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Polyvinylpyrrolidone (PVP) can be used to produce upconversion nanoparticles (UCNPs) in an advantageous manner, i.e. at modest temperatures in open-to-air conditions with simple hotplate and flask apparatus. However, the influence of PVP parameters on the formation of UCNPs has not been previously investigated. In this exploratory study, we establish that PVP molecular weight and relative amount of PVP can greatly influence the morphology and diameter of NaYF4:Yb,Er UCNPs produced via the PVP-assisted route. At nominal amounts of PVP, varying the molecular weight of PVP in synthesis between 10,000 g/mol (PVP10), 40,000 g/mol (PVP40), and 55,000 g/mol (PVP55), had minimal effect on UCNP morphology, whereas reducing the quantity of PVP10 and PVP40 in the reaction to 10% of the nominal amount resulted in two notable effects: (1) the generation of a greater range of UCNP diameters and (2) the production of an unexpected sub-population of rhombus-shaped UCNPs. Bulk and individual nanoparticle analysis indicates that all UCNP morphologies were cubic (α-phase) crystal structure and consisted of NaYF4:Yb,Er. Optical emission properties exhibited only modest green and red luminescence emission ratio when PVP parameters were varied. However, separately produced PVP40 NaYF4:Yb,Tm UCNPs exhibited a much more intense and dual-band blue /red emission. This exploratory work demonstrates that tailoring PVP content in synthesis of UCNPs can greatly alter morphology of UCNPs produced and should be carefully considered in experimental design. However, the underlying mechanisms of action of the role PVP plays in this synthesis remain unclear. Ultimately, significant further work is still required to fully elucidate the relevant chemistry to achieve full control of PVP-UCNP synthesis.

Funding: LKJ acknowledges funding from UKRI-FLF through MR/T022094/1. LKJ and PG acknowledge Dr Ben F. Spencer for the XPS data acquisition, which was supported by the Henry Royce Institute, funded through UK EPSRC grants EP/R00661X/1, EP/P025021/1 and EP/P025498/1 and Dr Julia L. Payne for all the support with the XRD and FTIR measurements. JB and CTC acknowledge funding from UK EPSRC grant EP/P015719/1. Indoor photovoltaic devices have garnered profound research attention in recent years due to their prospects of powering ‘smart’ electronics for the Internet of Things (IoT). Here it is shown that all-inorganic Cs-based halide perovskites are promising for indoor light harvesting due to their wide bandgap matched to the indoor light spectra. Highly crystalline and compact CsPbIBr2 perovskite based photovoltaic devices have demonstrated a power conversion efficiency (PCE) of 14.1% under indoor illumination of 1000 lx and 5.9% under 1 Sun. This study revealed that a reduction in grain misorientation, as well as suppression of defects in the form of metallic Pb in the perovskite film are crucial for maximising the photovoltaic properties of CsPbIBr2 based devices. It was demonstrated that a pinhole free CsPbIBr2/Spiro-OMeTAD interface preserves the perovskite α phase and enhances the air stability of the CsPbIBr2 devices. These devices, despite being unencapsulated, retained > 55% of the maximum PCE even when stored under 30% relative humidity for a shelf-life duration of 40 days and is one of the best stability data reported so far for CsPbIBr2 devices. Postprint

A novel overgrowth approach has been developed in order to create a multiple-facet structure consisting of only non-polar and semi-polar GaN facets without involving any c-plane facets, allowing the major drawbacks of utilising c-plane GaN for the growth of III-nitride optoelectronics to be eliminated. Such a multiple-facet structure can be achieved by means of overgrowth on non-polar GaN micro-rod arrays on r-plane sapphire. InGaN multiple quantum wells (MQWs) are then grown on the multiple-facet templates. Due to the different efficiencies of indium incorporation on non-polar and semi-polar GaN facets, multiple-colour InGaN/GaN MQWs have been obtained. Photoluminescence (PL) measurements have demonstrated that the multiple-colour emissions with a tunable intensity ratio of different wavelength emissions can be achieved simply through controlling the overgrowth conditions. Detailed cathodoluminescence measurements and excitation-power dependent PL measurements have been performed, further validating the approach of employing the multiple facet templates for the growth of multiple colour InGaN/GaN MQWs. It is worth highlighting that the approach potentially paves the way for the growth of monolithic phosphor-free white emitters in the future.

This chapter discusses an alternative approach for generating white light through hybrid inorganic–organic light-emitting diodes (LEDs), combining blue-emitting organic LEDs with organic energy-down converters. Inorganic LEDs, based on III-nitride semiconductors, exhibit extremely high efficiencies, whereas organic color converters are low-cost and have versatile absorption and emission properties. An extensive background is provided to introduce nitride semiconductors and LEDs, but also to give the background to colorimetry and radiometry of light sources, important for the characterization of the hybrid device and an understanding of how the emission properties influence the color parameters, such as color rendering and luminous efficacy. A short introduction to the synthesis of color converters aims to illustrate the controlling factors in the design of the converter materials. Two types of organic materials will be introduced. The first are light-emitting polymers, which are readily commercially available and cost effective. The second type are luminescent small molecules, which will be discussed in more detail and the examples given showcase the evolution of a series of small molecules and their use in hybrid inorganic–organic LEDs.

With a view to supporting the development of ultra-violet light-emitting diodes and related devices, the compositional, emission and morphology properties of Si-doped n-type Al x Ga1-x N alloys are extensively compared. This study has been designed to determine how the different Al x Ga1-x N crystal orientations (polar (0001) and semipolar (11–22)) affect group-III composition and Si incorporation. Wavelength dispersive x-ray (WDX) spectroscopy was used to determine the AlN mole fraction (x ≈ 0.57–0.85) and dopant concentration (3 × 1018–1 × 1019 cm−3) in various series of Al x Ga1-x N layers grown on (0001) and (11–22) AlN/sapphire templates by metalorganic chemical vapor deposition. The polar samples exhibit hexagonal surface features with Ga-rich boundaries confirmed by WDX mapping. Surface morphology was examined by atomic force microscopy for samples grown with different disilane flow rates and the semipolar samples were shown to have smoother surfaces than their polar counterparts, with an approximate 15% reduction in roughness. Optical characterization using cathodoluminescence (CL) spectroscopy allowed analysis of near-band edge emission in the range 4.0–5.4 eV as well as various deep impurity transition peaks in the range 2.7–4.8 eV. The combination of spatially-resolved characterization techniques, including CL and WDX, has provided detailed information on how the crystal growth direction affects the alloy and dopant concentrations.

In this article we describe the scanning electron microscopy (SEM) techniques of electron channelling contrast imaging and electron backscatter diffraction. These techniques provide information on crystal structure, crystal misorientation, grain boundaries, strain and structural defects on length scales from tens of nanometres to tens of micrometres. Here we report on the imaging and analysis of dislocations and sub-grains in nitride semiconductor thin films (GaN and AlN) and tungsten carbide-cobalt (WC-Co) hard metals. Our aim is to illustrate the capability of these techniques for investigating structural defects in the SEM and the benefits of combining these diffraction-based imaging techniques.

It is well-known that it is crucial to insert either a single InGaN underlayer or an InGaN superlattice (SLS) structure (both with low InN content) as a pre-layer prior to the growth of InGaN/GaN multiple quantum wells (MQWs) served as an active region for a light-emitting diode (LED). So far, this growth scheme has achieved a great success in the growth of III-nitride LEDs on c-plane substrates, but has not yet been applied in the growth of any other orientated III-nitride LEDs. In this paper, we have applied this growth scheme in the growth of semi-polar (11–22) green LEDs, and have investigated the impact of the SLS pre-layer on the optical performance of semi-polar (11–22) green LEDs grown on patterned (113) silicon substrates. Our results demonstrate that the semi-polar LEDs with the SLS pre-layer exhibit an improvement in both internal quantum efficiency and light output, which is similar to their c-plane counterparts. However, the performance improvement is not so significant as in the c-plane case. This is because the SLS pre-layer also introduces extra misfit dislocations for the semi-polar, but not the c-plane case, which act as non-radiative recombination centres.

The development of organic down-converting materials continues to attract attention in hybrid LED technology by obviating the need for non-sustainable rare-earth elements. In this work, a benzodiimidazole-based system (TPA-BDI) has been employed as a down-converting layer in a hybrid organic-inorganic LED device. A commercially available poly(urethane)-based resin is used as the encapsulating material, providing a dilute layer of TPA-BDI that is deposited on top of the GaN-based LED. Crucially, the solution-state emissive performance is generally maintained when encapsulated at low concentrations within this resin. A maximum luminous efficacy of 87 lm W -1 was demonstrated using a 1.0 mg ml -1 concentration of TPA-BDI in the resin. The suitability of using organic down-converters to produce green light from hybrid devices was demonstrated by the excellent repeatability of the device characteristics across a series of encapsulated LEDs.

We investigate the influence of different types of template micro-patterning on defect reduction and optical properties of non-polar GaN using detailed luminescence studies. Non-polar (112ˉ0) (or a-plane) GaN exhibits a range of different extended defects compared with its more commonly used c-plane counterpart. In order to reduce the number of defects and investigate their impact on luminescence uniformity, non-polar GaN was overgrown on four different GaN microstructures. The micro-patterned structures consist of a regular microrod array; a microrod array where the −c-side of the microrods has been etched to suppress defect generation; etched periodic stripes and finally a subsequent combination of etched stripes and etched microrods (double overgrowth). Overall the presence of extended defects, namely threading dislocations and stacking faults (SFs) is greatly reduced for the two samples containing stripes compared with the two microrod samples. This is evidenced by more uniform emission and reduction in dark regions of non-radiative recombination in room temperature cathodoluminescence imaging as well as a reduction of the SF emission line in low temperature photoluminescence. The observed energy shifts of the GaN near band edge emission are related to anisotropic strain relaxation occurring during the overgrowth on these microstructures. A combination of stripes and microrods is a promising approach for defect reduction and emission uniformity in non-polar GaN for applications in light-emitting devices as well as power electronics., publishedVersion

Pushing the emission wavelength of efficient ultraviolet (UV) emitters further into the deep-UV requires material with high crystal quality, while also reducing the detrimental effects of built-in electric fields. Crack-free semi-polar $$\mathrm{(11}\bar{2}\mathrm{2)}$$ (11 2 ¯ 2) Al x Ga1−x N epilayers with AlN contents up to x = 0.56 and high crystal quality were achieved using an overgrowth method employing GaN microrods on m-sapphire. Two dominant emission peaks were identified using cathodoluminescence hyperspectral imaging. The longer wavelength peak originates near and around chevron-shaped features, whose density is greatly increased for higher contents. The emission from the majority of the surface is dominated by the shorter wavelength peak, influenced by the presence of basal-plane stacking faults (BSFs). Due to the overgrowth technique BSFs are bunched up in parallel stripes where the lower wavelength peak is broadened and hence appears slightly redshifted compared with the higher quality regions in-between. Additionally, the density of threading dislocations in these region is one order of magnitude lower compared with areas affected by BSFs as ascertained by electron channelling contrast imaging. Overall, the luminescence properties of semi-polar AlGaN epilayers are strongly influenced by the overgrowth method, which shows that reducing the density of extended defects improves the optical performance of high AlN content AlGaN structures.

Electron channelling contrast imaging (ECCI) performed in a scanning electron microscope (SEM) is a rapid and non-destructive structural characterisation technique for imaging, identifying and quantifying extended defects in crystalline materials. In this review, we will demonstrate the application of ECCI to the characterisation of III-nitride semiconductor thin films grown on different substrates and with different crystal orientations. We will briefly describe the history and the theory behind electron channelling and the experimental setup and conditions required to perform ECCI. We will discuss the advantages of using ECCI, especially in combination with other SEM based techniques, such as cathodoluminescence imaging. The challenges in using ECCI are also briefly discussed.

In this chapter, the authors discuss microscopy techniques that can be useful in addressing defects in semiconductors. They focus on three main families: scanning probe microscopy, scanning electron microscopy and transmission electron microscopy. They first address the basic principles of the selected microscopy techniques In discussions of image formation, they elucidate the mechanisms by which defects are typically imaged in each technique. Then, in the latter part of the chapter, they describe some key examples of the application of microscopy to semiconductor materials, addressing both point and extended defects and both two-dimensional (2D) and three-dimensional (3D) materials.

The crystal polarity of noncentrosymmetric wurtzite GaN nanowires is determined nondestructively in the scanning electron microscope using electron backscatter diffraction (EBSD). The impact of the nanowire polarity on light emission is then investigated using cathodoluminescence (CL) spectroscopy. EBSD can determine polarity of noncentrosymmetric crystals by interrogating differences in the intensity distribution of bands of the EBSD pattern associated with semipolar planes. Experimental EBSD patterns from an array of GaN nanowires are compared with theoretical patterns produced using dynamical electron simulations to reveal whether they are Ga- or N-polar or, as in several cases, of mixed polarity. CL spectroscopy demonstrates the effect of the polarity on light emission, with spectra obtained from nanowires of known polarity revealing a small but measurable shift (≈28 meV) in the GaN near band edge emission energy between those with Ga and N polarity. We attributed this energy shift to a difference in impurity incorporation in nanowires of different crystal polarity. This approach can be employed to nondestructively identify polarity in a wide range of noncentrosymmetric nanoscale material systems and provide direct comparison with their luminescence.

One of the most important non-radiative relaxation processes that limits the quantum yield of a fluorophore is related to aggregation of the molecules in the solid-state causing excimer quenching. To limit this quenching mechanism, the fluorophore can be contained within a well-ordered 3D system that minimises aggregation through rigid bonds and spatial separation in a defined topological construct. Herein, the synthesis, characterisation and application as a down-converter of a new luminescent 3D material (MOF-BTBMBA) that incorporates a building block based on a benzothiadiazole (BT) derivative (BTBMBA) in a metal–organic framework (MOF) is presented. Notably, the photoluminescence quantum yield and hybrid LED performance are significantly improved for the MOF-based device compared to that prepared with the free ligand, highlighting the effectiveness of the rigid scaffold arrangement.

The scanning electron microscopy techniques of electron backscatter diffraction (EBSD), electron channelling contrast imaging (ECCI) and cathodoluminescence (CL) hyperspectral imaging provide complementary information on the structural and luminescence properties of materials rapidly and non-destructively, with a spatial resolution of tens of nanometres. EBSD provides crystal orientation, crystal phase and strain analysis, whilst ECCI is used to determine the planar distribution of extended defects over a large area of a given sample. CL reveals the influence of crystal structure, composition and strain on intrinsic luminescence and/or reveals defect-related luminescence. Dark features are also observed in CL images where carrier recombination at defects is non-radiative. The combination of these techniques is a powerful approach to clarifying the role of crystallography and extended defects on a material’s light emission properties. Here we describe the EBSD, ECCI and CL techniques and illustrate their use for investigating the structural and light emitting properties of UV-emitting nitride semiconductor structures. We discuss our investigations of the type, density and distribution of defects in GaN, AlN and AlGaN thin films and also discuss the determination of the polarity of GaN nanowires.

In this work, we report on the innovative growth of semipolar “bow-tie”-shaped GaN structures containing InGaN/GaN multiple quantum wells (MQWs) and their structural and luminescence characterization. We investigate the impact of growth on patterned (113) Si substrates, which results in the bow-tie cross section with upper surfaces having the ( 10 1 ¯ 1 ) orientation. Room temperature cathodoluminescence (CL) hyperspectral imaging reveals two types of extended defects: black spots appearing in intensity images of the GaN near band edge emission and dark lines running parallel in the direction of the Si stripes in MQW intensity images. Electron channeling contrast imaging (ECCI) identifies the black spots as threading dislocations propagating to the inclined ( 10 1 ¯ 1 ) surfaces. Line defects in ECCI, propagating in the [ 1 2 ¯ 10 ] direction parallel to the Si stripes, are attributed to misfit dislocations (MDs) introduced by glide in the basal (0001) planes at the interfaces of the MQW structure. Identification of these line defects as MDs within the MQWs is only possible because they are revealed as dark lines in the MQW CL intensity images, but not in the GaN intensity images. Low temperature CL spectra exhibit additional emission lines at energies below the GaN bound exciton emission line. These emission lines only appear at the edge or the center of the structures where two (0001) growth fronts meet and coalesce (join of the bow-tie). They are most likely related to basal-plane or prismatic stacking faults or partial dislocations at the GaN/Si interface and the coalescence region.In this work, we report on the innovative growth of semipolar “bow-tie”-shaped GaN structures containing InGaN/GaN multiple quantum wells (MQWs) and their structural and luminescence characterization. We investigate the impact of growth on patterned (113) Si substrates, which results in the bow-tie cross section with upper surfaces having the ( 10 1 ¯ 1 ) orientation. Room temperature cathodoluminescence (CL) hyperspectral imaging reveals two types of extended defects: black spots appearing in intensity images of the GaN near band edge emission and dark lines running parallel in the direction of the Si stripes in MQW intensity images. Electron channeling contrast imaging (ECCI) identifies the black spots as threading dislocations propagating to the inclined ( 10 1 ¯ 1 ) surfaces. Line defects in ECCI, propagating in the [ 1 2 ¯ 10 ] direction parallel to the Si stripes, are attributed to misfit dislocations (MDs) introduced by glide in the basal (0001) planes at the interfaces of the MQW struc...

While the use of electron probe microanalysis (EPMA) is widespread in the geological and metallurgical sciences, it remains less prevalent in the field of semiconductor research. For these materials, trace element (i.e. dopant) levels typically lie near or beneath the detection limit of wavelength-dispersive Xray (WDX) spectrometers, while alloy compositions of ternary mixtures and multilayer structures can more readily be determined using X-ray diffraction techniques. The electron beam measurements more commonly applied to semiconductors remain transmission electron microscopy (for structural characterization), and scanning electron microscopy (topographic, optical and electrical information). Despite this, there are many aspects of the EPMA that make it an attractive platform for all of thesetypes of semiconductor characterization, particularly when combining compositional information fromWDX with complementary and simultaneously-acquired signals. These advantages include: built-inlight optics; a stable, quantified and high-current beam; and a combined large-area and high-resolutionmapping capability. This allows the measurement of cathodoluminescence (CL), electron beam-inducedcurrent (EBIC) and electron channelling contrast imaging (ECCI) signals alongside WDX, which weapply to the investigation of visible and UV AlxInyGa1-x-yN materials, devices and nanostructures.

In this paper we describe the scanning electron microscopy techniques of electron backscatter diffraction, electron channeling contrast imaging, wavelength dispersive X-ray spectroscopy, and cathodoluminescence hyperspectral imaging. We present our recent results on the use of these non-destructive techniques to obtain information on the topography, crystal misorientation, defect distributions, composition, doping, and light emission from a range of UV-emitting nitride semiconductor structures. We aim to illustrate the developing capability of each of these techniques for understanding the properties of UV-emitting nitride semiconductors, and the benefits were appropriate, in combining the techniques.

The synthesis and characterisation of two novel organic down-converting molecules is disclosed, together with their performance as functional colour-converters in combination with inorganic blue light-emitting diodes (LEDs). Each molecule contains two fluorene-triphenylamine arms, connected to either a benzothiadiazole or bisbenzothiadiazole core. These molecules have been selected on the basis that they are free from absorption bands in the green region of the visible spectrum to maximise their performance and offer improvements compared with previous BODIPY-containing analogues. The inorganic InGaN/GaN LED emits at 444 nm, overlying the absorption of each of the organic molecules. The combination of the blue (inorganic) and yellow (organic) emission is shown to produce reasonable quality, white light-emitting hybrid devices for both down-converter molecules. Cool to warm white light is achieved for both molecules by increasing the concentration. An optimum colour rendering index (CRI) value of 66 is obtained for the mono-benzothiadiazole molecule. Also a high blue-to-white efficacy (defined as white luminous flux (lm)/blue radiant flux (W)) of 368 lm W$^{-1}$ is achieved, superseding the current phosphor converters of 200-300 lm W$^{-1}$. A comparison of these down-converting molecules to the older generation BODIPY-containing molecules is also provided.

We combine two scanning electron microscopy techniques to investigate the influence of dislocations on the light emission from nitride semiconductors. Combining electron channeling contrast imaging and cathodoluminescence imaging enables both the structural and luminescence properties of a sample to be investigated without structural damage to the sample. The electron channeling contrast image is very sensitive to distortions of the crystal lattice, resulting in individual threading dislocations appearing as spots with black–white contrast. Dislocations giving rise to nonradiative recombination are observed as black spots in the cathodoluminescence image. Comparison of the images from exactly the same micron-scale region of a sample demonstrates a one-to-one correlation between the presence of single threading dislocations and resolved dark spots in the cathodoluminescence image. In addition, we have also obtained an atomic force microscopy image from the same region of the sample, which confirms that both pure edge dislocations and those with a screw component (i.e., screw and mixed dislocations) act as nonradiative recombination centers for the Si-doped c-plane GaN thin film investigated.

Electron channelling contrast imaging (ECCI) performed in a scanning electron microscope (SEM) is a rapid and non-destructive structural characterisation technique for imaging, identifying and quantifying extended defects in crystalline materials. In this review, we will demonstrate the application of ECCI to the characterisation of III-nitride semiconductor thin films grown on different substrates and with different crystal orientations. We will briefly describe the history and the theory behind electron channelling and the experimental setup and conditions required to perform ECCI. We will discuss the advantages of using ECCI, especially in combination with other SEM based techniques, such as cathodoluminescence imaging. The challenges in using ECCI are also briefly discussed.

A novel BODIPY-containing organic small molecule is synthesized and employed as a down-converting layer on a commercial blue light-emitting diode (LED). The resulting hybrid device demonstrates white-light emission under low-current operation, with color coordinates of (0.34, 0.31) and an efficacy of 13.6 lm/W; four times greater than the parent blue LED.

The influence of substrate miscut on Al0.5Ga0.5N layers was investigated using cathodoluminescence (CL) hyperspectral imaging and secondary electron imaging in an environmental scanning electron microscope. The samples were also characterized using atomic force microscopy and high resolution X-ray diffraction. It was found that small changes in substrate miscut have a strong influence on the morphology and luminescence properties of the AlGaN layers. Two different types are resolved. For low miscut angle, a crack-free morphology consisting of randomly sized domains is observed, between which there are notable shifts in the AlGaN near band edge emission energy. For high miscut angle, a morphology with step bunches and compositional inhomogeneities along the step bunches, evidenced by an additional CL peak along the step bunches, are observed. (C) 2014 Author(s).

Significant improvements in the efficiency of optoelectronic devices can result from the exploitation of nanostructures. These require optimal nanocharacterization techniques to fully understand and improve their performance. In this study we employ room temperature cathodoluminescence hyperspectral imaging to probe single GaN-based nanorods containing multiple quantum wells (MQWs) with a simultaneous combination of very high spatial and spectral resolution. We have investigated the strain state and carrier transport in the vicinity of the MQWs, demonstrating the high efficiencies resulting from reduced electric fields. Power-dependent photoluminescence spectroscopy of arrays of these nanorods confirms that their fabrication results in partial strain relaxation in the MQWs. Our technique allows us to interrogate the structures on a sufficiently small length scale to be able to extract the important information.

Measurements of light emission from GaN nanorods of diameter between 80 and 350 nm, containing either a three-well multiple InGaN quantum well or a single quantum well, have been performed by photoluminescence (PL) and cathodoluminescence (CL) hyperspectral imaging. The PL underwent a Stark shift to the blue as the nanorod diameter was reduced, indicating substantial relaxation of the compressive strain in the quantum wells. The intensity of the nanorod emission per unit area can exceed that of the planar starting material. The CL measurements revealed that the wavelength of the quantum well emission varied with radial position in the nanorod. Simulations by a modal expansion method revealed that the light extraction efficiency varies with radial position and the variation is dependent on nanorod diameter. Finite difference time domain simulations showed that Bloch mode formation in the buffer layer below the nanorods impacts on the light extraction.

A family of linear oligofluorene-BODIPY structures, containing either a ter- or quaterfluorene unit, have been prepared, in which the attachment of the oligofluorene chain to the BODIPY unit is switched between the meso- and beta-positions. Each member of this family was investigated by UV-vis absorption and photoluminescence spectroscopy, cyclic voltammetry and thermal studies (TGA and DSC) to determine their suitability as emissive layers in hybrid luminescent devices. One candidate was then successfully deployed as a down converter to convert UV to visible light.

Hyperspectral cathodoluminescence imaging provides spectrally and spatially resolved information on luminescent materials within a single dataset. Pushing the technique toward its ultimate nanoscale spatial limit, while at the same time spectrally dispersing the collected light before detection, increases the challenge of generating low-noise images. This article describes aspects of the instrumentation, and in particular data treatment methods, which address this problem. The methods are demonstrated by applying them to the analysis of nanoscale defect features and fabricated nanostructures in III-nitride-based materials.

InGaN/GaN multiple quantum wells (MQWs) have been studied by using cathodoluminescence hyperspectral imaging with high spatial resolution. Variations in peak emission energies and intensities across trench-like features and V-pits on the surface of the MQWs are investigated. The MQW emission from the region inside trench-like features is red-shifted by approximately 45 meV and more intense than the surrounding planar regions of the sample, whereas emission from the V-pits is blue-shifted by about 20 meV and relatively weaker. By employing this technique to the studied nanostructures it is possible to investigate energy and intensity shifts on a 10 nm length scale., Comment: 3 pages, 3 figures

Cathodoluminescence (CL) hyperspectral imaging—the acquisition of a full optical emission spectrum at each pixel of an image—has become firmly established as a measurement mode in scanning electron microscopy (SEM) [1]. CL is sensitive to the structural, compositional and electrical properties of a sample, and the inherent multimode nature of SEM makes it possible to combine CL with other techniques which are also sensitive to one or more of these properties. For example, combining CL hyperspectral imaging with simultaneous X-ray microanalysis has been used to probe composition variations within semiconductors [2] and minerals [3]. In this work we present recent results combining CL hyperspectral imaging with other SEM modes, and also demonstrate the benefits of introducing additional measurement parameters, such as sample applied bias and microscope chamber pressure. Structural defects are central in determining the performance of electrical and optical devices based on III-nitride semiconductors. To better understand the effect of threading dislocations on carrier recombination in such materials, we have carried out CL imaging together with electron channeling contrast imaging (ECCI), which is sensitive to the lattice distortions associated with such defects. Using this combination of techniques we have shown that both pure edge dislocations and mixed (combination of edge + screw) dislocations act as nonradiative recombination centers in GaN epilayers [4]. Since CL provides information only about radiative recombination, it needs to be coupled with other techniques to provide a fuller picture of the different carrier loss mechanisms which limit device performance, an objective we achieved by measuring CL together with electron beam induced current (EBIC). This signal originates within the junction of an electrically contacted device (measured via an external circuit) and is dependent on the total (i.e. radiative + nonradiative) recombination. By carrying out both techniques simultaneously on InxGa1-xN/GaN light-emitting diodes (LEDs), we have separated out nonradiative recombination from other loss mechanisms, such as light extraction or electrical contacting issues [5]. These CL/EBIC measurements on contacted LEDs have opened up the possibility of introducing an additional variable into CL imaging: applied bias voltage. Figure 1 shows an example of such measurements for an InGaN/GaN LED device. This capability allows the emission to be imaged under conditions closer to those of a device in normal operation. It also allows us—by imaging at several bias values—to differentiate between the drift and diffusion components of the current, and to probe the influence of the quantum-confined Stark effect in the active region of the LED. Furthermore, comparison with electroluminescence (EL) hyperspectral images yields additional information: for example, in some areas of the LED we see correlations between contrast features in EL and EBIC images which are not present in the CL, implying that they originate in the diode junction or contacts rather than in the active layer itself [5]. Finally, we have demonstrated CL hyperspectral imaging in an environmental SEM operating with a variable pressure of water vapor. This has allowed us to measure for the first time such insulating

The self-assembled formation of ordered, vertically stacked rocksalt/wurtzite Mg x Zn 1−xO heterostructures by planar phase separation is shown. These heterostructures form quasi “natural” two-dimensional hetero-interfaces between the different phases upon annealing of MgO-oversaturated wurtzite Mg x Zn 1−xO layers grown by plasma-assisted molecular beam epitaxy on c-plane sapphire substrates. The optical absorption spectra show a red shift simultaneous with the appearance of a cubic phase upon annealing at temperatures between 900 °C and 1000 °C. Transmission electron microscopy reveals that these effects are caused by phase separation leading to the formation of a vertically ordered rock salt/wurtzite heterostructures. To explain these observations, we suggest a phase separation epitaxy model that considers this process being initiated by the formation of a cubic (Mg,Zn)Al2O4 spinel layer at the interface to the sapphire substrate, acting as a planar seed for the epitaxial precipitation of rock salt Mg x Zn 1−xO. The equilibrium fraction x of magnesium in the resulting wurtzite (rock salt) layers is approximately 0.15 (0.85), independent of the MgO content of the as-grown layer and determined by the annealing temperature. This model is confirmed by photoluminescence analysis of the resulting layer systems after different annealing temperatures. In addition, we show that the thermal annealing process results in a significant reduction in the density of edge- and screw-type dislocations, providing the possibility to fabricate high quality templates for quasi-homoepitaxial growth.

Combining a yellow-emitting organic material with a blue-emitting inorganic light-emitting device (LED) provides a hybrid white-light LED. This approach, demonstrated by R. W. Martin, P. J. Skabara, and co-workers on page 7290, couples very efficient blue emission with the flexibility, fast modulation speed, and cost effectiveness of the organic material. For the latter, BODIPY is used as the emitter and linked to a conjugated unit designed to efficiently absorb a suitable fraction of the blue light.

We are now all familiar with the bright blue, green and white LEDs that light up our electronic appliances; decorate our streets and buildings and illuminate airport runways. However, the ultimate performance of these nitride semiconductor based LEDs is limited by extended defects such as threading dislocations (TDs), partial dislocations (PDs) and stacking faults (SFs). If we want to develop LEDs to be an effective replacement for the light bulb, or have sufficient power to purify water; we need to eliminate these defects as they act as scattering centres for light and charge carriers and give rise to nonradiative recombination and to leakage currents, severely limiting device performance. The capability to rapidly detect and analyze TDs, PDs and SFs, with negligible sample preparation, represents a real step forward in the development of more efficient nitride-based semiconductor devices

Optoelectronic devices based on the III-nitride system exhibit remarkably good optical efficiencies despite suffering from a large density of defects. In this work we use cathodoluminescence (CL) hyperspectral imaging to study InGaN/GaN multiple quantum well (MQW) structures. Different types of trench defects with varying trench width, namely wide or narrow trenches forming closed loops and open loops, are investigated in the same hyperspectral CL measurement. A strong redshift (≈90 meV) and intensity increase of the MQW emission is demonstrated for regions enclosed by wide trenches, whereas those within narrower trenches only exhibit a small redshift (≈10 meV) and a slight reduction of intensity compared with the defect-free surrounding area. Transmission electron microscopy (TEM) showed that some trench defects consist of a raised central area, which is caused by an increase of about 40% in the thickness of the InGaN wells. The causes of the changes in luminescences are also discussed in relation to TEM results identifying the underlying structure of the defect. Understanding these defects and their emission characteristics is important for further enhancement and development of light-emitting diodes.

Threading dislocations, stacking faults, and associated partial dislocations significantly degrade the optical and electrical properties of materials such as non-polar III-nitride semiconductor thin films. Stacking faults are generally difficult to detect and quantify with existing characterization techniques. We demonstrate the use of electron channeling contrast imaging in the scanning electron microscope to non-destructively reveal basal plane stacking faults terminated by partial dislocations in m-plane GaN and InGaN/GaN multiple quantum well structures grown on γ-LiAlO2 by metal organic vapor phase epitaxy.