Bilayer and trilayer X-ray mirror coatings containing W, Pt, or Ir, in combination with C, C/Co, B4C, or B4C/Ni: X-ray reflectance, film stress, and temporal stability.

X-ray reflectance and film stress were measured for 12 bilayer and trilayer reflective interference coatings and compared with a single-layer Ir coating. The interference coatings comprise a base layer of W, Pt, or Ir, top layers of either C or B 4 C, and, in the case of the trilayer coatings, middle layers of either Co or Ni. The coatings were deposited by magnetron sputtering. Film stress was measured using the wafer curvature technique, while X-ray reflectance was measured at grazing incidence over the ∼0.1-10k e V energy band using synchrotron radiation. Re-measurements over a period of more than two years of both stress and X-ray reflectance were used to assess temporal stability. The X-ray reflectance of all 12 bilayer and trilayer coatings was found to be both stable over time and substantially higher than single-layer Ir over much of the energy range investigated, particularly below ∼4k e V, except near the B and C K-edges, and the Co and Ni L-edges, where we observe sharp, narrow drops in reflectance due to photo-absorption in layers containing these materials. Film stress was found to be substantially smaller than single-layer Ir in all cases as well; however, film stress was also found to change over time for all coatings (including the single-layer Ir coating). The effective area of future X-ray telescopes will be substantially higher if these high reflectance bilayer and/or trilayer coatings are used in place of single-layer coatings. Additionally, the smaller film stresses found in the bilayer and trilayer coatings relative to single-layer Ir will reduce coating-stress-driven mirror deformations. Nevertheless, as all the interference films studied here have stresses that are far from zero (albeit smaller than that of single-layer Ir), methods to mitigate such deformations must be developed in order to construct high-angular-resolution telescopes using thin mirror segments. Furthermore, unless film stress can be sufficiently stabilized over time, perhaps through thermal annealing, any such mitigation methods must also account for the temporal instability of film stress that was found in all coatings investigated here.

Advanced low blaze angle x-ray gratings via nanoimprint replication and plasma etch.

We developed a new method of making ultra-low blaze angle diffraction gratings for x-ray applications. The method is based on reduction of the blaze angle of a master grating by nanoimprint replication followed by a plasma etch. A master blazed grating with a relatively large blaze angle is fabricated by anisotropic wet etching of a Si single crystal substrate. The surface of the master grating is replicated by a polymer material on top of a quartz substrate by nanoimprinting. Then a second nanoimprinting is performed using the 1st replica as a mold to replicate the saw-tooth surface into a resist layer on top of a Si grating substrate. A reactive ion etch is used to transfer the grating grooves into the Si substrate. The plasma etch provides reduction of the groove depth by a factor defined by the ratio of the etch rates for the resist and Si. We demonstrate reduction of the blaze angle of a master grating by a factor of 5 during fabrication of a 200 lines/mm blazed grating with a blaze angle of 0.2°. We investigated the quality and performance of the fabricated low blaze angle gratings and evaluate process accuracy and reproducibility. The new blaze angle reduction method preserves the planarity of the optical surface of the grating substrate and at the same time provides improvement in the grating groove quality during the reduction process.

New method for the determination of photoabsorption from transmittance measurements in the extreme ultraviolet.

We have developed a new method for the determination of photoabsorption at extreme ultraviolet wavelengths longer than 20 nm, where reliable refractive index values are sparse or non-existent. Our method overcomes the obstacle of multiple reflections that occur inside thin films in this spectral range, which up until now has prevented the accurate determination of photoabsorption from transmittance measurements. We have derived a mathematical expression that is independent of internal reflection amplitudes, while taking advantage of the transmittance oscillations stemming from such reflections. The method is validated on measurements of aluminum thin films. This advance will enable accurate refractive index values for many important materials for optical instrumentation, thus facilitating high-priority research on topics including coherent light sources, planetary and solar physics, and semiconductor manufacturing.

Reflective binary amplitude grating for soft x-ray shearing and Hartmann wavefront sensing.

We demonstrate a reflective wavefront sensor grating suitable for the characterization of high-quality x-ray beamlines and optical systems with high power densities. Operating at glancing incidence angles, the optical element is deeply etched with a two-level pattern of shearing interferometry gratings and Hartmann wavefront sensor grids. Transverse features block unwanted light, enabling binary amplitude in reflection with high pattern contrast. We present surface characterization and soft x-ray reflectometry of a prototype grating array to demonstrate function prior to wavefront measurement applications. A simulation of device performance is shown.

Total-Electron-Yield Measurements by Soft X-Ray Irradiation of Insulating Organic Films on Conductive Substrates.

The photocurrent (sample current) of insulating 0.7-µm thick polyethylene terephthalate (PET) films on conductive substrates (C, Au, Cu) was clearly measured through the substrates during soft X-ray irradiation on the PET films. X-ray absorption measurements of the PET/conductive-substrates using the total-electron-yield (TEY) method by measuring sample current easily provide the X-ray absorption spectra (XAS) of PET films, which are independent of the substrates. From additional X-ray absorption measurements using self-standing PET/Au and Au/PET-films, I-V measurements, and thickness-dependent sample current measurements, it can be confirmed that electrically conductive paths form in the insulating PET film in thickness direction along the soft X-ray beam trajectory. Such phenomena enable easy and simple TEY-XAS measurements of insulating µm-order-thick samples.

High efficiency Al/Sc-based multilayer coatings in the EUV wavelength range above 40 nanometers.

In this Letter, we have developed new and highly efficient periodic multilayer mirrors Al/Sc, Al/Sc/SiC, and Mo/Al/Sc with optimized reflectance at wavelengths between 40 and 65 nm. We have reached record values in measured peak reflectance: 57.5% at 44.7 nm and 46.5% at 51 nm, with Al/Sc/SiC at near-normal incidence. Furthermore, to the best of our knowledge, we have achieved the largest reported bandwidth with Mo/Al/Sc at 57 nm and the narrowest bandwidth with Al/Sc at a 60 nm wavelength. These new and promising results demonstrate that Al/Sc-based multilayer coatings are excellent candidates for future generations of extreme ultraviolet (EUV) instruments for solar physics, EUV lasers, and attosecond science, in a wavelength range that has not been fully explored.

Lifetime Stability and Microstructure Properties of Cr/B4C X-ray Reflective Multilayer Coatings.

This paper demonstrates that highly reflective Cr/B4C multilayer interference coatings with nanometric layer thicknesses, designed to operate in the soft X-ray photon energy range, have stable reflective performance for a period of 3 years after deposition. The microstructure and chemical composition of layers and interfaces within Cr/B4C multilayers is also examined, with emphasis on the B4C-on-Cr interface where a significant diffusion layer is formed and on the oxide in the top B4C layer. Multiple characterization techniques (X-ray reflectivity at different photon energies, X-ray photoelectron spectroscopy, transmission electron microscopy, electron diffraction and X-ray diffraction) are employed and the results reveal a consistent picture of the Cr/B4C layer structure.

A carbonaceous two-dimensional lattice with FeN4 units.

A metal-containing carbonaceous two-dimensional lattice was formed on a graphene plane by sublimation, deposition, and pyrolysis of Fe phthalocyanine (Pc). The formation and growth of the FePc-derived π-conjugated planar system were reflected by its orientation conversion from the perpendicular to horizontal mode and by the N K-edge X-ray absorption near-edge structure.

Newly Developed Friction Tester for in situ Soft X-Ray Absorption Measurements of Frictional Engine-Oil/Metals Interfaces.

A novel friction tester has been developed to clarify the friction mechanism between engine oil and metals by in situ/operando measurements of the X-ray absorption near edge structure (XANES) using the total electron yield (TEY) method. The tester can perform frictional motion with engine oil and metals in a vacuum chamber under a vacuum of 10-7 Torr during TEY-XANES measurements in BL-6.3.2 at the Advanced Light Source (ALS). From in situ XANES measurements in the C K and Fe L regions, the organic molecule layers at the oil/metals interfaces have been successfully observed.

Impact of B4C co-sputtering on structure and optical performance of Cr/Sc multilayer X-ray mirrors.

The influence of B4C incorporation during magnetron sputter deposition of Cr/Sc multilayers intended for soft X-ray reflective optics is investigated. Chemical analysis suggests formation of metal: boride and carbide bonds which stabilize an amorphous layer structure, resulting in smoother interfaces and an increased reflectivity. A near-normal incidence reflectivity of 11.7%, corresponding to a 67% increase, is achieved at λ = 3.11 nm upon adding 23 at.% (B + C). The advantage is significant for the multilayer periods larger than 1.8 nm, where amorphization results in smaller interface widths, for example, giving 36% reflectance and 99.89% degree of polarization near Brewster angle for a multilayer polarizer. The modulated ion-energy-assistance during the growth is considered vital to avoid intermixing during the interface formation even when B + C are added.

Amplitude versus phase effects in extreme ultraviolet lithography mask scattering and imaging.

It is now well established that extreme ultraviolet (EUV) mask multilayer roughness leads to wafer-plane line-width roughness (LWR) in the lithography process. Analysis and modeling done to date has assumed, however, that the roughness leading to scatter is primarily a phase effect and that the amplitude can be ignored. Under this assumption, simple scattering measurements can be used to characterize the statistical properties of the mask roughness. Here, we explore the implications of this simplifying assumption by modeling the imaging impacts of the roughness amplitude component as a function of the balance between amplitude and phase induced scatter. In addition to model-based analysis, we also use an EUV microscope to compare experimental through focus data to modeling in order to assess the actual amount of amplitude roughness on a typical EUV multilayer mask. The results indicate that amplitude roughness accounts for less than 1% of the total scatter for typical EUV masks.

Modular soft x-ray spectrometer for applications in energy sciences and quantum materials.

Over the past decade, the advances in grating-based soft X-ray spectrometers have revolutionized the soft X-ray spectroscopies in materials research. However, these novel spectrometers are mostly dedicated designs, which cannot be easily adopted for applications with diverging demands. Here we present a versatile spectrometer design concept based on the Hettrick-Underwood optical scheme that uses modular mechanical components. The spectrometer's optics chamber can be used with gratings operated in either inside or outside orders, and the detector assembly can be reconfigured accordingly. The spectrometer can be designed to have high spectral resolution, exceeding 10 000 resolving power when using small source (∼1µm) and detector pixels (∼5µm) with high line density gratings (∼3000 lines/mm), or high throughput at moderate resolution. We report two such spectrometers with slightly different design goals and optical parameters in this paper. We show that the spectrometer with high throughput and large energy window is particularly useful for studying the sustainable energy materials. We demonstrate that the extensive resonant inelastic X-ray scattering (RIXS) map of battery cathode material LiNi1/3Co1/3Mn1/3O2 can be produced in few hours using such a spectrometer. Unlike analyzing only a handful of RIXS spectra taken at selected excitation photon energies across the elemental absorption edges to determine various spectral features like the localized dd excitations and non-resonant fluorescence emissions, these features can be easily identified in the RIXS maps. Studying such RIXS maps could reveal novel transition metal redox in battery compounds that are sometimes hard to be unambiguously identified in X-ray absorption and emission spectra. We propose that this modular spectrometer design can serve as the platform for further customization to meet specific scientific demands.

Performance of a ruthenium beam separator used to separate soft x rays from light generated by a high-order harmonic light source.

We describe the design and fabrication of a ruthenium beam separator used to simultaneously attenuate infrared light and reflect soft x rays. Measurements in the infrared and soft x-ray regions showed the beam separator to have a reflectivity of 50%-85% in the wavelength region from 6 to 10 nm at a grazing incidence angle of 7.5 deg and 4.3% at 800 nm and the same angle of grazing incidence, indicating that the amount of attenuation is 0.05-0.09. These results show that this beam separator could provide an effective means for separating IR light from soft x rays in light generated by high-order harmonic generation sources.

Pd/B4C/Y multilayer coatings for extreme ultraviolet applications near 10 nm wavelength.

A new extreme ultraviolet (EUV) multilayer coating has been developed comprising Pd and Y layers with thin B4C barrier layers at each interface, for normal incidence applications near 10 nm wavelength. Periodic, nonperiodic, and dual-stack coatings have been investigated and compared with similar structures comprising either Mo/Y or Pd/B4C bilayers. We find that Pd/B4C/Y multilayers provide higher reflectance than either Mo/Y or Pd/B4C, with much lower film stress than Pd/B4C. We have also investigated the performance of periodic multilayers comprising repetitions of Pd/Y, Ru/Y, or Ru/B4C/Y, as well as Pd/B4C multilayers deposited using reactive sputtering with an Ar:N2 gas mixture in order to reduce stress: these material combinations were all found to provide poor EUV performance. The temporal stability of a periodic Pd/B4C/Y multilayer stored in air was investigated over a period of 16 months, and a slight reduction in peak reflectance was observed. Periodic Pd/B4C/Y multilayers were also found to be thermally stable up to 100°C; at higher temperatures (200°C and 300°C) we observe a slight reduction in peak reflectance and a slight increase in multilayer period. High-resolution transmission electron microscopy and selected area diffraction of an as-deposited Pd/B4C/Y film indicates a fully amorphous structure, with interfaces that are both smoother and more abrupt than those observed in a comparable Pd/B4C multilayer in which the Pd layers are polycrystalline. The new Pd/B4C/Y multilayers are suitable for normal-incidence imaging and spectroscopy applications, including solar physics, plasma physics, high-brightness EUV light sources, and others.

Ion polished Cr/Sc attosecond multilayer mirrors for high water window reflectivity.

Recent advances in the development of attosecond soft X-ray sources ranging into the water window spectral range, between the 1s states of carbon and oxygen (284 eV-543 eV), are also driving the development of suited broadband multilayer optics for steering and shaping attosecond pulses. The relatively low intensity of current High Harmonic Generation (HHG) soft X-ray sources calls for an efficient use of photons, thus the development of low-loss multilayer optics is of uttermost importance. Here, we report about the realization of broadband Cr/Sc attosecond multilayer mirrors with nearly atomically smooth interfaces by an optimized ion beam deposition and assisted interface polishing process. This yields to our knowledge highest multilayer mirror reflectivity at 300 eV near normal incidence. The results are verified by transmission electron microscopy (TEM) and soft/hard X-ray reflectometry.

Concentration and chemical-state profiles at heterogeneous interfaces with sub-nm accuracy from standing-wave ambient-pressure photoemission.

Heterogeneous processes at solid/gas, liquid/gas and solid/liquid interfaces are ubiquitous in modern devices and technologies but often difficult to study quantitatively. Full characterization requires measuring the depth profiles of chemical composition and state with enhanced sensitivity to narrow interfacial regions of a few to several nm in extent over those originating from the bulk phases on either side of the interface. We show for a model system of NaOH and CsOH in an ~1-nm thick hydrated layer on α-Fe2O3 (haematite) that combining ambient-pressure X-ray photoelectron spectroscopy and standing-wave photoemission spectroscopy provides the spatial arrangement of the bulk and interface chemical species, as well as local potential energy variations, along the direction perpendicular to the interface with sub-nm accuracy. Standing-wave ambient-pressure photoemission spectroscopy is thus a very promising technique for measuring such important interfaces, with relevance to energy research, heterogeneous catalysis, electrochemistry, and atmospheric and environmental science.

Electro-optical system for scanning microscopy of extreme ultraviolet masks with a high harmonic generation source.

A self-contained electro-optical module for scanning extreme ultraviolet (EUV) reflection microscopy at 13.5 nm wavelength has been developed. The system has been designed to work with stand-alone commercially available EUV high harmonic generation (HHG) sources through the implementation of narrowband harmonic selecting multilayers and off-axis elliptical short focal length zoneplates. The module has been successfully integrated into an EUV mask scanning microscope achieving diffraction limited imaging performance (84 nm point spread function).

Investigation of surface topology of printed nanoparticle layers using wide-angle low-Q scattering.

A new small-angle scattering technique in reflection geometry is described which enables a topological study of rough surfaces. This is achieved by using long-wavelength soft X-rays which are scattered at wide angles but in the low-Q range normally associated with small-angle scattering. The use of nanometre-wavelength radiation restricts the penetration to a thin surface layer which follows the topology of the surface, while moving the scattered beam to wider angles preventing shadowing by the surface features. The technique is, however, only applicable to rough surfaces for which there is no specular reflection, so that only the scattered beam was detected by the detector. As an example, a study of the surfaces of rough layers of silicon produced by the deposition of nanoparticles by blade-coating is presented. The surfaces of the blade-coated layers have rough features of the order of several micrometers. Using 2 nm and 13 nm X-rays scattered at angular ranges of 5° ≤ θ ≤ 51° and 5° ≤ θ ≤ 45°, respectively, a combined range of scattering vector of 0.00842 Å(-1) ≤ Q ≤ 0.4883 Å(-1) was obtained. Comparison with previous transmission SAXS and USAXS studies of the same materials indicates that the new method does probe the surface topology rather than the internal microstructure.

Aperiodic CrSc multilayer mirrors for attosecond water window pulses.

Extending single attosecond pulse technology from currently sub-200 eV to the so called 'water window' spectral range may enable for the first time the unique investigation of ultrafast electronic processes within the core states of bio-molecules as proteins or other organic materials. Aperiodic multilayer mirrors serve as key components to shape these attosecond pulses with a high degree of freedom and enable tailored short pulse pump-probe experiments. Here, we report on chirped CrSc multilayer mirrors, fabricated by ion beam deposition with sub-angstrom precision, designed for attosecond pulse shaping in the 'water window' spectral range.

Full field tabletop EUV coherent diffractive imaging in a transmission geometry.

We demonstrate the first general tabletop EUV coherent microscope that can image extended, non-isolated, non-periodic, objects. By implementing keyhole coherent diffractive imaging with curved mirrors and a tabletop high harmonic source, we achieve improved efficiency of the imaging system as well as more uniform illumination at the sample, when compared with what is possible using Fresnel zone plates. Moreover, we show that the unscattered light from a semi-transparent sample can be used as a holographic reference wave, allowing quantitative information about the thickness of the sample to be extracted from the retrieved image. Finally, we show that excellent tabletop image fidelity is achieved by comparing the retrieved images with scanning electron and atomic force microscopy images, and show superior capabilities in some cases.