New opportunities for time-resolved imaging using diffraction-limited storage rings.

The advent of diffraction-limited storage rings (DLSRs) has boosted the brilliance or coherent flux by one to two orders of magnitude with respect to the previous generation. One consequence of this brilliance enhancement is an increase in the flux density or number of photons per unit of area and time, which opens new possibilities for the spatiotemporal resolution of X-ray imaging techniques. This paper studies the time-resolved microscopy capabilities of such facilities by benchmarking the ForMAX beamline at the MAX IV storage ring. It is demonstrated that this enhanced flux density using a single harmonic of the source allows micrometre-resolution time-resolved imaging at 2000 tomograms per second and 1.1 MHz 2D acquisition rates using the full dynamic range of the detector system.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

Nanoscale mapping of carrier collection in single nanowire solar cells using X-ray beam induced current.

Here it is demonstrated how nanofocused X-ray beam induced current (XBIC) can be used to quantitatively map the spatially dependent carrier collection probability within nanostructured solar cells. The photocurrent generated by a 50 nm-diameter X-ray beam was measured as a function of position, bias and flux in single p-i-n doped solar-cell nanowires. The signal gathered mostly from the middle segment decays exponentially toward the p- and n-segments, with a characteristic decay length that varies between 50 nm and 750 nm depending on the flux and the applied bias. The amplitude of the XBIC shows saturation at reverse bias, which indicates that most carriers are collected. At forward bias, the relevant condition for solar cells, the carrier collection is only efficient in a small region. Comparison with finite element modeling suggests that this is due to unintentional p-doping in the middle segment. It is expected that nanofocused XBIC could be used to investigate carrier collection in a wide range of nanostructured solar cells.

Nanobeam X-ray Fluorescence Dopant Mapping Reveals Dynamics of in Situ Zn-Doping in Nanowires.

The properties of semiconductors can be controlled using doping, making it essential for electronic and optoelectronic devices. However, with shrinking device sizes it becomes increasingly difficult to quantify doping with sufficient sensitivity and spatial resolution. Here, we demonstrate how X-ray fluorescence mapping with a nanofocused beam, nano-XRF, can quantify Zn doping within in situ doped III-V nanowires, by using large area detectors and high-efficiency focusing optics. The spatial resolution is defined by the focus size to 50 nm. The detection limit of 7 ppm (2.8 × 1017 cm-3), corresponding to about 150 Zn atoms in the probed volume, is bound by a background signal. In solar cell InP nanowires with a p-i-n doping profile, we use nano-XRF to observe an unintentional Zn doping of 5 × 1017 cm-3 in the middle segment. We investigated the dynamics of in situ Zn doping in a dedicated multisegment nanowire, revealing significantly sharper gradients after turning the Zn source off than after turning the source on. Nano-XRF could be used for quantitative mapping of a wide range of dopants in many types of nanostructures.

Spectrally resolved x-ray beam induced current in a single InGaP nanowire.

We demonstrate x-ray absorption fine structure spectroscopy (XAFS) detected by x-ray beam induced current (XBIC) in single n + -i-n + doped nanowire devices. Spatial scans with the 65 nm diameter beam show a peak of the XBIC signal in the middle segment of the nanowire. The XBIC and the x-ray fluorescence signals were detected simultaneously as a function of the excitation energy near the Ga K absorption edge at 10.37 keV. The spectra show similar oscillations around the edge, which shows that the XBIC is limited by the primary absorption. Our results reveal the feasibility of the XBIC detection mode for the XAFS investigation in nanostructured devices.

Bending and Twisting Lattice Tilt in Strained Core-Shell Nanowires Revealed by Nanofocused X-ray Diffraction.

We have investigated strained GaAs-GaInP core-shell nanowires using transmission electron microscopy and nanofocused scanning X-ray diffraction. Nominally identical growth conditions for each sample were achieved by using nanoimprint lithography to create wafer-scale arrays of Au seed particles. However, we observe large individual differences, with neighboring nanowires showing either straight, bent, or twisted morphology. Using scanning X-ray diffraction, we reconstructed and quantified the bending and twisting of the nanowires in three dimensions. In one nanowire, we find that the shell lattice is tilted with respect to the core lattice, with an angle that increases from 2° at the base to 5° at the top. Furthermore, the azimuthal orientation of the tilt changes by 30° along the nanowire axis. Our results demonstrate how strained core-shell nanowire growth can lead to a rich interplay of composition, lattice mismatch, bending and lattice tilt, with additional degrees of complexity compared with thin films.

Simulated sample heating from a nanofocused X-ray beam.

Recent developments in synchrotron brilliance and X-ray optics are pushing the flux density in nanofocusing experiments to unprecedented levels, which increases the risk of different types of radiation damage. The effect of X-ray induced sample heating has been investigated using time-resolved and steady-state three-dimensional finite-element modelling of representative nanostructures. Simulations of a semiconductor nanowire indicate that the heat generated by X-ray absorption is efficiently transported within the nanowire, and that the temperature becomes homogeneous after about 5 ns. The most important channel for heat loss is conduction to the substrate, where the heat transfer coefficient and the interfacial area are limiting the heat transport. While convective heat transfer to air is significant, the thermal radiation is negligible. The steady-state average temperature in the nanowire is 8 K above room temperature at the reference parameters. In the absence of heat transfer to the substrate, the temperature increase at the same flux reaches 55 K in air and far beyond the melting temperature in vacuum. Reducing the size of the X-ray focus at constant flux only increases the maximum temperature marginally. These results suggest that the key strategy for reducing the X-ray induced heating is to improve the heat transfer to the surrounding.

Carrier Recombination Dynamics in Sulfur-Doped InP Nanowires.

Measuring lifetime of photogenerated charges in semiconductor nanowires (NW) is important for understanding light-induced processes in these materials and is relevant for their photovoltaic and photodetector applications. In this paper, we investigate the dynamics of photogenerated charge carriers in a series of as-grown InP NW with different levels of sulfur (S) doping. We observe that photoluminescence (PL) decay time as well as integrated PL intensity decreases with increasing S doping. We attribute these observations to hole trapping with the trap density increased due to S-doping level followed by nonradiative recombination of trapped charges. This assignment is proven by observation of the trap saturation in three independent experiments: via excitation power and repetition rate PL lifetime dependencies and by PL pump-probe experiment.

Au-seeded growth of vertical and in-plane III-V nanowires on graphite substrates.

Graphene is promising as a transparent, flexible, and possibly cost-effective substrate for nanowire-based devices. We have investigated Au-seeded III-V nanowire growth with graphite as a model substrate. The highest yield of undoped vertical nanowires was found for InAs, but we also observed vertical nanowires for the InP, GaP, and GaAs materials. The yield of vertical nanowires for GaP and GaAs was strongly improved by supplying the p-dopant DEZn before nanowire growth but not by supplying H2S or HCl. In-plane GaAs and GaP nanowire growth exhibited an unexpected behavior, where the seed particles seemingly reflected on the side facets of other nanowires. These results pave the way for vertical and in-plane hybrid graphene- nanowire devices.

Hard X-ray detection using a single 100 nm diameter nanowire.

Submicron sized sensors could allow higher resolution in X-ray imaging and diffraction measurements, which are ubiquitous for materials science and medicine. We present electrical measurements of a single 100 nm diameter InP nanowire transistor exposed to hard X-rays. The X-ray induced conductance is over 5 orders of magnitude larger than expected from reported data for X-ray absorption and carrier lifetimes. Time-resolved measurements show very long characteristic lifetimes on the order of seconds, tentatively attributed to long-lived traps, which give a strong amplification effect. As a proof of concept, we use the nanowire to directly image an X-ray nanofocus with submicron resolution.