Cathodoluminescence Hyperspectral Imaging Research Articles

3D Perovskite Passivation with a Benzotriazole-Based 2D Interlayer for High-Efficiency Solar Cells.

2H-Benzotriazol-2-ylethylammonium bromide and iodide and its difluorinated derivatives are synthesized and employed as interlayers for passivation of formamidinium lead triiodide (FAPbI3) solar cells. In combination with PbI2 and PbBr2, these benzotriazole derivatives form two-dimensional (2D) Ruddlesden-Popper perovskites (RPPs) as evidenced by their crystal structures and thin film characteristics. When used to passivate n-i-p FAPbI3 solar cells, the power conversion efficiency improves from 20% to close to 22% by enhancing the open-circuit voltage. Quasi-Fermi level splitting experiments and scanning electron microscopy cathodoluminescence hyperspectral imaging reveal that passivation provides a reduced nonradiative recombination at the interface between the perovskite and hole transport layer. Photoluminescence spectroscopy, angle-resolved grazing-incidence wide-angle X-ray scattering, and depth profiling X-ray photoelectron spectroscopy studies of the 2D/three-dimensional (3D) interface between the benzotriazole RPP and FAPbI3 show that a nonuniform layer of 2D perovskites is enough to passivate defects, enhance charge extraction, and decrease nonradiative recombination.

Nanoscale Mapping of Light Emission in Nanospade-Based InGaAs Quantum Wells Integrated on Si(100): Implications for Dual Light-Emitting Devices.

III–V semiconductors outperform Si in many optoelectronics applications due to their high carrier mobility, efficient light emission and absorption processes, and the possibility to engineer their band gap through alloying. However, complementing Si technology with III–V semiconductors by integration on Si(100) remains a challenge still today. Vertical nanospades (NSPDs) are quasi-bi-crystal III–V nanostructures that grow on Si(100). Here, we showcase the potential of these structures in optoelectronics application by demonstrating InGaAs heterostructures on GaAs NSPDs that exhibit bright emission in the near-infrared region. Using cathodoluminescence hyperspectral imaging, we are able to study light emission properties at a few nanometers of spatial resolution, well below the optical diffraction limit. We observe a symmetric spatial luminescence splitting throughout the NSPD. We correlate this characteristic to the structure’s crystal nature, thus opening new perspectives for dual wavelength light-emitting diode structures. This work paves the path for integrating optically active III–V structures on the Si(100) platform.

Defect characterization of {101¯3} GaN by electron microscopy

Advances in obtaining untwinned (101¯3)-oriented semi-polar GaN enable a new crystal orientation for the growth of green and red LED structures. We present a scanning electron microscopy study that combines the structural characterization of electron channeling contrast imaging with the optical characterization of cathodoluminescence hyperspectral imaging on a (101¯3) GaN layer. An extensive defect analysis revealed that the dominant defects consist of basal plane stacking faults (BSFs), prismatic stacking faults, partial dislocations, and threading dislocations. With a defect density of about an order of magnitude lower than in comparable. The optical properties of the defects have been characterized from 10 to 320 K, showing BSF luminescence at room temperature indicating a reduced density of non-radiative recombination centers in the as-grown samples compared to established semi- and non-polar orientations. Our findings suggest that growth along (101¯3) has the potential for higher radiative efficiency than established semi-polar orientations.

Correlation between deep-level defects and functional properties of β-(SnxGa1-x)2O3 on Si photodetectors

Heterogeneous integration of β-(SnxGa1−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.

Blue to yellow emission from (Ga,In)/GaN quantum wells grown on pixelated silicon substrate

It is shown that substrate pixelisation before epitaxial growth can significantly impact the emission color of semiconductor heterostructures. The wavelength emission from InxGa1−xN/GaN quantum wells can be shifted from blue to yellow simply by reducing the mesa size from 90 × 90 µm2 to 10 × 10 µm2 of the patterned silicon used as the substrate. This color shift is mainly attributed to an increase of the quantum well thickness when the mesa size decreases. The color is also affected, in a lesser extent, by the trench width between the mesas. Cathodoluminescence hyperspectral imaging is used to map the wavelength emission of the InxGa1−xN/GaN quantum wells. Whatever the mesa size is, the wavelength emission is red-shifted at the mesa edges due to a larger quantum well thickness and In composition.

Structural and luminescence imaging and characterisation of semiconductors in the scanning electron microscope

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.

Luminescence behavior of semipolar (101¯1) InGaN/GaN “bow-tie” structures on patterned Si substrates

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 (101¯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 (101¯1) surfaces. Line defects in ECCI, propagating in the [12¯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.

Scanning electron microscopy as a flexible technique for investigating the properties of UV-emitting nitride semiconductor thin films

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.

Correlated Nanoscale Analysis of the Emission from Wurtzite versus Zincblende (In,Ga)As/GaAs Nanowire Core–Shell Quantum Wells

While the properties of wurtzite GaAs have been extensively studied during the past decade, little is known about the influence of the crystal polytype on ternary (In,Ga)As quantum well structures. We address this question with a unique combination of correlated, spatially resolved measurement techniques on core-shell nanowires that contain extended segments of both the zincblende and wurtzite polytypes. Cathodoluminescence hyperspectral imaging reveals a blue-shift of the quantum well emission energy by 75 ± 15 meV in the wurtzite polytype segment. Nanoprobe X-ray diffraction and atom probe tomography enable k·p calculations for the specific sample geometry to reveal two comparable contributions to this shift. First, there is a 30% drop in In mole fraction going from the zincblende to the wurtzite segment. Second, the quantum well is under compressive strain, which has a much stronger impact on the hole ground state in the wurtzite than in the zincblende segment. Our results highlight the role of the crystal structure in tuning the emission of (In,Ga)As quantum wells and pave the way to exploit the possibilities of three-dimensional band gap engineering in core-shell nanowire heterostructures. At the same time, we have demonstrated an advanced characterization toolkit for the investigation of semiconductor nanostructures.

Influence of InN and AlN concentration on the compositional inhomogeneity and formation of InN-rich regions in InxAlyGa1−x−yN

The application of quaternary InxAlyGa1−x−yN active regions is a promising path towards high efficiency UVB-light emitting diodes (LEDs). For the utilization of InxAlyGa1−x−yN, 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 InxAlyGa1−x−yN 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 InxAlyGa1−x−yN LEDs.

Deep UV Emission from Highly Ordered AlGaN/AlN Core-Shell Nanorods.

Three-dimensional core-shell nanostructures could resolve key problems existing in conventional planar deep UV light-emitting diode (LED) technology due to their high structural quality, high-quality nonpolar growth leading to a reduced quantum-confined Stark effect and their ability to improve light extraction. Currently, a major hurdle to their implementation in UV LEDs is the difficulty of growing such nanostructures from Al xGa1- xN materials with a bottom-up approach. In this paper, we report the successful fabrication of an AlN/Al xGa1- xN/AlN core-shell structure using an original hybrid top-down/bottom-up approach, thus representing a breakthrough in applying core-shell architecture to deep UV emission. Various AlN/Al xGa1- xN/AlN core-shell structures were grown on optimized AlN nanorod arrays. These were created using displacement Talbot lithography (DTL), a two-step dry-wet etching process, and optimized AlN metal organic vapor phase epitaxy regrowth conditions to achieve the facet recovery of straight and smooth AlN nonpolar facets, a necessary requirement for subsequent growth. Cathodoluminescence hyperspectral imaging of the emission characteristics revealed that 229 nm deep UV emission was achieved from the highly uniform array of core-shell AlN/Al xGa1- xN/AlN structures, which represents the shortest wavelength achieved so far with a core-shell architecture. This hybrid top-down/bottom-up approach represents a major advance for the fabrication of deep UV LEDs based on core-shell nanostructures.

Cathodoluminescence studies of chevron features in semi-polar (112¯2) InGaN/GaN multiple quantum well structures

Epitaxial overgrowth of semi-polar III-nitride layers and devices often leads to arrowhead-shaped surface features, referred to as chevrons. We report on a study into the optical, structural, and electrical properties of these features occurring in two very different semi-polar structures, a blue-emitting multiple quantum well structure, and an amber-emitting light-emitting diode. Cathodoluminescence (CL) hyperspectral imaging has highlighted shifts in their emission energy, occurring in the region of the chevron. These variations are due to different semi-polar planes introduced in the chevron arms resulting in a lack of uniformity in the InN incorporation across samples, and the disruption of the structure which could cause a narrowing of the quantum wells (QWs) in this region. Atomic force microscopy has revealed that chevrons can penetrate over 150 nm into the sample and quench light emission from the active layers. The dominance of non-radiative recombination in the chevron region was exposed by simultaneous measurement of CL and the electron beam-induced current. Overall, these results provide an overview of the nature and impact of chevrons on the luminescence of semi-polar devices.

Multi-wavelength emission from a single InGaN/GaN nanorod analyzed by cathodoluminescence hyperspectral imaging

Multiple luminescence peaks emitted by a single InGaN/GaN quantum-well(QW) nanorod, extending from the blue to the red, were analysed by a combination of electron microscope based imaging techniques. Utilizing the capability of cathodoluminescence hyperspectral imaging it was possible to investigate spatial variations in the luminescence properties on a nanoscale. The high optical quality of a single GaN nanorod was demonstrated, evidenced by a narrow band-edge peak and the absence of any luminescence associated with the yellow defect band. Additionally two spatially confined broad luminescence bands were observed, consisting of multiple peaks ranging from 395 nm to 480 nm and 490 nm to 650 nm. The lower energy band originates from broad c-plane QWs located at the apex of the nanorod and the higher energy band from the semipolar QWs on the pyramidal nanorod tip. Comparing the experimentally observed peak positions with peak positions obtained from plane wave modelling and 3D finite difference time domain(FDTD) modelling shows modulation of the nanorod luminescence by cavity modes. By studying the influence of these modes we demonstrate that this can be exploited as an additional parameter in engineering the emission profile of LEDs.

Spatially-resolved optical and structural properties of semi-polar mathrm{(11}bar{2}mathrm{2)} AlxGa1\u2212xN with x up to 0.56

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)} AlxGa1−xN 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.

Characteristics of GaN-based light emitting diodes with different thicknesses of buffer layer grown by HVPE and MOCVD

GaN-based light emitting diodes (LEDs) have been fabricated on sapphire substrates with different thicknesses of GaN buffer layer grown by a combination of hydride vapor phase epitaxy and metalorganic chemical vapor deposition. We analyzed the LED efficiency and modulation characteristics with buffer thicknesses of 12 μm and 30 μm. With the buffer thickness increase, cathodoluminescence hyperspectral imaging shows that the dislocation density in the buffer layer decreases from  ∼1.3  ×  108 cm−2 to  ∼1.0  ×  108 cm−2, and Raman spectra suggest that the compressive stress in the quantum wells is partly relaxed, which leads to a large blue shift in the peak emission wavelength of the photoluminescence and electroluminescent spectra. The combined effects of the low dislocation density and stress relaxation lead to improvements in the efficiency of LEDs with the 30 μm GaN buffer, but the electrical-to-optical modulation bandwidth is higher for the LEDs with the 12 μm GaN buffer. A rate equation analysis suggests that defect-related nonradiative recombination can help increase the modulation bandwidth but reduce the LED efficiency at low currents, suggesting that a compromise should be made in the choice of defect density.

Self-Healing Thermal Annealing: Surface Morphological Restructuring Control of GaN Nanorods

With advances in nanolithography and dry etching, top-down methods of nanostructuring have become a widely used tool for improving the efficiency of optoelectronics. These nano dimensions can offer various benefits to the device performance in terms of light extraction and efficiency, but often at the expense of emission color quality. Broadening of the target emission peak and unwanted yellow luminescence are characteristic defect-related effects due to the ion beam etching damage, particularly for III–N based materials. In this article we focus on GaN based nanorods, showing that through thermal annealing the surface roughness and deformities of the crystal structure can be “self-healed”. Correlative electron microscopy and atomic force microscopy show the change from spherical nanorods to faceted hexagonal structures, revealing the temperature-dependent surface morphology faceting evolution. The faceted nanorods were shown to be strain- and defect-free by cathodoluminescence hyperspectral imaging, micr...

Structural and Optical Emission Uniformity of m-Plane InGaN Single Quantum Wells in Core–Shell Nanorods

Controlling the long-range homogeneity of core–shell InGaN/GaN layers is essential for their use in light-emitting devices. This paper demonstrates variations in optical emission energy as low as ∼7 meV·μm–1 along the m-plane facets from core–shell InGaN/GaN single quantum wells as measured through high-resolution cathodoluminescence hyperspectral imaging. The layers were grown by metal organic vapor phase epitaxy on etched GaN nanorod arrays with a pitch of 2 μm. High-resolution transmission electron microscopy and spatially resolved energy-dispersive X-ray spectroscopy measurements demonstrate a long-range InN-content and thickness homogeneity along the entire 1.2 μm length of the m-plane. Such homogeneous emission was found on the m-plane despite the observation of short-range compositional fluctuations in the InGaN single quantum well. The ability to achieve this uniform optical emission from InGaN/GaN core–shell layers is critical to enable them to compete with and replace conventional planar light-e...

Site controlled red-yellow-green light emitting InGaN quantum discs on nano-tipped GaN rods.

We report a method of growing site controlled InGaN multiple quantum discs (QDs) at uniform wafer scale on coalescence free ultra-high density (>80%) nanorod templates by metal organic chemical vapour deposition (MOCVD). The dislocation and coalescence free nature of the GaN space filling nanorod arrays eliminates the well-known emission problems seen in InGaN based visible light sources that these types of crystallographic defects cause. Correlative scanning transmission electron microscopy (STEM), energy-dispersive X-ray (EDX) mapping and cathodoluminescence (CL) hyperspectral imaging illustrates the controlled site selection of the red, yellow and green (RYG) emission at these nano tips. This article reveals that the nanorod tips' broad emission in the RYG visible range is in fact achieved by manipulating the InGaN QD's confinement dimensions, rather than significantly increasing the In%. This article details the easily controlled method of manipulating the QDs dimensions producing high crystal quality InGaN without complicated growth conditions needed for strain relaxation and alloy compositional changes seen for bulk planar GaN templates.

Influence of stress on optical transitions in GaN nanorods containing a single InGaN/GaN quantum disk

Cathodoluminescence (CL) hyperspectral imaging has been performed on GaN nanorods containing a single InGaN quantum disk (SQD) with controlled variations in excitation conditions. Two different nanorod diameters (200 and 280 nm) have been considered. Systematic changes in the CL spectra from the SQD were observed as the accelerating voltage of the electron beam and its position of incidence are varied. It is shown that the dominant optical transition in the SQD varies across the nanorod as a result of interplay between the contributions of the deformation potential and the quantum-confined Stark effect to the transition energy as consequence of radial variation in the pseudomorphic strain.

Cathodoluminescence Hyperspectral Imaging of Nitride Semiconductors: Introducing New Variables

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