Controlling the size and alignment of ZnO microrods using ZnO thin film templates deposited by pulsed laser ablation

The production of dense arrays of well aligned ZnO nano- and microrods with a controllable distribution of diameters is demonstrated. The rods were grown using a hydrothermal method, on pre-deposited ZnO thin films exhibiting a range of different grain sizes. These template ZnO thin films were deposited by pulsed laser ablation, at 193 nm, in a low background pressure of O₂; average grain sizes ranged from 10 nm (room temperature deposition) to 50 nm when deposited at a substrate temperature (T_sub) of 500 °C. The morphology of the ZnO microrod arrays grown onto these ZnO thin films was found to depend on the T_sub used during film deposition. Increasing T_sub resulted in a lower density of larger nanorods, with a more pronounced [0001] alignment. The diameters of the rods produced are typically an order of magnitude greater than the grain size of the template ZnO film. Thus the rods cannot be a direct continuation of the grain structure of the template films. Rather, we suggest that the rod diameter is controlled by the density of sites at which the initial nucleation occurs, which is expected to be higher on the smaller grain size films deposited at lower temperatures. The factor controlling the final size of the rods is thus the available free space into which they can grow, which is smaller at the higher nucleation densities. The increased extent of [0001] texturing of the thin film templates deposited at higher T_sub is proposed as the reason for the improved [0001] alignment of rods grown on these templates. PACS 81.07.De; 81.10.Dn; 52.38.Mf     

Electron microscope studies of sodium and lithium intercalation in TiS2

Lithium and sodium intercalation in TiS₂ have been studied by transmission electron microscopy using lattice imaging and diffraction contrast techniques. Na_xTiS₂ samples (0 ≤ x ≤ 0.6) from $\text{Na}\text{NaI}$ in propylene carbonate/TiS₂ batteries were found to contain a complex variety of phases inhomogeneous on a fine scale. Observations showed variable staging and a 2H phase not previously reported for this system at ambient temperatures. Observations on both Na_xTiS₂ and chemically prepared Li_xTiS₂ showed highly dislocated structures. A model is proposed whereby dislocations are introduced to accommodate misfit strains caused by nonuniform intercalation and, in the case of Na_xTiS₂, to initiate phase transformations, leading to potentially irreversible structural changes in cycled material.     

Surface characterizations of fluorescent-functionalized silica nanoparticles: from the macroscale to the nanoscale

Journal of Nanoparticle Research - Fluorescent silica nanoparticles are widely used for various applications from mechanical reinforcement to biology. In many cases, their surface has to be...     

Nano-cracks in a synthetic graphite composite for nuclear applications

Mrozowski nano-cracks in nuclear graphite were studied by transmission electron microscopy and selected area diffraction. The material consisted of single crystal platelets typically 1–2 nm thick and stacked with large relative rotations around the c-axis; individual platelets had both hexagonal and cubic stacking order. The lattice spacing of the (0002) planes was about 3% larger at the platelet boundaries which were the source of a high fraction of the nano-cracks. Tilting experiments demonstrated that these cracks were empty, and not, as often suggested, filled by amorphous material. In addition to conventional Mrozowski cracks, a new type of nano-crack is reported, which originates from the termination of a graphite platelet due to crystallographic requirements. Both types are crucial to understanding the evolution of macro-scale graphite properties with neutron irradiation.     

Profiling band structure in GaN devices by electron holography

Electron holography in a field emission gun transmission electron microscope has been used to profile the inner potential V₀ across GaN/x nm In_0.1Ga_0.9N/GaN/(0 0 0 1) sapphire samples (x=10, 40 nm) grown by molecular beam epitaxy and viewed in cross-section. Results are presented which suggest a decrease in V₀ of 3–4 V across the InGaN layer in the [0 0 0 1] direction. It is proposed that the results can be explained by charge accumulation across the InGaN layer and that the opposing contributions due to piezoelectric and polarisation fields are effectively masked by Fermi level pinning.     

A complementary geometric model for the growth of GaN nanocolumns prepared by plasma-assisted molecular beam epitaxy

In this article, we propose a new complementary geometrical growth mechanism, which may partially explain some of the apparent anomalies in our understanding of the growth of GaN nanocolumns by plasma-assisted molecular beam epitaxy (PA-MBE). This geometrical addition to any complete model for nanocolumn growth is based on the fact that most samples are grown using substrate rotation and it predicts an enhanced growth rate in the plane normal to the surface, i.e. vertically compared with the lateral growth rate of the columns. It also suggests a mechanism for the enhanced diffusion of gallium on the sidewalls of the columns even under strongly nitrogen-rich conditions. Finally, geometrical considerations also predict the growth of non-(0 0 0 1) oriented samples from the same mechanism. Some experimental evidence supporting this complementary geometrical model is presented.     

Growth of nanostructured ZnO thin films on sapphire

Growth of ZnO nanostructures on c-plane sapphire has been investigated using three different methods. Pulsed laser deposition (PLD) at low incident pulse energies can yield nanorods, the majority of which are aligned at an angle of ∼50° to the substrate plane. Selected area electron diffraction reveals that the nanorods display two distinct epitaxial relationships with the sapphire substrate. Those inclined to the surface normal exhibit the relationships (112̄4)_ZnO//(0001)_sap; [101̄0]_ZnO//[112̄0]_sap and (0001)_ZnO//(101̄4)_sap; [101̄0]_ZnO//[112̄0]_sap. Members of the second family are aligned along the surface normal, with (0001)_ZnO//(0001)_sap and [101̄0]_ZnO//[112̄0]_sap; the relative yield of this latter class increases at higher incident pulse energies. Hydrothermal synthesis and chemical vapour deposition on sapphire substrates that have been pre-coated (by PLD) with a thin ZnO layer result, respectively, in well-aligned ZnO microrod and nanorod arrays, both of which satisfy the relationships (0001)_ZnO//(0001)_sap; [101̄0]_ZnO//[112̄0]_sap. In contrast, employing these latter methods with a bare sapphire substrate results in, respectively, poorly aligned structures and localized islands of growth. PACS  81.07.-b; 81.10.-h; 81.15.Aa; 81.15-z; 68.65.-k     

Electron energy loss near edge structure (ELNES) spectra of AlN and AlGaN: a theoretical study using the Wien2k and Telnes programs

Several aspects of the modelling of the energy loss near edge structure (ELNES) using the Wien2k code and the Telnes program are discussed in this paper. A case study with ground state, partial and full core-hole calculations of wurtzite AlN was performed and the results were compared with experimental transmission electron microscopy data. The best agreement with the experimental observations was obtained for the full core-hole case. Changes in the ELNES spectra for various core-hole charges are explained by investigating the site and symmetry projected density of states. Directionally resolved N K-edge ELNES of AlN are discussed and the magic angle beta approximately 2.5mrad is identified which is in a good agreement with other theoretical predictions. Finally, preliminary results on a compositional study of Al(x)Ga(1-x)N are explored.     

Luminescence studies of defects and piezoelectric fields in InGaN/GaN single quantum wells

Transmission electron microscopy (TEM), cathodoluminescence in the scanning electron microscope (SEM-CL) and photoluminescence (PL) studies were performed on a 30 nm GaN/2 nm In_0.28Ga _0.72N/2 μm GaN/(0 0 0 1) sapphire single quantum well (SQW) sample. SEM-CL was performed at low temperatures ≈8 K, and at an optimum accelerating voltage, around 4–6 kV to maximise the quantum well (QW) luminescence. The CL in the vicinity of characteristic “V-shaped” pits was investigated. The near band edge (BE) luminescence maps from the GaN showed bright rings inside the boundaries of the pits while the QW luminescence maps showed pits to be regions of low intensity. These observations are consistent with TEM observations showing the absence of QW material in the pits. Variations in both the BE and QW maps in the regions between the pits are ascribed to threading edge dislocations. The CL and PL QW luminescence was observed to blue-shift and broaden with increasing excitation intensity. This was accompanied by decreasing spatial resolution in the CL QW maps implying an increasing carrier diffusion length in the InGaN layer. The reasons for this behaviour are discussed. It is argued that screening of the piezoelectric field in the material may account for these observations.