The growth of porous ZnO nanowires by thermal oxidation of ZnS nanowires

The growth of porous ZnO nanowires (NWs) via phase transformation of ZnS NWs at 500-850 degrees C in air was studied. The ZnS NWs were first synthesized by thermal evaporation of ZnS powder at 1100 degrees C in Ar. On subsequent annealing at 500 degrees C in air, discrete ZnO epilayers formed on the surface of ZnS NWs. At 600 degrees C, polycrystalline ZnO and the crack along the (0001) interface between the ZnO epilayer and ZnS NW were observed. At 700-750 degrees C ZnS NWs transformed to ZnO NWs, meanwhile nanopores and interfacial cracks were observed in the ZnO NWs. Two factors, the evaporation of SO2 and SO3 and the stress induced by the incompatible structure at the interface of ZnO epilayer and ZnS NW, can be responsible for the formation of porous ZnO NWs from ZnS NW templates on annealing at 700-750 degrees C in air. Rapid growth of ZnO at 850 degrees C could heal the pores and cracks and thus resulted in the well-crystallized ZnO NWs.     

High-energy emission band nature in ZnS-type phosphors activated with silver and chlorine

The cathodoluminescence emission spectra of cubic blue-emitting ZnS:Ag, Cl, hexagonal green-emitting (Zn_0.675, Cd_0.325) S:Ag, Cl as well as hexagonal red-emitting (Zn_0.27, Cd_0.73) S:Ag, Cl phosphors have been measured at 293, 77 and 4.2 K. The measured spectra of the phosphors exhibited a single broad emission band at 293 K, while they had two emission bands at 77 and 4.2 K. The two emission bands shifted to a lower energy with increase of their corresponding half-widths as the temperature at which the spectra were measured was raised. The time-resolved emission spectra measured showed that the low-energy band also shifted in the lower energy direction during the decay of luminescence, confirming its donor-acceptor (DA) transition nature. The high-energy band decayed faster than the low-energy one and no energy shift occurred during its decay; it was attributed to donor-isoelectronic pair (DI) transition. The lifetimes of 0.625 and 4.2 µsec were estimated for high- and low-energy bands, respectively, in the emission spectra of ZnS:Ag, Cl at 4.2 K.     

Correlated micro-photoluminescence and electron microscopy studies of the same individual heterostructured semiconductor nanowires

To correlate optical properties to structural characteristics, we developed a robust strategy for characterizing the same individual heterostructured semiconductor nanowires (NWs) by alternating low temperature micro-photoluminescence (μ-PL), low voltage scanning (transmission) electron microscopy and conventional transmission electron microscopy. The NWs used in this work were wurtzite GaAs core with zinc blende GaAsSb axial insert and AlGaAs radial shell grown by molecular beam epitaxy. The series of experiments demonstrated that high energy (200 kV) electrons are detrimental for the optical properties, whereas medium energy (5-30 kV) electrons do not affect the PL response. Thus, such medium energy electrons can be used to select NWs for correlated optical-structural studies prior to μ-PL or in NW device processing. The correlation between the three main μ-PL bands and crystal phases of different compositions, present in this heterostructure, is demonstrated for selected NWs. The positions where a NW fractures during specimen preparation can considerably affect the PL spectra of the NW. The effects of crystal-phase variations and lattice defects on the optical properties are discussed. The established strategy can be applied to other nanosized electro-optical materials, and other characterization tools can be incorporated into this routine.     

Direct observation of enhanced cathodoluminescence emissions from ZnO nanocones compared with ZnO nanowire arrays

We report, for the first time, direct observation of enhanced cathodoluminescence (CL) emissions from ZnO nanocones (NCs) compared with ZnO nanowires (NWs). For direct and unambiguous comparison of CL emissions from NWs and nanocones, periodic arrays of ZnO NW were converted to nanocone arrays by our unique HCl [aq] etching technique, enabling us to compare the CL emissions from original NWs and final nanocones at the same location. CL measurements on NW and nanocone arrays reveal that emission intensity of the nanocone at ～ 387 nm is over two times larger than that of NW arrays. The enhancement of CL emission from nanocones has been confirmed by finite-difference time-domain simulation of enhanced light extraction from ZnO nanocones compared to ZnO NWs. The enhanced CL from nanocones is attributed to its sharp morphology, resulting in more chances of photons to be extracted at the interface between ZnO and air.     

Synthesis and raman scattering from Zn(1-x)Mn(x)S diluted magnetic semiconductor nanowires

The growth of Diluted Magnetic Semiconducting (DMS) Zn(1-x)Mn(x)S (0 < or = x < 0.6) nanowires (NWs) using a three-zone furnace and two solid sources is reported. The approach is generally applicable to many binary and ternary NW systems that grow by the Vapor-Liquid-Solid growth mechanism. Mn concentration was controlled by the temperature of the Mn source. The Zn/Mn ratio was found to determine the crystalline structure, i.e., wurtzite or zinc blende. High-resolution transmission electron microscopy measurements revealed highly crystalline single phase NWs. The vibrational properties of the DMS NWs with different Zn/Mn ratios were studied by correlating their Raman scattering spectra with the composition measured by Energy Dispersive X-Ray Spectroscopy (EDS). We find that the transverse optical (TO) phonon band disappears at the lowest Mn concentrations, while the longitudinal optical (LO) phonon band position was found insensitive to x. Three additional Raman bands were observed between the ZnS q = 0 TO and LO phonons when Mn atoms were present in the NWs. These bands are similar to those reported previously for bulk Zn(1-x)Mn(x)S and their origin is still controversial.     

Low-energy cathodoluminescence microscopy for the characterization of nanostructures

Spatially and spectrally resolved low-energy cathodoluminescence (CL) microscopy was applied to the characterization of nanostructures. CL has the advantage of revealing not only the presence of luminescence centers but also their spatial distribution. The use of electrons as an excitation source allows a direct comparison with other electron-beam techniques. Thus, CL is a powerful method to correlate luminescence with the sample structure and to clarify the origin of the luminescence. However, caution is needed in the quantitative analysis of CL measurements. In this review, the advantages of cathodoluminescence for qualitative analysis and disadvantages for quantitative analysis are presented on the example of nanostructures.     

Low-energy cathodoluminescence microscopy for the characterization of nanostructures

Abstract

Spatially and spectrally resolved low-energy cathodoluminescence (CL) microscopy was applied to the characterization of nanostructures. CL has the advantage of revealing not only the presence of luminescence centers but also their spatial distribution. The use of electrons as an excitation source allows a direct comparison with other electron-beam techniques. Thus, CL is a powerful method to correlate luminescence with the sample structure and to clarify the origin of the luminescence. However, caution is needed in the quantitative analysis of CL measurements. In this review, the advantages of cathodoluminescence for qualitative analysis and disadvantages for quantitative analysis are presented on the example of nanostructures.     

Effect of the doped nitrogen on the optical properties of β-Ga2O3 nanowires

In this study, optical properties of the nitrogen-doped β-Ga₂O₃ nanowires (N-doped β-Ga₂O₃ NWs) were synthesized by exposing β-Ga₂O₃ NWs under high input power nitrogen plasma (2 kW), using a microwave plasma enhanced chemical vapor deposition (MPECVD) system. The nitrogen contents in the NWs were as-prepared about 7.4, 8.9, 9.7, 13.9, 19.3, and 26.6 at.%, respectively. Low temperature (10 K) cathodoluminescence (CL) spectra exhibit significantly different optical properties for the different nitrogen contents. The CL result of the N-doped β-Ga₂O₃ NWs (210 s N₂ plasma treatment) exhibited four distinct emission peaks at 378, 516, 759, and 970 nm. The possible light emission mechanism including the effect of the nitrogen dopant was discussed.     

Single crystal ZnSr:Mn prepared by ion implantation

Single crystal ZnS was implanted with 100 keV Mn⁺ ions. Low-temperature ZnS:Mn emission spectra were obtained using 5 keV electrons for excitation. Phonon structure was observed in thermally annealed material, and Mn diffusion was measured using a depth-selective emission profile.     

Spatial distribution of impurities in ZnO nanotubes characterized by cathodoluminescence

Low-energy cathodoluminescence (CL) imaging and spectroscopy technique was employed to study the impurity distribution in individual ZnO hexagonal nanotubes fabricated by metalorganic chemical vapor deposition on the sapphire (0001) substrate. The CL spectra at 10 K show that acceptor and donor impurities are incorporated in the ZnO nanotubes. CL monochromatic images indicate that the concentration of donor is higher at the bottom part and the distribution of acceptors is more inhomogeneous at the surface of the nanotubes. The non-uniform defects and impurities distributions are explained by unstable growth conditions and contamination from the environment. These results indicate that the low-energy CL is a very powerful method to investigate the inhomogeneity of luminescence properties in the individual nanostructures.     

Luminescence of er doped ZnS quantum dots excited by infrared lasers

ZnS:Er quantum dots were prepared in aqueous medium from readily available precursors. The construction, morphology and luminescence properties of the ZnS:Er quantum dots were evaluated by X-ray diffraction (XRD), transmission electron microscopy (TEM), and photoluminescence spectra. The average particle size was calculated using the Scherrer formula to be 4 nm, which is also observed from high resolution transmission electron microscopy (HRTEM) image. Different laser wavelengths at 976 +/- 2 nm and 1480 nm were utilized as the excitation source. ZnS:Er quantum dots had a fluorescence spectrum in 1550 nm region through the 4I13/2 --> 4I15/2 transition. Furthermore, intensity increased with increasing excitation intensity and dopant concentration. The reason for the photoluminescence spectra broadening is discussed. It is because the energy levels of Er3+ are split by a coulombic interaction between electrons, including spin correction and spin-orbit coupling, and eventually by the Stark effect due to ZnS QDs crystal field and local coordination.     

Blueshift of electroluminescence from single n-InP nanowire/p-Si heterojunctions due to the Burstein-Moss effect

Single-crystalline n-type InP nanowires (NWs) with different electron concentrations were synthesized on Si substrates via the vapor phase transport method. The electrical properties of the InP nanowires were investigated by fabricating and measuring single NW field-effect transistors (FETs). Single InP NW/p(+)-Si heterojunctions were fabricated, and electroluminescence (EL) spectra from them were studied. It was found that both the photoluminescence (PL) spectra of the InP NWs and the EL spectra of the heterojunctions blueshift from 920 to 775?nm when the electron concentrations of the InP NWs increase from 2 × 10(17) to 1.4 × 10(19)?cm(-3). The blueshifts can be attributed to the Burstein-Moss effect rather than the quantum confinement effect in the InP NWs. The large blueshifts observed in this study indicate a potential application of InP NWs in nano-multicolour displays.     

Organic light-emitting devices fabricated utilizing core/shell CdSe/ZnS quantum dots embedded in a polyvinylcarbazole

Electrical and the optical properties of organic light-emitting devices (OLEDs) fabricated utilizing core/shell CdSe/ZnS quantum dots (QDs) embedded in a polyvinylcarbazole (PVK) layer were investigated. An abrupt increase of the current density above an applied voltage of 12 V for OLEDs consisting of Al/LiF/4,7-diphenyl-1,10-phenanthroline/bis-(2-methyl-8-quinolinolate)-4-(phenylphenolato) aluminium/[CdSe/ZnS QDs embedded in PVK]/poly(3,4-ethylenedioxythiophene) and poly(styrenesulfonate)/ITO/glass substrate was attributed to the existence of the QDs. Photoluminescence spectra showed that the peaks at 390 and 636 nm corresponding to the PVK layer and the CdSe/ZnS QDs were observed. While the electroluminescence (EL) peak of the OLEDs at low voltage range was related to the PVK layer, the EL peak of the OLEDs above 12 V was dominantly attributed to the CdSe/ZnS QDs. The Commission Internationale de l’Eclairage (CIE) chromaticity coordinates of the OLEDs at high voltages were (0.581, 0.380) indicative of a red color. When the holes existing in the PVK layer above 12 V were tunneled into the CdSe/ZnS QDs, the holes occupied by the CdSe/ZnS QDs combined with the electrons in the PVK layer to emit a red color related to the CdSe/ZnS QDs.     

Platinum-nanoparticle-modified TiO2 nanowires with enhanced photocatalytic property

Highly crystalline Pt nanoparticles with an average diameter of 5 nm were homogeneously modified on the surfaces of TiO(2) nanowires (Pt-TiO(2) NWs) by a simple hydrothermal and chemical reduction route. Photodegradation of methylene blue (MB) in the presence of Pt-TiO(2) NWs indicates that the photocatalytic activity of TiO(2) NWs can be greatly enhanced by Pt nanoparticle modification. The physical chemistry process and photocatalytic mechanism for Pt-TiO(2) NWs hybrids degrading MB were investigated and analyzed. The Pt attached on TiO(2) nanowires induces formation of a Schottky barrier between TiO(2) and Pt naonoparticles, leading to a fast transport of photogenerated electrons to Pt particles. Furthermore, Pt incoporation on TiO(2) surface can accelerate the transfer of electrons to dissolved oxygen molecules. Besides enhancing the electron-hole separation and charge transfer to dissolved oxygen, Pt may also serve as an effective catalyst in the oxidation of MB. However, a high Pt loading value does not mean a high photocatalytic activity. Higher content loaded Pt nanoparticles can absorb more incident photons which do not contribute to the photocatalytic efficiency. The highest photocatalytic activity for the Pt-TiO(2) nanohybrids on MB can be obtained at 1 at % Pt loading.     

Surface-enhanced Raman scattering of carbon nanotubes by decoration of ZnS nanoparticles

ZnS nanoparticles anchored on the single-walled carbon nanotubes (SWNTs) were fabricated by a chemical vapor deposition (CVD) method. The CVD method shows no selectivity for growth of ZnS nanoparticles on types and defects of the SWNTs, and thus ensures the uniform decoration of all SWNTs on the substrate. ZnS nanoparticles with a diameter of 10 nm were decorated on the SWNTs surface with an interparticle distance of about 20 nm. This method provides the possibility to realize the optimal configurations of ZnS nanoparticles on SWNTs for obtaining surface-enhanced Raman spectroscopy (SERS) of SWNTs. Investigations of mechanism reveal that charge transfer (a small amount of excitation electrons) from ZnS nanoparticles to SWNTs weakly affects Raman intensity, and the coupled surface plasmon resonance (SPR) formed from plenty of excitation electrons on the surface of ZnS nanoparticles contributes to the strong surface enhancement. It would be an alternative approach for SERS after metal (normally gold or silver) nanoparticles' decoration on the SWNTs surface.     

Estimation of a radiation weighting factor for 99mTc

Decaying (99m)Tc does not only emit a gamma ray (140.5 keV), but also low-energy Auger and conversion electrons. These electrons cause a serious problem in the determination of a radiation weighting factor for (99m)Tc due to their extremely short range in tissue. Therefore, for comparison ultrasoft X rays are used here, which deposit their energy mainly via the photoeffect thus also initiating low-energy photoelectrons. Monte Carlo computer codes provided electron emission spectra of (99m)Tc and subsequent track structure calculations simulated the induction of DNA damage of different degrees of complexity. For the modelling of ultrasoft X rays carbon K photons with an energy of 270 eV were selected, for which experimental results are available from the literature. On average, four electrons were found to be emitted per (99m)Tc decay. Simulation of DNA damage revealed a nearly identical spectrum of primary strand breaks for (99m)Tc and C-K radiation. On this basis, a total radiation weighting factor of 1.2 was evaluated for (99m)Tc.     

Acoustically driven photon antibunching in nanowires

The oscillating piezoelectric field of a surface acoustic wave (SAW) is employed to transport photoexcited carriers, as well as to spatially control exciton recombination in GaAs-based nanowires (NWs) on a subns time scale. The experiments are carried out in core-shell NWs transferred to a SAW delay line on a LiNbO(3) crystal. Carriers generated in the NW by a focused laser spot are acoustically transferred to a second location, leading to the remote emission of subns light pulses synchronized with the SAW phase. The dynamics of the carrier transport, investigated using spatially and time-resolved photoluminescence, is well-reproduced by computer simulations. The high-frequency contactless manipulation of carriers by SAWs opens new perspectives for applications of NWs in opto-electronic devices operating at gigahertz frequencies. The potential of this approach is demonstrated by the realization of a high-frequency source of antibunched photons based on the acoustic transport of electrons and holes in (In,Ga)As NWs.     

A thermoluminescence study on the state of Cl in ZnS:Ag by electron beam

The degradation behavior of ZnS:Ag, Cl as a phosphor for CL by EB irradiation at 7 kV was examined by TL measurement. After EB irradiation, TL intensity decreased and the TL peak shifted to the lower temperature side. By comparing TL thermograms of mechanically damaged ZnS:Ag, Cl, ZnS:Cl with varying Cl concentration as well as ZnS:Ag, Al after EB irradiation, we conclude that the decrease in the effective concentration of Cl⁻, serving as active luminescence center, is responsible for the CL degradation of ZnS:Ag, Cl by EB irradiation.     

p-Type ZnO nanowire arrays

Well-aligned ZnO nanowire (NW) arrays with durable and reproducible p-type conductivity were synthesized on alpha-sapphire substrates by using N2O as a dopant source via vapor-liquid-solid growth. The nitrogen-doped ZnO NWs are single-crystalline and grown predominantly along the [110] direction, in contrast to the [001] direction of undoped ZnO NWs. Electrical transport measurements reveal that the nondoped ZnO NWs exhibit n-type conductivity, whereas the nitrogen-doped ZnO NWs show compensated highly resistive n-type and finally p-type conductivity upon increasing N2O ratio in the reaction atmosphere. The electrical properties of p-type ZnO NWs are stable and reproducible with a hole concentration of (1-2) x 10(18) cm(-3) and a field-effect mobility of 10-17 cm2 V(-2) s(-1). Surface adsorptions have a significant effect on the transport properties of NWs. Temperature-dependent PL spectra of N-doped ZnO NWs show acceptor-bound-exciton emission, which corroborates the p-type conductivity. The realization of p-type ZnO NWs with durable and controlled transport properties is important for fabrication of nanoscale electronic and optoelectronic devices.     

Effects of strain on the carrier mobility in silicon nanowires

We investigate electron and hole mobilities in strained silicon nanowires (Si NWs) within an atomistic tight-binding framework. We show that the carrier mobilities in Si NWs are very responsive to strain and can be enhanced or reduced by a factor >2 (up to 5×) for moderate strains in the ± 2% range. The effects of strain on the transport properties are, however, very dependent on the orientation of the nanowires. Stretched 100 Si NWs are found to be the best compromise for the transport of both electrons and holes in ≈10 nm diameter Si NWs. Our results demonstrate that strain engineering can be used as a very efficient booster for NW technologies and that due care must be given to process-induced strains in NW devices to achieve reproducible performances.