Arrays of dislocation free uniform Ga-polar GaN columns have been realized on patterned SiO x /GaN/sapphire templates by metal organic vapor phase epitaxy using a continuous growth mode. The key parameters and the physical principles of growth of Ga-polar GaN three-dimensional columns are identified, and their potential for manipulating the growth process is discussed. High aspect ratio columns have been achieved using silane during the growth, leading to n-type columns. The vertical growth rate increases with increasing silane flow. In a core–shell columnar LED structure, the shells of InGaN/GaN multi quantum wells and p-GaN have been realized on a core of n-doped GaN column. Cathodoluminescence gives insight into the inner structure of these core–shell LED structures.

A new solution based route for depositing Cu 2 ZnSnS 4 (CZTS) thin films is described, focusing on the effects of Sb and Na co-doping. X-ray diffraction and Raman spectroscopy confirm formation of the kesterite phase with a measurable improvement in crystallinity upon doping. A sharp band gap absorption edge at 1.4 eV is determined from diffuse reflectance measurements, whilst improvement in the photoluminescence yield and sharpening of the band-to-band emission spectra are observed in the presence of Na and Sb. The performance of devices with the configuration: glass/Mo/CZTS/CdS/i-ZnO/ ZnO:Al/Ni-Al and total area of 0.5 cm 2 is reported.Analysis of over 200 cells shows that introduction of Na and Sb leads to an increase of the average power conversion efficiency from 3.2±0.6 to 5.2±0.3%. The best cell with efficiency of 5.7% is obtained upon Na and Sb doping, featuring 14.9 mA cm -2 short-circuit current, 610 mV open circuit voltage and 63% fill factor under simulated AM 1.5 illumination. This performance ranks among the highest in pure sulphide CZTS cells. We propose that the improvement in crystallinity and cell performance is linked to the formation of alkali antimony chalcogenides flux during the annealing step, in addition to Sb and Na decreasing disorder in specific lattice positions of the CZTS unit cell.

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Transmission and scanning electron microscopies are used to examine the epitaxial lateral overgrowth of GaN on GaN nanocolumns grown on AlN/(0001)sapphire by molecular beam epitaxy. Initially, N-rich growth gave a bimodal morphology consisting of defect-free Ga-polar nanocolumns emanating from a compact, highly defective N-polar layer. Under subsequent Ga-rich conditions, the nanocolumns grew laterally to produce continuous Ga-polar overlayers. Threading dislocation (TD) densities in the overlayer were in the range of 108–109cm−2, up to two orders of magnitude less than in the N-polar underlayer. It is proposed that the change in polarity is a key factor controlling the reduction in TD density.

As an instrument, the scanning transmission electron microscope is unique in being able to simultaneously explore both local structural and chemical variations in materials at the atomic scale. This is made possible as both types of data are acquired serially, originating simultaneously from sample interactions with a sharply focused electron probe. Unfortunately, such scanned data can be distorted by environmental factors, though recently fast-scanned multi-frame imaging approaches have been shown to mitigate these effects. Here, we demonstrate the same approach but optimized for spectroscopic data; we offer some perspectives on the new potential of multi-frame spectrum-imaging (MFSI) and show how dose-sharing approaches can reduce sample damage, improve crystallographic fidelity, increase data signal-to-noise, or maximize usable field of view. Further, we discuss the potential issue of excessive data-rates in MFSI, and demonstrate a file-compression approach to significantly reduce data storage and transmission burdens.

Atomic resolution transmission electron microscopy has been used to examine antisite defects in Cu2ZnSnS4 (CZTS) kesterite crystals grown by a hot injection method. High angle annular dark field (HAADF) imaging at sub-0.1 nm resolution, and lower magnification dark field imaging using reflections sensitive to cation ordering, are used to reveal antisite domain boundaries (ADBs). These boundaries, typically 5-20 nm apart, and extending distances of 100 nm or more into the crystals, lie on a variety of planes and have displacements of the type ½[110] or ¼[201], which translate Sn, Cu and Zn cations into antisite positions. It is shown that some ADBs describe a change in the local stoichiometry by removing planes of S and either Cu or Zn atoms, implying that these boundaries can be electrically charged. The observations also showed a marked increase in cation disorder in regions within 1-2 nm of the grain surfaces suggesting that growth of the ordered crystal takes place at the interface with a disordered shell. It is estimated that the ADBs contribute on average ∼0.1 antisite defect pairs per unit cell. Although this is up to an order of magnitude less than the highest antisite defect densities reported, the presence of high densities of ADBs that may be charged suggests these defects may have a significant influence on the efficiency of CZTS solar cells.

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