparent, conductive and antibacterial films made of spin-coated silver nanowires and a protective ZnO layer

We prepared highly flexible, transparent, conductive and antibacterial film by spin coating a silver nanowire suspension on a poly (ethylene terephthalate) (PET) substrate. The ZnO layer covered the conductive silver nanowire (AgNW) network to protect the metal nanowires from oxidization and enhance both wire-to-wire adhesion and wire-to-substrate adhesion. It is found that the number of AgNW coatings correlates with both the sheet resistance (R_s) and the transmittance of the AgNW/ZnO composite films. An excellent 92% optical transmittance in the visible range and a surface sheet resistance of only 9 Ω sq⁻¹ has been achieved, respectively. Even after bending 1000 times (5 mm bending radius), we found no significant change in the sheet resistance or optical transmittance. The real-time sheet resistance measured as a function of bending radius also remains stable even at the smallest measured bending radius (1 mm). The AgNW/ZnO composite films also show antibacterial effects which could be useful for the fabrication of wearable electronic devices.     

Growth and characterization of type-II ZnO/ZnTe core-shell nanowire arrays for solar cell applications

Large area, well-aligned type-II ZnO/ZnTe core-shell nanowire arrays have been fabricated on an a-plane sapphire substrate. The ZnO nanowires were grown in a furnace by chemical vapor deposition with gold as catalyst and then were coated with a ZnTe shell on the ZnO nanowires surface by a metal-organic chemical deposition chamber. The morphology and size distribution of the ZnO/ZnTe core-shell nanowire arrays were studied by scanning electron microscopy (SEM) and the crystal structure was examined by x-ray diffraction (XRD). Transmission measurement was used to study the optical properties of the core-shell nanowires. The results indicated that the ZnO/ZnTe core-shell nanowire arrays have good crystalline quality. In addition, it was found that the nanowire arrays have good light absorption characteristics and these properties make it suitable for making photovoltaic devices.     

One step synthesis of vertically aligned ZnO nanowire arrays with tunable length

Length control of ZnO nanowire arrays is a valuable concern for both fundamental research and future device application. In this article, vertically aligned ZnO nanowire arrays were synthesized by a seed layer catalyzed vapor phase transport method in a single experiment cycle. The length of these nanowire arrays exhibits a quasi-continuous evolution. It was found that the type and flow rate of carrier gas have a significant influence on the length modulation of ZnO arrays along the tube. A feasible route to tune the length of ZnO nanowire arrays from several micrometers to nearly 100 μm could be achieved by adjusting proper deposition position and carrier gas.     

Optical and structural properties of Eu-diffused and doped ZnO nanowires

Single crystal ZnO nanowires diffused with europium (Eu) from a solid source at 900 °C for 1 h or doped with Eu during growth have been characterized. The ZnO nanowires were grown by chemical vapor deposition on Si substrates employing Au as a catalyst. The diameter of the resulting nanowires was 200 nm with a length of 1 μm. Photoluminescence spectra excited by a He–Cd laser at room temperature showed the green luminescence at 515 nm in Eu-diffused nanowires. A small red shift of near-band-edge emission of ZnO nanowires was observed in the diffused wires, but sharp emission from Eu³ ions was not present. Transmission electron microscopy shows crystalline Eu₂O₃ formation on the diffused nanowire surface, which forms a coaxial heterostructure system. When Eu was incorporated during the nanowire growth, the sharp ⁵D_O–⁷F₂ transition of the Eu³⁺ ion at around 615 nm was observed.     

Controllable hydrothermal synthesis of ZnO nanowires arrays on Al-doped ZnO seed layer and patterning of ZnO nanowires arrays via surface modification of substrate

ZnO nanowire (NW) arrays are assembled on the Al-doped ZnO (AZO) seed layer by a hydrothermal process. Effects of the temperature and growth time of the hydrothermal process on morphological and photoluminescence properties of the as-assembled ZnO NW arrays are characterized and studied. Results indicate that the length and diameter of the ZnO NWs increase with a lengthening of the growth time at 80 °C and the hydrothermal temperature has a significant effect on the growth rate and the photoluminescence properties of the ZnO NW arrays. The patterned AZO seed layer is fabricated on a silicon substrate by combining a sol-gel process with an electron-beam lithography process, as well as a surface fluorination technique, and then the ZnO NW arrays are selectively grown on those patterned regions of the AZO seed layer by the hydrothermal process. Room-temperature photoluminescence spectra of the patterned ZnO NW arrays shows that only a strong UV emission at about 380 nm is observed, which implies that few crystal defects exist inside the as-grown ZnO NW arrays.     

Electron transport simulation in bulk wurtzite ZnO and its n+–n–n+ diode,compared with GaN

We study the electron transport within bulk wurtzite ZnO and its n⁺–n–n⁺ diode by the Ensemble Monte Carlo method. In bulk ZnO we study the steady state and transient situation with three valley model for the conduction band and compare the results with GaN. Our results show that ZnO's threshold field occurs at a higher applied electric field than GaN. Also, velocity overshoot in ZnO occurs at higher electric fields, too. But the overshoot relaxation time is about 0.3 ps for both of them. As the results show, the role of the third valley is tiny, so for a diode we use two valley conduction bands. For anode voltage ranges from 0.25 to 3 V, we simulate the profiles of the electron density, electric field, potential, average electron velocity, and compare the results with that for GaN. Our results show, as we expect, electron velocity in active layer in the GaN diode is faster than in ZnO.