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Funding: LKJ acknowledges funding from UKRI-FLF through MR/T022094/1. LKJ also acknowledges, Professor Iain Baikie for assistance with the work function and APS measurements, and Professor Phil King and Gordon Kentish, School of Physics and Astronomy, University of St Andrews for the XRD measurements and would like to acknowledge (EPSRC): EP/T023449/1. This research used resources of the Advanced Light Source, a U.S. DOE Office of Science User Facility under contract no. DE-AC02-05CH11231. Work was performed at beamline 12.3.2, beamline scientist Nobumichi Tamura. M. A. acknowledges support by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Materials Sciences and Engineering Division under Contract No. DE-AC02-05-CH11231 (D2S2 program KCD2S2). Work at the Molecular Foundry was supported by the Office of Science, Office of Basic Energy Sciences, of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. IDWS acknowledges funding from EPSRC through EP/l017008/1. Indoor photovoltaics are receiving tremendous attention due to the continuous development of the Internet of Things. The present study reports how the fast processing of the triple halide perovskite enables the retention of chlorine and the beneficial role of chlorine in enhancing the indoor light harvesting of a wide bandgap triple anion (TA) perovskite CH3NH3PbI2.6Br0.2Cl0.2. The kinetics of chlorine incorporation/escape investigated by in situ grazing incidence wide-angle X-ray scattering revealed the escape of chlorine after the first ten minutes of thermal annealing and the findings were corroborated with elemental analysis by wavelength dispersive X-ray spectroscopy. The best-performing TA perovskite indoor-photovoltaic device achieved a steady-state power conversion efficiency (PCE) of 25.1% with an output power density of ∼75 μW cm−2 under 1000 lux indoor illumination (0.3 mW cm−2 irradiance). Improved crystalline quality, reduced density of trap states and longer carrier lifetime were achieved by the triple anion alloying method. The detrimental role of the commonly used hole transporting layer (HTL) of Spiro-MeOTAD under indoor lighting conditions leading to J–V hysteresis was also investigated, which could then be effectively suppressed by replacing Spiro-MeOTAD with undoped P3HT. The optimized TA perovskite indoor PV cells were then successfully used to wirelessly power a textile fiber-based temperature sensor. The results from the present study demonstrate a novel route to incorporate chlorine effectively and maximize the steady state power output from halide perovskite indoor photovoltaic devices and their promising potential for the IoT industry. Publisher PDF

The impact of secondary fluorescence on the material compositions measured by X-ray analysis for layered semiconductor thin films is assessed using simulations performed by the DTSA-II and CalcZAF software tools. Three technologically important examples are investigated: AlxGa1−xN layers on either GaN or AlN substrates, InxAl1−xN on GaN, and Si-doped (SnxGa1−x)2O3 on Si. Trends in the differences caused by secondary fluorescence are explained in terms of the propensity of different elements to reabsorb either characteristic or bremsstrahlung X-rays and then to re-emit the characteristic X-rays used to determine composition of the layer under investigation. Under typical beam conditions (7–12 keV), the quantification of dopants/trace elements is found to be susceptible to secondary fluorescence and care must be taken to prevent erroneous results. The overall impact on major constituents is shown to be very small with a change of approximately 0.07 molar cation percent for Al0.3Ga0.7N/AlN layers and a maximum change of 0.08 at% in the Si content of (SnxGa1−x)2O3/Si layers. This provides confidence that previously reported wavelength-dispersive X-ray compositions are not compromised by secondary fluorescence.

Wavelength-dispersive X-ray (WDX) spectroscopy was used to measure silicon atom concentrations in the range 35–100 ppm [corresponding to (3–9) × 1018 cm−3] in doped AlxGa1–xN films using an electron probe microanalyser also equipped with a cathodoluminescence (CL) spectrometer. Doping with Si is the usual way to produce the n-type conducting layers that are critical in GaN- and AlxGa1–xN-based devices such as LEDs and laser diodes. Previously, we have shown excellent agreement for Mg dopant concentrations in p-GaN measured by WDX with values from the more widely used technique of secondary ion mass spectrometry (SIMS). However, a discrepancy between these methods has been reported when quantifying the n-type dopant, silicon. We identify the cause of discrepancy as inherent sample contamination and propose a way to correct this using a calibration relation. This new approach, using a method combining data derived from SIMS measurements on both GaN and AlxGa1–xN samples, provides the means to measure the Si content in these samples with account taken of variations in the ZAF corrections. This method presents a cost-effective and time-saving way to measure the Si doping and can also benefit from simultaneously measuring other signals, such as CL and electron channeling contrast imaging.

We report ultra-high responsivity of epitaxial [Formula: see text] (TGO) Schottky UV-C photodetectors and experimentally identified the source of gain as deep-level defects, supported by first principles calculations. Epitaxial TGO films were grown by plasma-assisted molecular beam epitaxy on (−201) oriented n-type β-[Formula: see text] substrates. Fabricated vertical Schottky devices exhibited peak responsivities as high as 3.5 [Formula: see text] A/W at −5 V applied bias under 250 nm illumination with sharp cutoff shorter than 280 nm and fast rise/fall time in milliseconds order. Hyperspectral imaging cathodoluminescence (CL) spectra were examined to find the mid-bandgap defects, the source of this high gain. Irrespective of different tin mole fractions, the TGO epilayer exhibited extra CL peaks at the green band (∼2.20 eV) not seen in β-[Formula: see text] along with enhancement of the blue emission-band (∼2.64 eV) and suppression of the UV emission-band. Based on hybrid functional calculations of the optical emission expected for defects involving Sn in β-[Formula: see text], VGa–Sn complexes are proposed as potential defect origins of the observed green and blue emission-bands. Such complexes behave as acceptors that can efficiently trap photogenerated holes and are predicted to be predominantly responsible for the ultra-high photoconductive gain in the Sn-alloyed [Formula: see text] devices by means of thermionic emission and electron tunneling. Regenerating the VGa–Sn defect complexes by optimizing the growth techniques, we have demonstrated a planar Schottky UV-C photodetector of the highest peak responsivity.

(Hydroxy)apatite (HAp) [Ca10(PO4)6(OH)2], has emerging potential as a cement coating material, with applications in environmental remediation, nuclear waste storage and architectural preservation. In these low temperature environments and when precipitating from aqueous solution on to a porous substrate, the crystal size, nucleation sites and modified surface properties created are key to designing the most effective coating. In this study we show that bacterial (biogenic) or chemical (abiotic) syntheses on to Portland cement alter these critical performance parameters. We identify that the most significant difference between these two methods is the rate of pH change of the solution during synthesis, as this alters the surface properties and layer structure of HAp formed on cement. We show that iron present in Portland cement is not incorporated into the HAp structure; that formation of nanoparticulate/nanocrystalline HAp begins in the top 20–50 μm of the cement pore structure; and that a slow pH rise in the deposition solution controlled by bacteria metabolic activity leads to a rougher and more hydrophilic HAp coating compared to the abiotic synthesis. The results present the possibility of tailoring the surface topography and hydrophilicity of (hydroxy)apatite coated cement.

Wavelength-dispersive X-ray (WDX) spectroscopy was used to measure silicon atom concentrations in the range 35-100 ppm [corresponding to (3-9) × 1018 cm-3] in doped AlxGa1-xN films using an electron probe microanalyser also equipped with a cathodoluminescence (CL) spectrometer. Doping with Si is the usual way to produce the n-type conducting layers that are critical in GaN- and AlxGa1-xN-based devices such as LEDs and laser diodes. Previously, we have shown excellent agreement for Mg dopant concentrations in p-GaN measured by WDX with values from the more widely used technique of secondary ion mass spectrometry (SIMS). However, a discrepancy between these methods has been reported when quantifying the n-type dopant, silicon. We identify the cause of discrepancy as inherent sample contamination and propose a way to correct this using a calibration relation. This new approach, using a method combining data derived from SIMS measurements on both GaN and AlxGa1-xN samples, provides the means to measure the Si content in these samples with account taken of variations in the ZAF corrections. This method presents a cost-effective and time-saving way to measure the Si doping and can also benefit from simultaneously measuring other signals, such as CL and electron channeling contrast imaging.

A photoluminescence (PL) study of Cu(In,Ga)Se2 (CIGSe) single crystals, (grown by the vertical Bridgman technique) with the [Ga]/[Ga + In] ratio of 7 and 12% and the [Cu]/[In + Ga] ratio greater than unity, as measured by energy dispersive spectroscopy, is presented. Analysis of the excitation intensity and temperature dependence of the PL spectra suggested the excitonic nature of the observed near-band-edge emissions peaks. Free and bound excitons in CIGSe single crystals with both 7 and 12% Ga content are clearly observed, analyzed and identified. An activation energy of 19 meV is determined for the free exciton in the PL spectra of the sample with 12% Ga. The presence of the excitons demonstrated a high structural quality of the material.

Cu2ZnSnSe4 (CZTSe) is amongst leading candidates for the absorber layer in sustainable solar cells. We examine CZTSe thin films with [Cu]/[Zn + Sn] of 0.99 and [Zn]/[Sn] of 1.07, deposited on Mo/glass substrates, and solar cells fabricated from these films. The bandgap (Eg) of the as deposited films and solar cells was examined by photoluminescence excitation (PLE) whereas the temperature and excitation intensity dependence of photoluminescence (PL) spectra was used to examine the nature of radiative recombination. The 6 K PL spectra of CZTSe/Mo exhibit an intense broad and asymmetrical band P1 at 0.822 eV and a lower intensity band P2 at 0.93 eV. The shape of this band, high rates of blue shift with excitation intensity rise ( j-shift) j(P1) = 14 meV and j(P2) = 8 meV per decade, and red shifts of both bands with increasing temperature suggest that both bands are associated with valence band tails due to potential fluctuations caused by high populations of charged defects. The mean depth of such fluctuation γ of 24 meV was estimated from the low energy side of P1. Device processing increased Eg, blue shifted P1, decreased its width, j-shift and the mean depth of potential fluctuations. These can be due to the annealing and/or can partly be related to KCN etching and the chemical effect of Cd, from CdS replacing copper at the CdS–CZTSe interface layer. Processing induced a new broad band P3 at 1.3 eV (quenching with Ea = 200 meV). We attributed P3 to defects in the CdS layer.

We demonstrate a high figure-of-merit UV–C solar-blind photodetectors fabricated from polycrystalline beta-gallium oxide (β-Ga2O3) grown on n-Si substrates by plasma assisted molecular beam epitaxy (PAMBE). We developed film growth sequences for nucleation of Ga2O3 on (100) and (111) oriented Si substrates, and systematically investigate the influence of crucial growth parameters, namely substrate temperature, oxygen flow rate and plasma power on the functional properties of the photodetectors. The photodetectors show ultra-high responsivity of 837 A/W and fast ON/OFF time below 4ms observed under 248 nm illumination at –5V. In addition, they display strong rectifying properties and sharp cut-off below 280 nm with average responsivities between 10-80 A/W, detectivity on the order of 1010 Jones, and rise/fall times between 4 to 500 ms at –5V. High photoconductive gain is shown to likely be due to the mid-bandgap donor/acceptor defect levels, including oxygen vacancies in the form of self-trapped holes. We demonstrate that these defect levels can be modified by controlling the growth conditions, thereby, allowing for tailoring of the photodetector characteristics for specific applications. Our methodology represents a cost-effective solution over homoepitaxial approaches, with characteristics that meet or exceed those reported previously, offering new possibilities for on-wafer integration with Si electronics.

During the epitaxy of AlGaN on sapphire for deep UV emitters, significant lattice mismatch leads to highly strained heterojunctions and the formation of threading dislocations. Combining cathodoluminescence, electron beam induced current and x-ray microanalysis reveal that dislocations with a screw component permeate through a state-of-the-art UVC LED heterostructure into the active region and perturb their local environment in each layer as growth progresses. In addition to acting as non-radiative recombination centers, these dislocations encourage high point defect densities and three-dimensional growth within their vicinity. We find that these point defects can add parasitic recombination pathways and compensate intentional dopants.

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.

Solar cells with the structure ZnO/CdS/Cu2ZnSnSe4/Mo/glass were studied by photoluminescence (PL) before and after irradiation with a dose of 1.8 × 1015 cm−2 and then 5.4 × 1015 cm−2 of 10 MeV electrons carried out at 77 K in liquid nitrogen bath. The low temperature PL spectra before irradiation revealed two bands, a broad and asymmetrical dominant band at 0.94 eV from the CZTSe layer and a lower intensity high energy band (HEB) at 1.3 eV, generated by defects in the CdS buffer layer. Analysis of the excitation intensity and temperature dependencies suggested that the dominant band is free-to-bound (FB): the recombination of free electrons with holes localised at acceptors whose energy levels are affected by potential fluctuations of the valence band due to high concentrations of randomly distributed charged defects. Irradiation did not induce any new band in the examined spectral range (from 0.5 μm to 1.65 μm) but reduced the intensity of both bands in the PL spectra measured at 77 K without warming the cells. The higher the dose the greater was the reduction. After this the cells were warmed to 300 K and moved to a variable temperature cryostat to measure temperature dependencies of the PL spectra. After irradiation the red shift rate of the FB band with temperature rise was found to increase. Electrons displace atoms in the lattice creating primary defects: interstitials and vacancies. These defects recombine during and shortly after irradiation forming secondary defect complexes which work as deep non-radiative traps of charge carriers reducing the PL intensity and increasing the rate of the temperature red shift. Irradiation did not affect the mean depth of the band tails estimated from the shape of the low energy side of the dominant PL band. © 2020 Elsevier Ltd European Commission, EC European Regional Development Fund, FEDER: TK141 Ministry of Science and Higher Education of the Russian Federation: АААА-А18-118020290104-2 The research was supported by the Ministry of Science and Higher Education of the Russian Federation (topic “Spin” № АААА-А18-118020290104-2 ) and the European Union through the European Regional Development Fund, Project TK141 .

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.

Understanding defects and their roles in plastic deformation and device reliability is important for the development of a wide range of novel materials for the next generation of electronic and optoelectronic devices. We introduce the use of gaseous secondary electron detectors in a variable pressure scanning electron microscope for non-destructive imaging of extended defects using electron channelling contrast imaging. We demonstrate that all scattered electrons, including the secondary electrons, can provide diffraction contrast as long as the sample is positioned appropriately with respect to the incident electron beam. Extracting diffraction information through monitoring the modulation of the intensity of secondary electrons as a result of diffraction of the incident electron beam, opens up the possibility of performing low energy electron channelling contrast imaging to characterise low atomic weight and ultra-thin film materials. Our methodology can be adopted for large area, nanoscale structural characterisation of a wide range of crystalline materials including metals and semiconductors, and we illustrate this using the examples of aluminium nitride and gallium nitride. The capability of performing electron channelling contrast imaging, using the variable pressure mode, extends the application of this technique to insulators, which usually require conducting coatings on the sample surface for traditional scanning electron microscope based microstructural characterisation.

We investigate the effects of V-pits on the optical properties of a state-of-the art highly efficient, blue InGaN/GaN multi-quantum-well (MQW) light emitting diode (LED) with high internal quantum efficiency (IQE) of > 80%. The LED is structurally enhanced by incorporating pre-MQW InGaN strain relief layer with low InN content and patterned sapphire substrate. For comparison, a conventional (unenhanced) InGaN/GaN MQW LED (with IQE of 46%) grown under similar conditions was subjected to the same measurements. Scanning transmission electron microscopy (STEM) reveals the absence of V-pits in the unenhanced LED, whereas in the enhanced LED, V-pits with {10-11} facets, emerging from threading dislocations (TDs) were prominent. Cathodoluminescence mapping reveals the luminescence properties near the V-pits, showing that the formation of V-pit defects can encourage the growth of defect-neutralizing barriers around TD defect states. The diminished contribution of TDs in the MQWs allows indium-rich localization sites to act as efficient recombination centers. Photoluminescence and time-resolved spectroscopy measurements suggest that the V-pits play a significant role in the generated carrier rate and droop mechanism, showing that the quantum confined Stark effect is suppressed at low generated carrier density, after which the carrier dynamics and droop are governed by the carrier overflow effect.

Heterogeneous integration of β-(Sn xGa1− x)2O3 (TGO) UV-C photodetectors on silicon substrates by molecular beam epitaxy is demonstrated. Multimodal electron microscopy and spectroscopy techniques reveal a direct correlation between structural, compositional, and optical properties of TGO and the functional properties of the photodetectors. Wavelength dispersive x-ray spectroscopy results accurately determine Sn concentrations ( x) in the region of 0.020, and room temperature cathodoluminescence (CL) hyperspectral imaging shows changes in the CL emission intensity in TGO compared with a Ga2O3 sample with no Sn. Alloying Ga2O3 with Sn is shown to quench the red emission and enhance the blue emission. The increase in blue emission corresponds to the rise in VGa-related deep acceptors responsible for the high gain observed in the TGO detectors. A Ga2O3 nucleation layer is shown to improve the TGO surface quality and give better device properties compared to TGO grown directly onto the Si substrate, including a higher specific detectivity on the order of 1012 Jones.

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.

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.

The application of quaternary In x Al y Ga1−x− y N active regions is a promising path towards high efficiency UVB-light emitting diodes (LEDs). For the utilization of In x Al y Ga1−x−y N, detailed knowledge of the interplay between growth parameters, adatom incorporation, optical and structural properties is crucial. We investigated the influence of the trimethylaluminium (TMAl) and trimethylindium (TMIn) flux on the composition and luminescence properties of In x Al y Ga1−x−y N layers by multi-mode scanning electron microscopy. We found that varying the molar TMIn flow from 0 to 17.3 μmol min−1 led to an InN concentration between 0% and 3.2% and an emission energy between 4.17 and 3.75 eV. The variation of the molar TMAl flow from 3.5 to 35.4 μmol min−1 resulted in a AlN composition between 7.8% and 30.7% with an emission energy variation between 3.6 and 4.1 eV. Cathodoluminescence hyperspectral imaging provided evidence for the formation of nanoscale InN-rich regions. Analyzing the emission properties of these InN-rich regions showed that their emission energy is inhomogeneous and varies by ≈150 meV. We provide evidence that the formation of these InN-rich regions is highly dependent on the AlN and InN composition of the layer and that their formation will strongly affect the performance of In x Al y Ga1−x−y N LEDs.

Small gold nanorods have a significantly large absorption/scattering ratio and are especially beneficial in exploiting photothermal effects, for example in photothermal therapy and remote drug release. This work systematically investigates the influence of growth conditions on the size, growth yield and stability of small gold nanorods. The silver-assisted seed-mediated growth method was optimised to synthesize stable small gold nanorods with a high growth yield (>85%). Further study on the influence of silver ions on the growth facilitates the growth of small gold nanorods with tuneable longitudinal surface plasmon resonance from 613 nm to 912 nm, with average dimensions of 13-25 nm in length and 5-6 nm in diameter. Moreover, the small gold nanorods were successfully functionalized with thiol- modified hairpin oligonucleotides (hpDNA) labelled with Cy5. Fluorescence intensity measurements show an increase in the presence of target DNA and an enhanced signal/background ratio when the longitudinal surface plasmon resonance of small gold nanorods overlaps with the excitation and emission wavelength of Cy5. This coincides with a reduced fluorescence lifetime of Cy5 in the hairpin structure, indicating surface plasmon resonance enhanced energy transfer to the small gold nanorods. This study may provide insight on the synthesis and functionalization of small gold nanorods in biomedical sensing and therapy.

Threading dislocations in thick layers of InxGa1−xN (5% 12%, the facets of the V-defect featured dislocation bundles instead of the low indium fraction region. In this sample, the origin of the dark halo may relate to a compound effect of the dislocation bundles, of a variation of surface potential, and perhaps, of an increase in carrier diffusion length.

The effect of solar cell processing (including etching in KCN along with deposition of CdS and ZnO) on photoluminescence (PL) spectra and bandgap E g (measured at 4.2 K by photoluminescence excitation) of Cu 2 ZnSnSe 4 films, produced by selenising metallic precursors at 450 °C, 500 °C and 550 °C, was studied. Temperature and excitation intensity analysis of the P1 dominant band in the PL spectra of solar cells suggests that after processing this band still can be assigned to the free-to-bound recombination of free electrons with holes bound at deep acceptor levels influenced by valence band-tails. However processing increased the intensity of P1 and blue shifted it. The strongest effect was observed for the film selenised at 500 °C. For the film selenised at 450 °C the blue shift and increase in the intensity were smaller and only a slight intensity rise was found for the film selenised at 550 °C. The intensity increase we assign to a reduction in the concentration of non-radiative recombination centers on the surface because of the etching and changes in doping due to inter-diffusion of Cd, S, Se and Zn after the deposition of CdS. Such an inter-diffusion depends on the elemental composition of the films defining the chemistry of defects and influencing E g which increased in the film selenised at 500 °C but decreased in the other films. Processing increased the P1 shift rate (j-shift) with excitation power change in all the films demonstrating a higher compensation degree in the solar cells which is consistent with the formation of an interface layer containing new donors Cd Cu . © 2019 Elsevier B.V.

International audience; This paper reports a cathodoluminescence (CL) spectroscopic study of nanogranular AlNOErx samples with erbiumcontent, x, in the range 0.5–3.6 at%. A wide range of erbium concentration was studied with the aim ofunderstanding the concentration quenching of CL. The composition of thin films, deposited by radiofrequencyreactive magnetron sputtering, was accurately determined by Energy Dispersive X-ray Spectroscopy (EDS). CLemission was investigated in the extended visible spectral range from 350 nm to 850 nm. The critical concentrationof luminescent activator Er3+ above which CL quenching occurs is 1%; the corresponding criticaldistance between Er3+ ions in AlNOErx is about 1.0 nm. The quenching mechanism is discussed. We discount anexchange-mediated interaction in favour of a multipole-multipole phonon-assisted interaction.

Cu2ZnSnSe4 (CZTSe) is one of the leading candidates for the absorber layer in sustainable solar cells. Thin films of CZTSe with a near stoichiometric [Cu]/[Zn + Sn] were used to produce solar cells with conversion efficiency η = 6.4% by a standard solar cell processing including KCN etching and the deposition of CdS and ZnO. Both CZTSe films and solar cells were examined using photoluminescence (PL) to analyse the nature of radiative recombination and photoluminescence excitation (PLE) at 4.2 K to determine the bandgap (E g). Low temperature PL spectra of the films reveal an intense band P1 at 0.81 eV and a low intensity band P2 at 0.93 eV. Their temperature and excitation intensity dependencies suggest that they both involve recombinations of free electrons with holes localised at acceptors with the energy level influenced by potential fluctuations in the valence band. We associate P1 and P2 with different fractions of CZTSe: with a lower and higher degree of order of Cu and Zn on the cation sub-lattice, respectively. Device processing reduced the intensity of P1 by 2.5 whereas the intensity of P2 increased by a 1.5. We assign this to a low temperature annealing due to CdS and ZnO deposition which increased the fraction of CZTSe with high degree of Cu/Zn order and decreased the fraction with low degree of Cu/Zn order. Device processing increased E g, blue shifted P1, decreased its width, j-shift and the mean depth of potential fluctuations. These can also be related to the annealing and/or KCN etching and the chemical effect of Cd, due to CdS replacing copper at the CdS-CZTSe interface layer. Processing induced a new broad band P3 at 1.3 eV (quenching with E a = 200 meV) which we attributed to defects in the CdS layer. © 2018 IOP Publishing Ltd.

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.

The spectroscopic techniques of cathodoluminescence (CL) and photoluminescence (PL) are used to study the origin of red emission in β-Ga 2O 3 grown using the edge-defined film-fed grown (EFG) method and hydride vapor phase epitaxy. Room-temperature CL shows red emission peaks from samples doped with Fe, Sn, and Si and from unintentionally doped (UID) samples. Narrow emission lines around 690 nm are seen strongly in the Fe and UID samples. Temperature-dependent PL analysis of the two prominent red emission lines reveals properties similar to the R lines in sapphire for all samples but with different levels of emission intensities. These lines are attributed to Cr 3+ ionic transitions rather than Fe 3+, as reported previously. The most likely origin of the unintentional Cr incorporation is the source material used in the EFG method.

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.

The dual nature of the magnesium acceptor in gallium nitride results in dynamic defect complexes. Europium spectator ions reveal switching between two spectrally unique metastable centers, each corresponding to a particular acceptor state. By ion co-implantation of europium and oxygen into GaN(Mg), we produce, in addition, an anchored state system. In doing so, we create an abundance of previously unidentified stable centers, which we denote as “Eu0(Ox).” We introduce a microscopic model for these centers with oxygen substituting for nitrogen in the bridging site.

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...

Cu2ZnSnSe4 (CZTSe) is a semiconductor used as the absorber layer in highly promising sustainable thin film solar cells. The authors study the effect of Ar+ etching of copper deficient and zinc excess CZTSe thin films deposited on Mo/glass substrates on the surface elemental composition, measured by x-ray photoelectron spectroscopy, and photoluminescence (PL) spectra. Low temperature PL spectra reveal a broad asymmetrical band at 0.95 eV. The temperature and excitation intensity dependencies of this band suggest that it is a free-to-bound (FB) recombination of electrons from the conduction band with holes localized at an acceptor affected by potential fluctuations. The surface composition of the as grown films demonstrates a strong copper deficiency: [Cu]/[Zn + Sn] = 0.33. The etching of the film surface using Ar+ beam increases [Cu]/[Zn + Sn] to 0.51, which is significantly smaller than that of 0.78 in the bulk, measured by wavelength dispersive x-ray analysis, demonstrating the presence on the surface of a copper-depleted layer. The Ar+ etching drastically reduces the FB band intensity by a factor of 4.5, broadens it and develops a low energy tail. Ar ions displace atoms in CZTSe lattice creating primary radiation defects, vacancies, and interstitials, which recombine at room temperature forming antisite defects with deep energy levels. Some of them generate the observed low energy tail and increase the mean depth of potential fluctuation γ, determined from the shape of the low energy side of FB band, from 24 meV before Ar+ etching to 35 meV after. Other deep defects work as nonradiative recombination centers reducing the intensity of the FB band. © 2018 Author(s).

Europium is the most-studied and least-well-understood rare earth ion (REI) dopant in GaN. While attempting to increase the efficiency of red GaN light-emitting diodes (LEDs) by implanting Eu+ into p-type GaN templates, the Strathclyde University group, in collaboration with IST Lisbon and Unipress Warsaw, discovered hysteretic photochromic switching (HPS) in the photoluminescence spectrum of doubly doped GaN(Mg):Eu. Our recent work, summarised in this contribution, has used time-, temperature- and light-induced changes in the Eu intra-4f shell emission spectrum to deduce the microscopic nature of the Mg-Eu defects that form in this material. As well as shedding light on the Mg acceptor in GaN, we propose a possible role for these emission centres in quantum information and computing.

International audience; The structural properties of Er-doped AlNO epilayers grown by radio frequency magnetron sputtering were studied by Extended X-ray Absorption Fine Structure (EXAFS) spectra recorded at the Er L 3 edge. The analysis revealed that Er substitutes for Al in all the studied samples and the increase in Er concentration from 0.5 to 3.6 at.% is not accompanied by formation of ErN, Er 2 O 3 or Er clusters. Simultaneously recorded X-ray Absorption Near Edge Structure (XANES) spectra verify that the bonding configuration of Er is similar in all studied samples. The Er-N distance is 2 constant at 2.18-2.19 Å i.e. approximately 15% larger than the Al-N bondlength, revealing that the introduction of Er in the cation sublattice causes considerable local distortion. The Debye-Waller factor, which measures the static disorder, of the second nearest shell of Al neighbors, has a local minimum for the sample containing 1% Er that coincides with the highest photoluminescence efficiency of the sample set.

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.

Europium is the most-studied and least-well-understood rare earth ion (REI) dopant in GaN. While attempting to increase the efficiency of red GaN light-emitting diodes (LEDs) by implanting Eu+ into p-type GaN templates, the Strathclyde University group, in collaboration with IST Lisbon and Unipress Warsaw, discovered hysteretic photochromic switching (HPS) in the photoluminescence spectrum of doubly doped GaN(Mg):Eu. Our recent work, summarised in this contribution, has used time-, temperature- and light-induced changes in the Eu intra-4f shell emission spectrum to deduce the microscopic nature of the Mg-Eu defects that form in this material. As well as shedding light on the Mg acceptor in GaN, we propose a possible role for these emission centres in quantum information and computing.

In our original paper, we estimated the maximum field of view (FOV) that would result when collecting luminescence over a cone half-angle u and coupling this into a spectrograph with a given f /number and a slit width d. Due to the use of the low-angle approximation outwith the paraxial regime, the expression given in Equation 2 used the tangent of the angle rather than the correct sine function.

We present a simple and robust method to acquire quantitative maps of compositional fluctuations in nanostructures from low magnification high-angle annular dark field (HAADF) micrographs calibrated by energy-dispersive X-ray (EDX) spectroscopy in scanning transmission electron microscopy (STEM) mode. We show that a nonuniform background in HAADF-STEM micrographs can be eliminated, to a first approximation, by use of a suitable analytic function. The uncertainty in probe position when collecting an EDX spectrum renders the calibration of HAADF-STEM micrographs indirect, and a statistical approach has been developed to determine the position with confidence. Our analysis procedure, presented in a flowchart to facilitate the successful implementation of the method by users, was applied to discontinuous InGaN/GaN quantum wells in order to obtain quantitative determinations of compositional fluctuations on the nanoscale.

We present an optical spectroscopy study of Cu2ZnSnSe4 (CZTSe) thin films deposited on Mo/glass substrates. The [Cu]/[Zn+Sn] ratio in these films varies from nearly stoichiometric to strongly Cu deficient and Zn rich. Increasing Cu deficiency and Zn excess widens the bandgap Egdetermined using photoluminescence excitation (PLE) at 4.2 K, from 0.99 eV to 1.03 eV and blue shifts the dominant band in the photoluminescence (PL) spectra from 0.83 eV to 0.95 eV. The PL spectra of the near stoichiometric film reveal two bands: a dominant band centred at 0.83 eV and a lower intensity one at 0.93 eV. The temperature and excitation intensity dependence of the PL spectra help to identify the recombination mechanisms of the observed emission bands as free-to-bound: recombination of free electrons with holes localised at acceptors affected by randomly distributed potential fluctuations. Both the mean depth of such fluctuations, determined by analysing the shape of the dominant bands, and the broadening energy, estimated from the PLE spectra, become smaller with increasing Cu deficiency and Zn excess which also widens Eg due to an improved ordering of the Cu/Zn atoms. These changes in the elemental composition induce a significant blue shift of the PL bands exceeding the Eg widening. This is attributed to a change of the dominant acceptor for a shallow one, and is beneficial for the solar cell performance. Film regions with a higher degree of Cu/Zn ordering are present in the near stoichiometric film generating the second PL band at 0.93 eV. © 2017

Detailed knowledge of the dopant concentration and composition of wide band gap AlxGa1−xN layers is of crucial importance for the fabrication of ultra violet (UV) light emitting diodes (LEDs). This paper demonstrates the capabilities of wavelength dispersive X-ray (WDX) spectroscopy in accurately determining these parameters and compares the results with those from high resolution X-ray diffraction (HR-XRD) and secondary ion mass spectrometry (SIMS). WDX spectroscopy has been carried out on different silicon-doped wide bandgap AlxGa1−xN samples (x between 0.80 and 1). This study found a linear increase in the Si concentration with the SiH4/group-III ratio, measuring Si concentrations between 3×1018 cm−3 and 2.8×1019 cm−3, while no direct correlation between the AlN composition and the Si incorporation ratio was found. Comparison between the composition obtained by WDX and by HR-XRD showed very good agreement in the range investigated, while comparison of the donor concentration between WDX and SIMS found only partial agreement, which we attribute to a number of effects.

Although p-type activation of GaN by Mg underpins a mature commercial technology, the nature of the Mg acceptor in GaN is still controversial. Here, we use implanted Eu as a ‘spectator ion’ to probe the lattice location of Mg in doubly doped GaN(Mg):Eu. Photoluminescence spectroscopy of this material exemplifies hysteretic photochromic switching (HPS) between two configurations, Eu0 and Eu1(Mg), of the same Eu-Mg defect, with a hyperbolic time dependence on ‘switchdown’ from Eu0 to Eu1(Mg). The sample temperature and the incident light intensity at 355 nm tune the characteristic switching time over several orders of magnitude, from less than a second at 12.5 K, ~100 mW/cm2 to (an estimated) several hours at 50 K, 1 mW/cm2. Linking the distinct Eu-Mg defect configurations with the shallow transient and deep ground states of the Mg acceptor in the Lany-Zunger model, we determine the energy barrier between the states to be 27.7(4) meV, in good agreement with the predictions of theory. The experimental results further suggest that at low temperatures holes in deep ground states are localized on N atoms axially bonded to Mg acceptors.

Rare-earth doped III-N semiconductors have been studied for decades on account of their possible application in visible light-emitting diodes (LED) with built-in utility as red (e.g. Eu), green (Er) and blue (Tm) monochromatic sources (O'Donnell and Dierolf (eds.), Topics in Applied Physics, Vol. 124 (Springer, Dordrecht, 2010) [1]). However, to date, no commercial devices have been introduced on the basis of these materials. Recently, we discovered thermally activated hysteresis in the emission spectrum of p-type GaN thin films that were co-doped with Mg and Eu (O'Donnell et al., Proc. ICPS31, Zurich, July 2012 [2]). We have also reported an unexpected Zeeman splitting and induced magnetic moment of Eu3+ ions in GaN (Kachkanov et al., Scientific Rep. 2, 969 (2012) and MRS Proc. 1290–i03–06 (2011) [3, 4]). These findings encourage speculation on taking the study of RE-doped III-N beyond the limited goal of improving LED efficiency into the realm of novel magneto-optic and quantum-optical devices. In particular we will describe in this presentation the spectroscopy of ion-implanted and annealed GaN(Mg): Eu samples and the possible exploitation of the Mg acceptor in GaN as a qubit.

Sequential multiple Eu ion implantations at low fluence (1×1013 cm-2 at 300 keV) and subsequent rapid thermal annealing (RTA) steps (30 s at 1000 °C or 1100 °C) were performed on high quality nominally undoped GaN films grown by metal organic chemical vapour deposition (MOCVD) and medium quality GaN:Mg grown by hydride vapour phase epitaxy (HVPE). Compared to samples implanted in a single step, multiple implantation/annealing shows only marginal structural improvement for the MOCVD samples, but a significant improvement of crystal quality and optical activation of Eu was achieved in the HVPE films. This improvement is attributed to the lower crystalline quality of the starting material, which probably enhances the diffusion of defects and acts to facilitate the annealing of implantation damage and the effective incorporation of the Eu ions in the crystal structure. Optical activation of Eu3+ ions in the HVPE samples was further improved by high temperature and high pressure annealing (HTHP) up to 1400 °C. After HTHP annealing the main room temperature cathodo- and photoluminescence line in Mg-doped samples lies at ∼ 619 nm, characteristic of a known Mg-related Eu3+ centre, while after RTA treatment the dominant line lies at ∼ 622 nm, typical for undoped GaN:Eu. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. ispartof: pages:253-257 ispartof: Physica Status Solidi C vol:11 issue:2 pages:253-257 ispartof: E-MRS Spring Meeting / Symposium J - Semicond Nanostructures towards Elect and Optoelectron Device Applicat - IV / Symposium L - Grp III Nitrides / Symposium P - Funct Nanowires - Synth, Characterizat and Applicat location:Strasbourg: FRANCE date:27 May - 31 May 2013 status: published

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.