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At least 91 records · Page 5

Role of defects in ultra-high gain in fast planar tin gallium oxide UV-C photodetector by MBE

Here we report ultra-high responsivity of epitaxial (Sn x Ga 1–x ) 2 O 3 (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-Ga 2 O 3 substrates. Fabricated vertical Schottky devices exhibited peak responsivities as high as 3.5 ×10 4 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-Ga 2 O 3 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-Ga 2 O 3 , V Ga –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 Ga 2 O 3 devices by means of thermionic emission and electron tunneling. Regenerating the V Ga –Sn defect complexes by optimizing the growth techniques, we have demonstrated a planar Schottky UV-C photodetector of the highest peak responsivity.

36 MATERIALS SCIENCE↗

Optoelectronic and structural characterization of trapezoidal defects in 4H-SiC epilayers and the effect on MOSFET reliability

To this day, trapezoidal defects are found in clusters and high counts in wafers representing the industry standard in terms of material quality being produced. This study sheds light on the nature, origin, behavior, and impact of this defect on device yield and reliability. Trapezoidal defects in 4H-SiC epitaxial layers were investigated by photoluminescence (PL) imaging, scanning electron microscopy (SEM), cathodoluminescence spectrum imaging (CLSI), SEM electron beam induced current (EBIC) imaging, and by transmission electron microscopy (TEM) observation. The bar-shaped stacking faults were identified by the PL and CL measurements with a peak emission wavelength of 420 and 450 nm. An optoelectronic behavioral study based on the recombination enhanced dislocation glide mechanism revealed how expanding dislocations and stacking faults interact with each other. Combining the luminescence and microscopy results, the nature of the stacking faults was identified as being a combination of Shockley-type and Frank-type stacking faults. The TEM analysis showed that these defects originate from the substrate and the stacking sequences of some of the faults were determined as (…2, 4, 2…) and (…2, 3, 2…) in the Zhdanov's notation by high-resolution TEM. The origin of this defect is speculated based on our results and previous reports. The EBIC imaging showed that the high density of SFs in these towers is a strong site of carrier recombination, which presumably has an impact on the transfer characteristics of SiC devices. Furthermore, these defects have shown to impact metal oxide semiconductor field effect transistors electrical performance via an increase in the on-state resistance depending on the coverage percentage of the tower of defects in the active area of the device.

4H-SiC↗

Nanoscale imaging of He-ion irradiation effects on amorphous TaO x toward electroforming-free neuromorphic functions

Resistive switching in thin films has been widely studied in a broad range of materials. Yet, the mechanisms behind electroresistive switching have been persistently difficult to decipher and control, in part due to their non-equilibrium nature. Here, we demonstrate new experimental approaches that can probe resistive switching phenomena, utilizing amorphous TaO x as a model material system. Specifically, we applied scanning microwave impedance microscopy and cathodoluminescence (CL) microscopy as direct probes of conductance and electronic structure, respectively. These methods provide direct evidence of the electronic state of TaO x despite its amorphous nature. For example, CL identifies characteristic impurity levels in TaO x , in agreement with first principles calculations. We applied these methods to investigate He-ion-beam irradiation as a path to activate conductivity of materials and enable electroforming-free control over resistive switching. However, we find that even though He-ions begin to modify the nature of bonds even at the lowest doses, the films' conductive properties exhibit remarkable stability with large displacement damage and they are driven to metallic states only at the limit of structural decomposition. Finally, we show that electroforming in a nanoscale junction can be carried out with a dissipated power of <20 nW, a much smaller value compared to earlier studies and one that minimizes irreversible structural modifications of the films. Importantly, the multimodal approach described here provides a new framework toward the theory/experiment guided design and optimization of electroresistive materials.

36 MATERIALS SCIENCE↗

Excitonic and deep-level emission from N- and Al-polar homoepitaxial AlN grown by molecular beam epitaxy

Using low-temperature cathodoluminescence spectroscopy, we study the properties of N- and Al-polar AlN layers grown by molecular beam epitaxy on bulk AlN{0001}. Compared with the bulk AlN substrate, layers of both polarities feature a suppression of deep-level luminescence, a total absence of the prevalent donor with an exciton binding energy of 28 meV, and a much increased intensity of the emission from free excitons. The dominant donor in these layers is characterized by an associated exciton binding energy of 13 meV. The observation of excited exciton states up to the exciton continuum allows us to directly extract the Γ 5 free exciton binding energy of 57 meV.

42 ENGINEERING↗

Multimodal microscopy of extended defects in β-Ga 2 O 3 (010) EFG crystals

Beta-phase gallium oxide (β-Ga 2 O 3 ) has attracted attention in recent years as a potentially low cost, large area substrate and active layer material for high power, high temperature power electronics and sensing devices. However, growth of β-Ga 2 O 3 crystals is complicated by easily activated (100) and (001) cleavage planes, the presence of low angle grain boundaries (LAGBs) and twins, and the potential formation of polycrystalline grains. In this study, β-Ga 2 O 3 crystals were grown by the edge-defined film-fed growth technique with an (010) principal face. Two crystals with apparently randomly formed high angle grain boundaries (HAGBs) were selected and analyzed by electron backscatter diffraction, electron channeling contrast imaging, and cathodoluminescence to investigate the nature of the LAGBs and the source of the HAGB formation. It was discovered that planar LAGBs lying parallel to the (010) plane exist in the region immediately preceding the start of an HAGB. Increased misorientation across the LAGB was observed, approaching the initiation of a new grain. We present multimodal microscopy characterization, correlating misorientation and variation in optoelectronic properties with LAGBs and the associated dislocations.

14 SOLAR ENERGY↗

Impact of metal diffusion, lattice distortions, native defects, and ambient on dielectric breakdown in Ni–Ga 2 O 3 Schottky diodes

Ga 2 O 3 unipolar devices are of high interest due to their ~8 MV/cm predicted breakdown fields, which have not yet been achieved due to premature device failure. Pre- and post-failure defect analysis of Ni–Ga 2 O 3 Schottky diodes in ultrahigh vacuum (UHV) and air were performed using depth-resolved cathodoluminescence, high angle annular dark field scanning transmission electron microscopy, and energy dispersive x-ray analysis to understand the physical mechanisms that precede premature breakdown. The breakdown voltage in UHV was dramatically reduced by nearly 40% compared with the breakdown in air. This reduction in the breakdown voltage correlated with post-breakdown differences in Ni distribution, indicating that the coordination and bonding of Ni contribute strongly to electrical behavior in Ni–Ga 2 O 3 Schottky diodes. Breakdown studies in UHV revealed that Ni diffuses away more from the metal–semiconductor interface than with air breakdown, where Ni localizes more near the interface, indicative of the preferential formation of a Ni oxide under O-poor conditions. These measurements also identified the formation of divacancy-interstitial complexes and their characteristic luminescence signature ~150 nm from the interface, the densities of which correlated with breakdown fields. These findings show that electric-field-induced degradation occurs via the rearrangement of native point defects, which act as an additional precursor to device failure. Macroscopically, they show the impact of both vacuum conditions and metal reactivity on Ga 2 O 3 device fabrication.

36 MATERIALS SCIENCE↗

Microstructure-Property Relationships in Epitaxial Cu(In, Ga)Se2 Solar-Cell Absorbers

Epitaxially grown Cu(In,Ga)Se 2 (CIGS) absorber layers were analyzed by various techniques in scanning electron microscopy in order to reveal microstructure-property relationships in these thin films. Owing to their epitaxial nature, these CIGS absorber layers do not contain any grain boundaries, but only anti-phase domains (APDs) and dislocations. By combining electron channeling-contrast imaging, electron backscatter diffraction, and cathodoluminescence (CL), in some cases on identical specimen positions of polished cross-sections of CIGS/Mo/glass stacks, it was possible to correlate the presence and orientations of APDs and dislocations with the lateral distributions of the CL intensity and emission-peak energy. We studied CIGS layers with three different [Ga]/([Ga]+[In]) ratios as well as with and without NaF/KF treatments. Considerable differences between the CIGS layer properties in the microstructure-property relationships were found, depending on the growth parameters. Dislocations in the epitaxial CIGS layers do not tend to exhibit strong CL intensity decreases, which contrasts with the situation in numerous other semiconductor materials.

anti-phase domains↗

Nanoscale interplay of native point defects near Sr-deficient SrxTiO 3 /SrTiO 3 interfaces

SrTiO 3 has many applications involving interfaces with other materials, but defects that affect the properties of SrTiO 3 films can also play a significant role at its heterointerfaces and even at junctions with nonstoichiometric SrTiO 3 . Depth-resolved cathodoluminescence spectroscopy (DRCLS) combined with systematic cation Sr content reduction in SrxTiO 3 ultrathin films grown on SrTiO 3 showed an interplay of native point defects and electronic structure within the Sr-deficient film and how interplay extends tens of nanometers into the substrate below. Understanding how defects form and affect interface electronic structure during epitaxial growth is central to improving complex oxide devices. Controlling the balance of oxygen vacancy defects with strontium vacancies and other acceptor-like defects can improve control over free carrier densities. Likewise, control over nanoscale defect charge distributions can advance new device features such as two-dimensional hole gases and the performance of existing devices such as ferroelectric tunnel junctions. This study shows how DRCLS directly measures the relative densities and spatial distributions of multiple native defects within and extending away from nanoscale SrxTiO 3 /SrTiO 3 junctions and how their interplay varies with controlled epitaxial growth. In turn, these growth-dependent defect variations can help guide SrTiO 3 epitaxial growth with other complex oxides.

36 MATERIALS SCIENCE↗

Revealing Micro-Scale Doping Variations in Thin-Films via Simultaneous Luminescence and Current Collection Measurements

Doping thin films used for photovoltaic absorbers is both critical to maximize device voltage and challenging due to complex interactions between point defects in these materials. Such interactions can result in compensation of the intended dopant species, meaning that the active charge-carrier concentration is lower than the concentration incorporated dopants. Charge-carrier compensation is directly related to the open-circuit voltage (VOC) deficit, or magnitude of VOC relative to the theoretical limit. Understanding how the carrier concentration varies within thin-films is necessary to design material processing schedules to minimize this VOC deficit and produce more efficient devices. Unfortunately, measurements of the free carrier concentration are generally relevant at the device level and cannot resolve local differences. Resolving local doping differences in thin-films such as Cd(Se,Te), CZTS, and CIGSe requires techniques with micron or sub-micron spatial resolution due to the polycrystalline structure as well as intended and unintended composition variations in these materials. In this contribution, we show how simultaneous measurement of cathodoluminescence (CL) and electron-beam-induced current (EBIC) can be used to expose doping variations in Cd(Se,Te) thin-films. Simultaneous collection of these signals reveals unexpected differences in the electric field strength through the device thickness due to spatial variation in the carrier concentration.

41 EE - Solar Energy Technologies Office (EE-4S)↗

Major to trace element imaging and analysis of iron age glasses using stage scanning in the analytical dual beam microscope (tandem)

Dark and clear silicate glasses formed during an iron age vitrification event ≈ 1500 years ago at the Broborg hillfort near Uppsala, Sweden have been analyzed using a scanning electron microscope equipped with a micro-X-ray fluorescence (μXRF) spectrometer. Correlated µXRF and electron beam-induced energy dispersive spectrometry (EDS) X-ray maps were collected via stage-scanning at constant velocity. This coupled procedure represents a new approach for the cultural heritage community to conduct analytical studies of archaeometric specimens composed of metal, ceramic, or mixed inorganic/organic materials, where major and trace element compositions are registered in space for areas up to the centimeter-length scale at micrometer-scale resolution. Overview images were used to select areas for EDS beam scan maps correlated with multispectral cathodoluminescence (CL) imaging and co-located quantitative EDS and μXRF point analysis. Fe, Ca, Mg, Ti, P, Mn, Zr, Zn, and Y are enriched in the dark glass, while Si, Al, K, Na, Ba, Sr, Rb, and Ga are enriched in the clear glass. Unmelted material is comprised predominately of quartz (SiO 2 ) along with trace apatite (Ca 5 (PO 4 ) 3 [Cl,OH]) and zircon (ZrSiO 4 ). Multivariate statistical analysis was used to measure the area fractions of high variance components while lower variance components represented phase mixtures. Differences between calculated melt viscosities for the glass compositions are consistent with field and laboratory observations. Coupled large area EDS and μXRF imaging shows significant promise for informed selection of higher spatial resolution and higher sensitivity follow-up studies, e.g., those performed using synchrotron analysis.

36 MATERIALS SCIENCE↗

Collaborative R&D with REEL Solar Inc (REEL) to Understand and Overcome Performance Limitations in CdTe Solar Cells: Cooperative Research and Development (Final Report)

This CRADA will focus on processing, advanced characterization, and testing of photovoltaic materials and devices to understand and improve REEL CdTe solar technology. This will include examining process variations and different buffer, absorber, and contact layers from REEL and NLR to maximize performance. The unique and diverse advanced characterization tools at NLR, such as time-resolved photoluminescence, capacitance-voltage measurements, electron beam scattered diffraction, cathodoluminescence, electron microscopy, TOF-SIMS, and other measurements will be applied to characterize REEL processing to improve understanding and guide experimental directions. Accelerated stability and potential induced degradation tests will be used to analyze metastability, short-and-long term degradation, and improve bankability. A second and major thrust this period will be joint development of Si/CdTe tandem solar cells to overcome industry wide terrestrial solar efficiency limits with the two lowest cost and manufacturable solar materials today. This will include developing novel transparent back contacts that can be incorporated into tandem structures and other novel solar applications, detailed analysis of designs and configurations for CdTe/Si tandem modules, and prototyping REEL CdTe Technology with Si bottom cells in tandem structures.

14 SOLAR ENERGY↗

Diverse Electron-Induced Optical Emissions from Space Observatory Materials at Low Temperatures

Electron irradiation experiments have investigated the diverse electron-induced optical and electrical signatures observed in ground-based tests of various space observatory materials at low temperature. Three types of light emission were observed: (i); long-duration cathodoluminescence which persisted as long as the electron beam was on (ii) short-duration (<1 s) arcing, resulting from electrostatic discharge; and (iii) intermediate-duration (~100 s) glow-termed "flares". We discuss how the electron currents and arcing-as well as light emission absolute intensity and frequency-depend on electron beam energy, power, and flux and the temperature and thickness of different bulk (polyimides, epoxy resins, and silica glasses) and composite dielectric materials (disordered SiO2 thin films, carbon- and fiberglass-epoxy composites, and macroscopically-conductive carbon-loaded polyimides). We conclude that electron-induced optical emissions resulting from interactions between observatory materials and the space environment electron flux can, in specific circumstances, make significant contributions to the stray light background that could possibly adversely affect the performance of space-based observatories.

long-duration cathodoluminescence↗

Microstructural Passivation of Patterned Al 2 O 3 Back Contacts on CdS/CdTe Solar Cells

Abstract Patterned aluminum oxide (Al 2 O 3 ) back contact on cadmium telluride (CdTe) solar cells can effectively mitigate the loss of the majority carriers while retaining the passivation benefits for minority carriers. This study investigates the impact of the point‐contact geometry on cell performance, where the spacing of the microholes is systematically varied at a constant microhole diameter (≈16 µm). Microhole arrays are created on an evaporated Al 2 O 3 layer (≈30 nm) on CdTe using laser‐beam lithography and selective wet etching processes. Comparative analysis indicates a significant decrease in fill factor (FF) and short‐circuit current ( I SC ) when the contact fraction falls below 30%, likely due to the Al 2 O 3 barrier impeding majority carriers. Above this fraction, FF and I SC are comparable to those of baseline CdTe cells without Al 2 O 3 . Open‐circuit voltage ( V OC ) shows a gradual decrease as Al 2 O 3 coverage is reduced but exhibits a slight increase (<15 mV) when the contact fraction exceeds 30%. Cathodoluminescence (CL) characterization reveals that significantly improved radiative recombination occurs within the CdTe grain bulk with Al 2 O 3 , whereas this effect on grain boundaries is minimal. The findings imply complex local carrier dynamics in the patterned back‐contact region, closely tied to the microstructural properties of CdTe‐based solar cells.

Roy, Etee Kawna↗

Electron-Beam-Related Studies of Halide Perovskites: Challenges and Opportunities

Electron beam microscopy and related characterization techniques play an important role in revealing the microstructural, morphological, physical, and chemical information of halide perovskites and their impact on associated optoelectronic devices. However, electron beam irradiation usually causes damage to these beam-sensitive materials, negatively impacting their device performance, and complicating this interpretation. Here, the electron microscopy and spectroscopy techniques are reviewed that are crucial for the understanding of the crystallization and microstructure of halide perovskites. In addition, special attention is paid to assessing and mitigating the electron beam-induced damage caused by these techniques. Since the halide perovskites are fragile, a protocol involving delicate control of both electron beam dose and dose rate, coupled with careful data analysis, is key to enable the acquisition of reliable structural and compositional information such as atomic-resolution images, chemical elemental mapping and electron diffraction patterns. Limiting the electron beam dose is critical parameter enabling the characterization of various halide perovskites. Novel methods to unveil the mechanisms of device operation, including charge carrier generation, diffusion, and extraction are presented in scanning electron microscopy studies combined with electron-beam-induced current and cathodoluminescence mapping. Future opportunities for electron-beam-related characterizations of halide perovskites are also discussed.

36 MATERIALS SCIENCE↗

Vacuum-Healing of Grain Boundaries in Sodium-Doped CuInSe 2 Solar Cell Absorbers

Alkali metal doping and grain boundaries (GB) have been at the center of attention within the Cu(In,Ga)(S,Se) 2 photovoltaics community for years. This study provides the first experimental evidence that the GB of sodium-doped CuInSe 2 thin films may undertake reversible oxidation even at room temperature, whereas undoped films may not. The findings are corroborated by cathodoluminescence imaging, secondary ion mass spectrometry, and Kelvin probe force microscopy on air-exposed films subsequently subject to vacuum. A thermochemical assessment identifies the likely solid-gas equilibria involved. These reactions open new research questions with respect to the beneficial role played by alkali metal dopants in chalcopyrite solar cells and may steer the community toward new breakthroughs.

14 SOLAR ENERGY↗

SnSe 1-x S x Alloys: Anisotropic Van der Waals Semiconductors with Tunable Bandgaps

Alloying is one of the main tools of bandgap engineering, allowing the tuning of crystal structure, lattice parameters, and electronic structure of 3D and 2D/layered semiconductors. Among the latter, it can play a key role in tailoring the properties of tin monochalcogenides, a class of van der Waals semiconductors of interest for optoelectronics, thermoelectrics, ferroelectrics, and valleytronics. Here, the study investigates the synthesis and properties of large flakes of the anion substitution alloys SnSe 1-x S x . Alloy flakes across a wide range of compositions are obtained systematically by repeated growth from the same mixed (SnS, SnSe) powder precursor. Combined experiment and theory show full miscibility for all compositions, along with tunable lattice constants, bandgaps, and vibrational modes. Atomic resolution imaging demonstrates the accumulation of S and Se in alternating layers in the SnSe 1-x S x unit cell, attributed to growth kinetics. Polarized Raman spectroscopy confirms anisotropic vibrational modes; the calculated and measured band structure shows systematic changes in the band edge energies and anisotropic electronic structure due to the anisotropic in-plane lattice of the monochalcogenides. Cathodoluminescence, finally, indicates that a unique configuration of two non-degenerate, direct valleys along orthogonal k-space directions persists all the way from SnS to SnSe, making SnSe 1-x S x alloys interesting for valleytronics.

36 MATERIALS SCIENCE↗

Kinetics and mechanism of light-induced phase separation in a mixed-halide perovskite

Halide ion phase separation is a barrier to the application of mixed-halide perovskites, whereby the presence of large populations of photo-generated or injected carriers causes undesirable changes in the local band gap. Here, we investigate the mechanism of phase separation in CsPbI x Br 3-x perovskite single crystals driven by light. The phase separation process and its dynamics are visualized at the nanometer scale at cryogenic temperatures using in-situ scanning transmission electron microscopy and cathodoluminescence. Combined with phase field modeling that accounts for the coupling between electronic and chemical driving forces, our observations point to a spinodal decomposition mechanism in which both the amplitude of composition fluctuation and the characteristic length scale grow non-linearly with time. Our findings provide microscopic insights that can assist in further engineering mixed-halide perovskites either for stability or for intentional programming of the local halide ion composition, opening pathways to a wide range of applications.

36 MATERIALS SCIENCE↗

Integration of layered group IV selenides: From SnSe–SnSe 2-x S x core-shell crystals to complex (SnSe–SnSe 2-x S x )-GeSe van der waals heterostructures

The layered semiconductor tin selenide (SnSe) has received extensive interest due to its promising thermoelectric and ferroelectric properties. Integrating SnSe with other layered crystals in heterostructures can enable the modification of charge- and thermal transport, electrical polarization, and other properties such as chemical stability, optoelectronics, and photonics. Here, we demonstrate the vapor transport synthesis of single-crystalline SnSe monochalcogenide flakes that are spontaneously encapsulated in a thin layered SnSe 2-x S x dichalcogenide shell. In a second growth step, such SnSe-SnSe 2-x S x heterostructures are integrated with the monochalcogenide GeSe, which is laterally stitched to the SnSe side facets while preserving the dichalcogenide shell across the basal facets. This architecture is confirmed by optical microscopy, electron microscopy and diffraction, energy dispersive X-ray and Raman spectroscopies, as well as cathodoluminescence spectroscopy. Furthermore, the results extend our capabilities for materials integration by forming complex heterostructures with both vertical van der Waals interfaces and covalent lateral interfaces between layered semiconductors.

2D layered crystals↗