Fast nanoscale imaging of strain in a multi-segment heterostructured nanowire with 2D Bragg ptychography.

Developing semiconductor devices requires a fast and reliable source of strain information with high spatial resolution and strain sensitivity. This work investigates the strain in an axially heterostructured 180 nm-diameter GaInP nanowire with InP segments of varying lengths down to 9 nm, simultaneously probing both materials. Scanning X-ray diffraction (XRD) is compared with Bragg projection ptychography (BPP), a fast single-projection method. BPP offers a sufficient spatial resolution to reveal fine details within the largest segments, unlike scanning XRD. The spatial resolution affects the quantitative accuracy of the strain maps, where BPP shows much-improved agreement with an elastic 3D finite element model compared with scanning XRD. The sensitivity of BPP to small deviations from the Bragg condition is systematically investigated. The experimental confirmation of the model suggests that the large lattice mismatch of 1.52% is accommodated without defects.

Beyond ray optics absorption of light in CsPbBr3perovskite nanowire arrays studied experimentally and with wave optics modelling.

We study experimentally and with wave optics modelling the absorption of light in CsPbBr3perovskite nanowire arrays fabricated into periodic pores of an anodized aluminum oxide matrix, for nanowire diameters from 30 to 360 nm. First, we find that all the light that couples into the array can be absorbed by the nanowires at sufficient nanowire length. This behavior is in strong contrast to the expectation from a ray-optics description of light where, for normally incident light, only the rays that hit the cross-section of the nanowires can be absorbed. In that case, the absorption in the sample would be limited to the area fill factor of nanowires in the hexagonal array, which ranges from 13% to 58% for the samples that we study. Second, we find that the absorption saturates already at a nanowire length of 1000-2000 nm, making these perovskite nanowires promising for absorption-based applications such as solar cells and photodetectors. The absorption shows a strong diameter dependence, but for all diameters the transmission is less than 24% already at a nanowire length of 500 nm. For some diameters, the absorption exceeds that of a calculated thin film with 100% coverage. Our analysis indicates that the strong absorption in these nanowires originates from light-trapping induced by the out-of-plane disorder due to random axial position of each nanowire within its pore in the matrix.

Nanoscale X-ray Imaging of Composition and Ferroelastic Domains in Heterostructured Perovskite Nanowires: Implications for Optoelectronic Devices.

Metal halide perovskites (MHPs) have garnered significant interest as promising candidates for nanoscale optoelectronic applications due to their excellent optical properties. Axially heterostructured CsPbBr3-CsPb(Br(1-x)Clx)3 nanowires can be produced by localized anion exchange of pregrown CsPbBr3 nanowires. However, characterizing such heterostructures with sufficient strain and real space resolution is challenging. Here, we use nanofocused scanning X-ray diffraction (XRD) and X-ray fluorescence (XRF) with a 60 nm beam to investigate a heterostructured MHP nanowire as well as a reference CsPbBr3 nanowire. The nano-XRD approach gives spatially resolved maps of composition, lattice spacing, and lattice tilt. Both the reference and exchanged nanowire show signs of diverse types of ferroelastic domains, as revealed by the tilt maps. The chlorinated segment shows an average Cl composition of x = 66 and x = 70% as measured by XRD and XRF, respectively. The XRD measurements give a much more consistent result than the XRF ones. These findings are consistent with photoluminescence measurements, showing x = 73%. The nominally unexchanged segment also has a small concentration of Cl, as observed with all three methods, which we attribute to diffusion after processing. These results highlight the need to prevent such unwanted processes in order to fabricate optoelectronic devices based on MHP heterostructures.

Optimization of phase contrast imaging with a nano-focus x-ray tube.

Propagation-based phase contrast imaging with a laboratory x-ray source is a valuable tool for studying samples that show only low absorption contrast, either because of low density, elemental composition, or small feature size. If a propagation distance between sample and detector is introduced and the illumination is sufficiently coherent, the phase shift in the sample will cause additional contrast around interfaces, known as edge enhancement fringes. The strength of this effect depends not only on sample parameters and energy but also on the experimental geometry, which can be optimized accordingly. Recently, x-ray lab sources using transmission targets have become available, which provide very small source sizes in the few hundred nanometer range. This allows the use of a high-magnification geometry with a very short source-sample distance, while still achieving sufficient spatial coherence at the sample position. Moreover, the high geometrical magnification makes it possible to use detectors with a larger pixel size without reducing the image resolution. Here, we explore the influence of magnification on the edge enhancement fringes in such a geometry. We find experimentally and theoretically that the fringes become maximal at a magnification that is independent of the total source-detector distance. This optimal magnification only depends on the source size, the steepness of the sample feature, and the detector resolution. A stronger influence of the sample feature on the optimal magnification compared to low-magnification geometries is observed.

A versatile laboratory setup for high resolution X-ray phase contrast tomography and scintillator characterization.

BACKGROUND: X-ray micro-tomography (µCT) is a powerful non-destructive 3D imaging method applied in many scientific fields. In combination with propagation-based phase-contrast, the method is suitable for samples with low absorption contrast. Phase contrast tomography has become available in the lab with the ongoing development of micro-focused tube sources, but it requires sensitive and high-resolution X-ray detectors. The development of novel scintillation detectors, particularly for microscopy, requires more flexibility than available in commercial tomography systems. OBJECTIVE: We aim to develop a compact, flexible, and versatile µCT laboratory setup that combines absorption and phase contrast imaging as well as the option to use it for scintillator characterization. Here, we present details on the design and implementation of the setup. METHODS: We used the setup for µCT in absorption and propagation-based phase-contrast mode, as well as to study a perovskite scintillator. RESULTS: We show the 2D and 3D performance in absorption and phase contrast mode, as well as how the setup can be used for testing new scintillator materials in a realistic imaging environment. A spatial resolution of around 1.3µm is measured in 2D and 3D. CONCLUSIONS: The setup meets the needs for common absorption µCT applications and offers increased contrast in phase contrast mode. The availability of a versatile laboratory µCT setup allows not only for easy access to tomographic measurements, but also enables a prompt monitoring and feedback beneficial for advances in scintillator fabrication.

Compositional analysis of oxide-embedded III-V nanostructures.

Nanowire growth enables creation of embedded heterostructures, where one material is completely surrounded by another. Through materials-selective post-growth oxidation it is also possible to combine amorphous oxides and crystalline, e.g. III-V materials. Such oxide-embedded structures pose a challenge for compositional characterization through transmission electron microscopy since the materials will overlap in projection. Furthermore, materials electrically isolated by an embedding oxide are more sensitive to electron beam-induced alterations. Methods that can directly isolate the embedded material, preferably at reduced electron doses, will be required in this situation. Here, we analyse the performance of two such techniques-local lattice parameter measurements from high resolution micrographs and bulk plasmon energy measurements from electron energy loss spectra-by applying them to analyse InP-AlInP segments embedded in amorphous aluminium oxide. We demonstrate the complementarity of the two methods, which show an overall excellent agreement. However, in regions with residual strain, which we analyse through molecular dynamics simulations, the two techniques diverge from the true value in opposite directions.

Perovskite-Compatible Electron-Beam-Lithography Process Based on Nonpolar Solvents for Single-Nanowire Devices.

Metal halide perovskites (MHPs) have been studied intensely as the active material for optoelectronic devices. Lithography methods for perovskites remain limited because of the solubility of perovskites in polar solvents. Here, we demonstrate an electron-beam-lithography process with a poly(methyl methacrylate) resist based on the nonpolar solvents o-xylene, hexane, and toluene. Features down to 50 nm size are created, and photoluminescence of CsPbBr3 nanowires exhibits no degradation. We fabricate metal contacts to single CsPbBr3 nanowires, which show a strong photoresponsivity of 0.29 A W-1. The presented method is an excellent tool for nanoscale MHP science and technology, allowing for the fabrication of complex nanostructures.

Free-Standing Metal Halide Perovskite Nanowire Arrays with Blue-Green Heterostructures.

Vertically aligned metal halide perovskite (MHP) nanowires are promising for various optoelectronic applications, which can be further enhanced by heterostructures. However, present methods to obtain free-standing vertically aligned MHP nanowire arrays and heterostructures lack the scalability needed for applications. We use a low-temperature solution process to prepare free-standing vertically aligned green-emitting CsPbBr3 nanowires from anodized aluminum oxide templates. The length is controlled from 1 to 20 µm by the precursor amount. The nanowires are single-crystalline and exhibit excellent photoluminescence, clear light guiding and high photoconductivity with a responsivity of 1.9 A/W. We demonstrate blue-green heterostructured nanowire arrays by converting the free-standing part of the nanowires to CsPbCl1.1Br1.9 in an anion exchange process. Our results demonstrate a scalable, self-aligned, and lithography-free approach to achieve high quality free-standing MHP nanowires arrays and heterostructures, offering new possibilities for optoelectronic applications.

Correction: Strain mapping inside an individual processed vertical nanowire transistor using scanning X-ray nanodiffraction.

Correction for 'Strain mapping inside an individual processed vertical nanowire transistor using scanning X-ray nanodiffraction' by Dmitry Dzhigaev et al., Nanoscale, 2020, 12, 14487-14493, DOI: 10.1039/D0NR02260H.

Single-Crystalline Perovskite Nanowire Arrays for Stable X-ray Scintillators with Micrometer Spatial Resolution.

X-ray scintillation detectors based on metal halide perovskites have shown excellent light yield, but they mostly target applications with spatial resolution at the tens of micrometers level. Here, we use a one-step solution method to grow arrays of 15-µm-long single-crystalline CsPbBr3 nanowires (NWs) in an AAO (anodized aluminum oxide) membrane template, with nanowire diameters ranging from 30 to 360 nm. The CsPbBr3 nanowires in AAO (CsPbBr3 NW/AAO) show increasing X-ray scintillation efficiency with decreasing nanowire diameter, with a maximum photon yield of ∼5 300 ph/MeV at 30 nm diameter. The CsPbBr3 NW/AAO composites also display high radiation resistance, with a scintillation-intensity decrease of only ∼20-30% after 24 h of X-ray exposure (integrated dose 162 Gyair) and almost no change after ambient storage for 2 months. X-ray images can distinguish line pairs with a spacing of 2 µm for all nanowire diameters, while slanted edge measurements show a spatial resolution of ∼160 lp/mm at modulation transfer function (MTF) = 0.1. The combination of high spatial resolution, radiation stability, and easy fabrication makes these CsPbBr3 NW/AAO scintillators a promising candidate for high-resolution X-ray imaging applications.

Optical demonstration of crystallography and reciprocal space using laser diffraction from Au microdisc arrays.

Crystallography is an invaluable tool in materials science, solid state physics and protein science. Understanding crystallography requires grasping the powerful but abstract concept of reciprocal space. Here a simple but insightful experiment using a laser pointer and Au microdisc arrays to explore and illustrate Bragg diffraction and reciprocal space is demonstrated. The Au microdisc arrays were manufactured using standard semiconductor fabrication techniques. The flexibility of the array design allows the demonstration of basic concepts such as lattice and atomic form factor, but also more advanced ones such as quasicrystal and shape function.

X-ray in-line holography and holotomography at the NanoMAX beamline.

Coherent X-ray imaging techniques, such as in-line holography, exploit the high brilliance provided by diffraction-limited storage rings to perform imaging sensitive to the electron density through contrast due to the phase shift, rather than conventional attenuation contrast. Thus, coherent X-ray imaging techniques enable high-sensitivity and low-dose imaging, especially for low-atomic-number (Z) chemical elements and materials with similar attenuation contrast. Here, the first implementation of in-line holography at the NanoMAX beamline is presented, which benefits from the exceptional focusing capabilities and the high brilliance provided by MAX IV, the first operational diffraction-limited storage ring up to approximately 300 eV. It is demonstrated that in-line holography at NanoMAX can provide 2D diffraction-limited images, where the achievable resolution is only limited by the 70 nm focal spot at 13 keV X-ray energy. Also, the 3D capabilities of this instrument are demonstrated by performing holotomography on a chalk sample at a mesoscale resolution of around 155 nm. It is foreseen that in-line holography will broaden the spectra of capabilities of MAX IV by providing fast 2D and 3D electron density images from mesoscale down to nanoscale resolution.

Off-axis multilayer zone plate with 16†nm × 28†nm focus for high-resolution X-ray beam induced current imaging.

Using multilayer zone plates (MZPs) as two-dimensional optics, focal spot sizes of less than 10 nm can be achieved, as we show here with a focus of 8.4 nm × 9.6 nm, but the need for order-sorting apertures prohibits practical working distances. To overcome this issue, here an off-axis illumination of a circular MZP is introduced to trade off between working distance and focal spot size. By this, the working distance between order-sorting aperture and sample can be more than doubled. Exploiting a 2D focus of 16 nm × 28 nm, real-space 2D mapping of local electric fields and charge carrier recombination using X-ray beam induced current in a single InP nanowire is demonstrated. Simulations show that a dedicated off-axis MZP can reach sub-10 nm focusing combined with reasonable working distances and low background, which could be used for in operando imaging of composition, carrier collection and strain in nanostructured devices.

Vertically Aligned CsPbBr3 Nanowire Arrays with Template-Induced Crystal Phase Transition and Stability.

Metal halide perovskites show great promise for a wide range of optoelectronic applications but are plagued by instability when exposed to air and light. This work presents low-temperature solution growth of vertically aligned CsPbBr3 nanowire arrays in AAO (anodized aluminum oxide) templates with excellent stability, with samples exposed to air for 4 months still exhibiting comparable photoluminescence and UV stability to fresh samples. The single-crystal nanowire length is adjusted from ∼100 nm to 5 µm by adjusting the precursor solution amount and concentration, and we observe length-to-diameter ratios as high as 100. Structural characterization results indicate that large-diameter CsPbBr3 nanowires have an orthorhombic structure, while the 10 nm- and 20 nm-diameter nanowires adopt a cubic structure. Photoluminescence shows a gradual blue-shift in emission with decreasing nanowire diameter and marginal changes under varying illumination power intensity. The CsPbBr3-nanowires/AAO composite exhibits excellent resistance to X-ray radiation and long-term air storage, which makes it promising for future optoelectronic applications such as X-ray scintillators. These results show how physical confinement in AAO can be used to realize CsPbBr3 nanowire arrays and control their morphology and crystal structure.

In Situ Imaging of Ferroelastic Domain Dynamics in CsPbBr3 Perovskite Nanowires by Nanofocused Scanning X-ray Diffraction.

The interest in metal halide perovskites has grown as impressive results have been shown in solar cells, light emitting devices, and scintillators, but this class of materials have a complex crystal structure that is only partially understood. In particular, the dynamics of the nanoscale ferroelastic domains in metal halide perovskites remains difficult to study. An ideal in situ imaging method for ferroelastic domains requires a challenging combination of high spatial resolution and long penetration depth. Here, we demonstrate in situ temperature-dependent imaging of ferroelastic domains in a single nanowire of metal halide perovskite, CsPbBr3. Scanning X-ray diffraction with a 60 nm beam was used to retrieve local structural properties for temperatures up to 140 °C. We observed a single Bragg peak at room temperature, but at 80 °C, four new Bragg peaks appeared, originating in different real-space domains. The domains were arranged in periodic stripes in the center and with a hatched pattern close to the edges. Reciprocal space mapping at 80 °C was used to quantify the local strain and lattice tilts, revealing the ferroelastic nature of the domains. The domains display a partial stability to further temperature changes. Our results show the dynamics of nanoscale ferroelastic domain formation within a single-crystal perovskite nanostructure, which is important both for the fundamental understanding of these materials and for the development of perovskite-based devices.

Experimental optimization of X-ray propagation-based phase contrast imaging geometry.

Propagation-based phase contrast imaging (PB-PCI) with an X-ray lab source is a powerful technique to study low absorption samples, e.g. soft tissue or plastics, on the micrometer scale but is often limited by the low flux and coherence of the source. The setup geometry is essential for the performance since there is a trade-off where a short source distance yields a high contrast-to-noise ratio (CNR) but a low relative fringe contrast. While theoretical optimization strategies based on Fresnel propagation have been reported, there is a need for experimental testing of these models. Here, we systematically investigate this trade-off experimentally using two different setups with high-resolution detectors: a custom-built system with a Cu X-ray source and a commercial system (Zeiss Xradia) with a W source. The fringe contrast, CNR and fringe separation for a low-absorption test sample were measured for 130 different combinations of magnification and overall distances. We find that these figures-of-merit are sensitive to the magnification and that an optimum can be found that is independent of the overall source-detector distance. In general, we find that the theoretical models show excellent agreement with the measurements. However, this requires the complicated X-ray spectrum to be considered, in particular for the broadband W source.

Direct Three-Dimensional Imaging of an X-ray Nanofocus Using a Single 60 nm Diameter Nanowire Device.

Nanoscale X-ray detectors could allow higher resolution in imaging and diffraction experiments than established systems but are difficult to design due to the long absorption length of X-rays. Here, we demonstrate X-ray detection in a single nanowire in which the nanowire axis is parallel to the optical axis. In this geometry, X-ray absorption can occur along the nanowire length, while the spatial resolution is limited by the diameter. We use the device to make a high-resolution 3D image of the 88 nm diameter X-ray nanofocus at the Nanomax beamline, MAX IV synchrotron, by scanning the single pixel device in different planes along the optical axis. The images reveal fine details of the beam that are unattainable with established detectors and show good agreement with ptychography.

Strain mapping inside an individual processed vertical nanowire transistor using scanning X-ray nanodiffraction.

Semiconductor nanowires in wrapped, gate-all-around transistor geometry are highly favorable for future electronics. The advanced nanodevice processing results in strain due to the deposited dielectric and metal layers surrounding the nanowires, significantly affecting their performance. Therefore, non-destructive nanoscale characterization of complete devices is of utmost importance due to the small feature sizes and three-dimensional buried structure. Direct strain mapping inside heterostructured GaSb-InAs nanowire tunnel field-effect transistor embedded in dielectric HfO2, W metal gate layers, and an organic spacer is performed using fast scanning X-ray nanodiffraction. The effect of 10 nm W gate on a single embedded nanowire with segment diameters down to 40 nm is retrieved. The tensile strain values reach 0.26% in the p-type GaSb segment of the transistor. Supported by the finite element method simulation, we establish a connection between the Ar pressure used during the W layer deposition and the nanowire strain state. Thus, we can benchmark our models for further improvements in device engineering. Our study indicates, how the significant increase in X-ray brightness at 4th generation synchrotron, makes high-throughput measurements on realistic nanoelectronic devices viable.

Three-Dimensional Coherent Bragg Imaging of Rotating Nanoparticles.

Bragg coherent diffraction imaging is a powerful strain imaging tool, often limited by beam-induced sample instability for small particles and high power densities. Here, we devise and validate an adapted diffraction volume assembly algorithm, capable of recovering three-dimensional datasets from particles undergoing uncontrolled and unknown rotations. We apply the method to gold nanoparticles which rotate under the influence of a focused coherent x-ray beam, retrieving their three-dimensional shapes and strain fields. The results show that the sample instability problem can be overcome, enabling the use of fourth generation synchrotron sources for Bragg coherent diffraction imaging to their full potential.

Simultaneous Growth of Pure Wurtzite and Zinc Blende Nanowires.

The opportunity to engineer III-V nanowires in wurtzite and zinc blende crystal structure allows for exploring properties not conventionally available in the bulk form as well as opening the opportunity for use of additional degrees of freedom in device fabrication. However, the fundamental understanding of the nature of polytypism in III-V nanowire growth is still lacking key ingredients to be able to connect the results of modeling and experiments. Here we show InP nanowires of both pure wurtzite and pure zinc blende grown simultaneously on the same InP [100]-oriented substrate. We find wurtzite nanowires to grow along [Formula: see text] and zinc blende counterparts along [Formula: see text]. Further, we discuss the nucleation, growth, and polytypism of our nanowires against the background of existing theory. Our results demonstrate, first, that the crystal growth conditions for wurtzite and zinc blende nanowire growth are not mutually exclusive and, second, that the interface energies predominantly determine the crystal structure of the nanowires.