A facile method for bright, colour-tunable light-emitting diodes based on Ga-doped ZnO nanorods.

Bottom-up fabrication of nanowire-based devices is highly attractive for oxide photonic devices because of high light extraction efficiency; however, unsatisfactory electrical injection into ZnO and poor carrier transport properties of nanowires severely limit their practical applications. Here, we demonstrate that ZnO nanorods doped with Ga donors by in situ dopant incorporation during vapour-solid growth exhibit superior optoelectronic properties that exceed those currently synthesised by chemical vapour deposition, and accordingly can be electrically integrated into Si-based photonic devices. Significantly, the doping method was found to improve the nanorod quality by decreasing the concentration of point defects. Light-emitting diodes (LEDs) fabricated from the Ga-doped ZnO nanorod/p-Si heterojunction display bright and colour-tunable electroluminescence (EL). These nanorod LEDs possess a dramatically enhanced performance and an order of magnitude higher EL compared with equivalent devices fabricated with undoped nanorods. These results point to an effective route for large-scale fabrication of conductive, single-crystalline ZnO nanorods for photonic and optoelectronic applications.

Defect-Free, Few-Atomic-Layer Thin ZnO Nanosheets with Superior Excitonic Properties for Optoelectronic Devices.

Two-dimensional (2D) wide bandgap materials are gaining significant interest for next-generation optoelectronic devices. However, fabricating electronic-grade 2D nanosheets from non-van der Waals (n-vdW) oxide semiconductors poses a great challenge due to their stronger interlayer coupling compared with vdW crystals. This strong coupling typically introduces defects during exfoliation, impairing the optoelectronic properties. Herein, we report the liquid-phase exfoliation of few-atomic-layer thin, defect-free, free-standing ZnO nanosheets. These micron-sized, ultrathin ZnO structures exhibit three different orientations aligned along both the polar c-plane as well as the nonpolar a- and m-planes. The superior crystalline quality of the ZnO nanosheets is validated through comprehensive characterization techniques. This result is supported by density functional theory (DFT) calculations, which reveals that the formation of oxygen vacancies is energetically less favorable in 2D ZnO and that the c-plane loses its polarity upon exfoliation. Unlike bulk ZnO, which is typically dominated by defect-induced emission, the exfoliated nanosheets exhibit a strong, ambient-stable excitonic UV emission. We further demonstrate the utility of solution processing of ZnO nanosheets by their hybrid integration with organic components to produce stable light emitting diodes (LEDs) for display applications.

Electron beam induced chemical dry etching and imaging in gaseous NH3 environments.

We report the use of ammonia (NH(3)) vapor as a new precursor for nanoscale electron beam induced etching (EBIE) of carbon, and an efficient imaging medium for environmental scanning electron microscopy (ESEM). Etching is demonstrated using amorphous carbonaceous nanowires grown by electron beam induced deposition (EBID). It is ascribed to carbon volatilization by hydrogen radicals generated by electron dissociation of NH(3) adsorbates. The volatilization process is also effective at preventing the buildup of residual hydrocarbon impurities that often compromise EBIE, EBID and electron imaging. We also show that ammonia is a more efficient electron imaging medium than H(2)O, which up to now has been the most commonly used ESEM imaging gas.

Three-dimensional electron energy deposition modeling of cathodoluminescence emission near threading dislocations in GaN and electron-beam lithography exposure parameters for a PMMA resist.

The Monte Carlo software CASINO has been expanded with new modules for the simulation of complex beam scanning patterns, for the simulation of cathodoluminescence (CL), and for the calculation of electron energy deposition in subregions of a three-dimensional (3D) volume. Two examples are presented of the application of these new capabilities of CASINO. First, the CL emission near threading dislocations in gallium nitride (GaN) was modeled. The CL emission simulation of threading dislocations in GaN demonstrated that a better signal-to-noise ratio was obtained with lower incident electron energy than with higher energy. Second, the capability to simulate the distribution of the deposited energy in 3D was used to determine exposure parameters for polymethylmethacrylate resist using electron-beam lithography (EBL). The energy deposition dose in the resist was compared for two different multibeam EBL schemes by changing the incident electron energy.

X-ray mapping and scatter diagram analysis of the discoloring products resulting from the interaction of artist's pigments.

The discoloring interaction between the artist's pigments cadmium yellow and the copper-containing malachite, an interaction that is conjectured to cause black spotting in oil paintings of the 19th and early 20th centuries, was examined using X-ray mapping and scatter diagram analysis. The application of these coupled techniques confirmed that copper sulfide phases were produced during discoloration reaction. Scatter diagram analysis indicated that two copper sulfide stoichiometries (CuS and Cu3S2) were present as reaction products where previously only crystalline CuS (covellite) had been identified by X-ray diffraction. The results demonstrate the potential of X-ray mapping coupled with scatter diagram analysis for the identification of both crystalline and X-ray amorphous phases produced by such complex heterogeneous interactions and their applicability to the investigation of interactions of artists' pigments.

Correlative Study of Enhanced Excitonic Emission in ZnO Coated with Al Nanoparticles using Electron and Laser Excitation.

Recently, metal nanoparticle surface coatings have been found to significantly enhance the ultra-violet luminescence intensity from ZnO, providing a viable means to mitigate optical losses and improve LED performance. Although there is general agreement that resonantly excited Localized Surface Plasmons (LSPs) in metal nanoparticles can directly couple to excitons in the semiconductor increasing their spontaneous emission rate, the exact mechanisms involved in this phenomenon are currently not fully understood. In this work, LSP-exciton coupling in bulk and nanostructured ZnO coated with a 2 nm Al nanoparticle layer is investigated using correlative photoluminescence and depth-resolved cathodoluminescence and time-resolved photoluminescence spectroscopy. Temperature-resolved cathodoluminescence and photoluminescence measurements from 10 K to 250 K show free exciton (FX) emission enhancement factors up to 12x at 80 K, and reveal that the FX couple more efficiently to the LSPs compared to the localized donor-bound excitons. A strong polarization dependence between the LSPs and FX is observed where FX transitions are more strongly enhanced when polarized in the same direction as the electric field of the incident excitation, which is different for laser and electron beam sources. This result indicates that selective enhancement of the excitonic emission peaks in the ZnO coated with Al nanoparticles can be achieved by choosing the appropriate ZnO substrate orientation.

Vacancy cluster in ZnO films grown by pulsed laser deposition.

Undoped and Ga-doped ZnO films were grown on c-sapphire using pulsed laser deposition (PLD) at the substrate temperature of 600 °C. Positron annihilation spectroscopy study (PAS) shows that the dominant VZn-related defect in the as-grown undoped ZnO grown with relative low oxygen pressure P(O2) is a vacancy cluster (most likely a VZn-nVO complex with n = 2, 3) rather than the isolated VZn which has a lower formation energy. Annealing these samples at 900 °C induces out-diffusion of Zn from the ZnO film into the sapphire creating the VZn at the film/sapphire interface, which favors the formation of vacancy cluster containing relatively more VZn. Increasing the P(O2) during growth also lead to the formation of the vacancy cluster with relatively more VZn. For Ga-doped ZnO films, the oxygen pressure during growth has significant influence on the electron concentration and the microstructure of the VZn-related defect. Green luminescence (GL) and yellow luminescence (YL) were identified in the cathodoluminescence study (CL) study, and both emission bands were quenched after hydrogen plasma treatment. The origin of the GL is discussed.

Radiative recombination of confined electrons at the MgZnO/ZnO heterojunction interface.

We investigate the optical signature of the interface in a single MgZnO/ZnO heterojunction, which exhibits two orders of magnitude lower resistivity and 10 times higher electron mobility compared with the MgZnO/Al2O3 film grown under the same conditions. These impressive transport properties are attributed to increased mobility of electrons at the MgZnO/ZnO heterojunction interface. Depth-resolved cathodoluminescence and photoluminescence studies reveal a 3.2 eV H-band optical emission from the heterointerface, which exhibits excitonic properties and a localization energy of 19.6 meV. The emission is attributed to band-bending due to the polarization discontinuity at the interface, which leads to formation of a triangular quantum well and localized excitons by electrostatic coupling.

Author Correction: Radiative recombination of confined electrons at the MgZnO/ZnO heterojunction interface.

A correction to this article has been published and is linked from the HTML version of this paper. The error has been fixed in the paper.

Electroluminescence from localized defects in zinc oxide: toward electrically driven single photon sources at room temperature.

Single photon sources are required for a wide range of applications in quantum information science, quantum cryptography, and quantum communications. However, the majority of room temperature emitters to date are only excited optically, which limits their proper integration into scalable devices. In this work, we overcome this limitation and present room temperature electrically driven light emission from localized defects in zinc oxide (ZnO) nanoparticles and thin films. The devices emit in the red spectral range and show excellent rectifying behavior. The emission is stable over an extensive period of time, providing an important prerequisite for practical devices. Our results open possibilities for building new ZnO-based quantum integrated devices that incorporate solid-state single photon sources for quantum information technologies.

Dynamic surface site activation: a rate limiting process in electron beam induced etching.

We report a new mechanism that limits the rate of electron beam induced etching (EBIE). Typically, the etch rate is assumed to scale directly with the precursor adsorbate dissociation rate. Here, we show that this is a special case, and that the rate can instead be limited by the concentration of active sites at the surface. Novel etch kinetics are expected if surface sites are activated during EBIE, and observed experimentally using the electron sensitive material ultra nanocrystalline diamond (UNCD). In practice, etch kinetics are of interest because they affect resolution, throughput, proximity effects, and the topography of nanostructures and nanostructured devices fabricated by EBIE.

Exploiting zinc oxide re-emission to fabricate periodic arrays.

The synthesis of hexagonal ring-shaped structures of zinc oxide using nanosphere lithography and metal/metal oxide sputtering is demonstrated. This synthesis exploits the surface re-emission of zinc oxide to deposit material in regions lying out of the line-of-sight of the sputtering source. These rings can nucleate the hydrothermal growth of zinc oxide crystals. Control over the growth could be exercised by varying growth solution concentration or temperature or by applying an external potential.

Luminescent properties of ZnO nanowires and as-grown ensembles.

Vertically aligned ZnO nanowires were synthesized on a sapphire ([Formula: see text]) substrate by vapour deposition and their light-emitting properties were characterized using photoluminescence and cathodoluminescence spectroscopies. Besides the nanowires, there exists a mosaic ZnO film on the substrate surface. Comparison of the luminescent properties of the as-grown ensemble and the nanowires extracted from it shows that the mosaic film is the major source of the defect-related green emission while the nanowires possess highly crystalline quality with virtually no defects. Photoemission spectroscopy shows that the valence band states associated with O 2p from the as-grown sample are diminished compared with those from the extracted nanowires. These findings suggest that the green emission partly arises from oxygen vacancies located on the surface of the mosaic film.

Nanocapacitive circuit elements.

"Natural" lithography was used to prepare arrays of nanoscale capacitors on silicon. The capacitance was verified by a novel technique based on the interaction of a charged substrate with the electron beam of a scanning electron microscope. The "nanocapacitors" possessed a capacitance of approximately 1 x 10(-16) F and were observed to hold charge for over an hour. Our results indicate that fabricating nanostructures using natural lithography may provide a viable alternative for future nanoelectronic devices.

Nanostructure fabrication by ultra-high-resolution environmental scanning electron microscopy.

Electron beam induced deposition (EBID) is a maskless nanofabrication technique capable of surpassing the resolution limits of resist-based lithography. However, EBID fabrication of functional nanostructures is limited by beam spread in bulk substrates, substrate charging, and delocalized film growth around deposits. Here, we overcome these problems by using environmental scanning electron microscopy (ESEM) to perform EBID and etching while eliminating charging artifacts at the nanoscale. Nanostructure morphology is tailored by slimming of deposits by ESEM imaging in the presence of a gaseous etch precursor and by pre-etching small features into a deposit (using a stationary or a scanned electron beam) prior to a final imaging process. The utility of this process is demonstrated by slimming of nanowires deposited by EBID, by the fabrication of gaps (between 4 and 7 nm wide) in the wires, and by the removal of thin films surrounding such nanowires. ESEM imaging provides a direct view of the slimming process, yielding process resolution that is limited by ESEM image resolution ( approximately 1 nm) and surface roughening occurring during etching.

Synthesis and characterization of doped and undoped ZnO nanostructures.

Zinc oxide (ZnO) nanoparticles have been produced using precipitation methods from ethanolic solution. Rare-earth metal doping was performed, and the effect of lithium codoping on the luminescence properties of the rare-earth doped products was assessed. The resulting particles were characterized using cathodoluminescence and scanning electron microscopy. It was found that lithium significantly enhanced the cathodoluminescence signal from the rare-earth ions, which has been attributed to the increased integration of the rare-earth ions into the ZnO structure. The nanophase ZnO products were also annealed in argon, hydrogen, and oxygen, with hydrogen being the most successful for removing the broad defect emission present in as-grown samples and enhancing the ZnO near band edge emission.

Monet's painting under the microscope.

An oil painting by Claude Monet, Port-Goulphar, Belle-Ile 1887 (collection of the Art Gallery of New South Wales), was examined to determine both the identity of the pigments used by the artist in this painting and his technique of mixing colors and laying paint on the canvas. The extremely complex construction of the painting was revealed by optical microscopy, scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDS), and X-ray mapping (XRM) analysis of cross sections of paint flakes excised from damaged regions of Port-Goulphar, Belle-Ile. Nine different pigments were found on the painting. Many of the identified colors were modern pigments that became available only late in the 19th century as a result of scientific advances in pigment chemistry. Although similar colors were available in a natural mineral form, they lacked the vivid color of their manufactured counterparts. The use of these new synthetic metallic oxide colors by Monet accounts for the brilliance of his paintings. In addition, a separation between successive paint layers was observed in some areas of paint chip cross sections, indicating that oil-based paint was applied to paint that had dried, and consequently, Port-Goulphar, Belle-Ile was painted over a long period of time. This observation is contrary to the general perception of Monet's technique of painting freely and quickly.

Cathodoluminescence efficiency dependence on excitation density in n-type gallium nitride.

Cathodoluminescence (CL) spectra from silicon doped and undoped wurtzite n-type GaN have been measured in a SEM under a wide range of electron beam excitation conditions, which include accelerating voltage, beam current, magnification, beam diameter, and specimen temperature. The CL intensity dependence on excitation density was analyzed using a power-law model (I CL proportional, variant J m ) for each of the observed CL bands in this material. The yellow luminescence band present in both silicon and undoped GaN exhibits a close to cube root (m = 0.33) dependence on electron beam excitation at both 77 K and 300 K. However, the blue (at 300 K) and donor-acceptor pair (at 77 K) emission peaks observed in undoped GaN follow power laws with exponents of m = 1 and m = 0.5, respectively. As expected from its excitonic character, the near band edge emission intensity depends linearly (m = 1) in silicon doped GaN and superlinearly (m = 1.2) in undoped GaN on the electron beam current. Results show that the intensities of the CL bands are highly dependent not only on the defect concentration but also on the electron-hole pair density and injection rate. Furthermore, the size of the focussed electron beam was found to have a considerable effect on the relative intensities of the CL emission peaks. Hence SEM parameters such as the objective lens aperture size, astigmatism, and the condenser lens setting must also be considered when assessing CL data based on intensity measurements from this material.