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A novel ultrahigh-resolution x-ray microscope achieves 8-nm spatial resolution and accurately maps chemistry in nanomaterials., The analysis of chemical states and morphology in nanomaterials is central to many areas of science. We address this need with an ultrahigh-resolution scanning transmission soft x-ray microscope. Our instrument provides multiple analysis tools in a compact assembly and can achieve few-nanometer spatial resolution and high chemical sensitivity via x-ray ptychography and conventional scanning microscopy. A novel scanning mechanism, coupled to advanced x-ray detectors, a high-brightness x-ray source, and high-performance computing for analysis provide a revolutionary step forward in terms of imaging speed and resolution. We present x-ray microscopy with 8-nm full-period spatial resolution and use this capability in conjunction with operando sample environments and cryogenic imaging, which are now routinely available. Our multimodal approach will find wide use across many fields of science and facilitate correlative analysis of materials with other types of probes.

Detailed mapping of the electronic structure is a crucial part of explaining the behavior of materials. It is the electronic structure that determines the conductivity and thermal properties. It is the electronic structure that determines chemical properties. Knowledge about the electronic structure can help in determining the atomic structure of molecules.

Fresnel zone plates are the most commonly used optic in x-ray microscopes. Following a short discussion of historical developments, the properties of zone plates are outlined, along with the microscope systems that employ them. A number of applications of x-ray microscopes are then surveyed, including in biology, environmental science, and materials science.

The performance of battery electrode materials is strongly affected by inefficiencies in utilization kinetics and cycle life as well as size effects. Observations of phase transformations in these materials with high chemical and spatial resolution can elucidate the relationship between chemical processes and mechanical degradation. Soft X-ray ptychographic microscopy combined with X-ray absorption spectroscopy and electron microscopy creates a powerful suite of tools that we use to assess the chemical and morphological changes in lithium iron phosphate (LiFePO4) micro- and nanocrystals that occur upon delithiation. All sizes of partly delithiated crystals were found to contain two phases with a complex correlation between crystallographic orientation and phase distribution. However, the lattice mismatch between LiFePO4 and FePO4 led to severe fracturing on microcrystals, whereas no mechanical damage was observed in nanoplates, indicating that mechanics are a principal driver in the outstanding electrode ...

R ADIOLOGICAL P ROTECTION S TUDIES FOR NGLS XTOD S HANJIE X IAO , M ARIO S ANTANA -L EITNER AND S AYED R OKNI SLAC N ATIONAL A CCELERATOR L ABORATORY R ICK D ONAHUE , P AUL E MMA , J AMES F LOYD AND T ONY W ARWICK L AWRENCE B ERKELEY N ATIONAL L ABORATORY SLAC-TN-13-003 LBNL-DOC-### December, 2013 P REPARED FOR THE D EPARTMENT OF E NERGY U NDER C ONTRACT N UMBER DE-AC02-76SF00515 & DE-AC02-05CH11231

The optical design of a two-dimensional imaging soft X-ray spectrometer is described. A monochromator will produce a dispersed spectrum in a narrow vertical illuminated stripe (∼2 µm wide by ∼2 mm tall) on a sample. The spectrometer will use inelastically scattered X-rays to image the extended field on the sample in the incident photon energy direction (vertical), resolving the incident photon energy. At the same time it will image and disperse the scattered photons in the orthogonal (horizontal) direction, resolving the scattered photon energy. The principal challenge is to design a system that images from the flat-field illumination of the sample to the flat field of the detector and to achieve sufficiently high spectral resolution. This spectrometer provides a completely parallel resonant inelastic X-ray scattering measurement at high spectral resolution (∼30000) over the energy bandwidth (∼5 eV) of a soft X-ray absorption resonance.

Super high quality aspherical x-ray mirrors with a residual slope error of ∼100 nrad (root-mean-square) and a height error of ∼1-2 nm (peak-to-valley), and even lower, are now available from a number of the most advanced vendors utilizing deterministic polishing techniques. The mirror specification for the fabrication is based on the simulations of the desired performance of the mirror in the beamline optical system and is normally given with the acceptable level of deviation of the mirror figure and finish from the desired ideal shape. For example, in the case of aspherical x-ray mirrors designed for the Advanced Light Source (ALS) QERLIN beamline, the ideal shape is defined with the beamline application (conjugate) parameters and their tolerances. In this paper, we first discuss an original procedure and dedicated software developed at the ALS X-Ray Optics Laboratory (XROL) for optimization of beamline performance of pre-shaped hyperbolic and elliptical mirrors. The optimization is based on results of ex situ surface slope metrology and consists in minimization of the mirror shape error by determining the conjugate parameters of the best-fit ideal shape within the specified tolerances. We describe novel optical metrology instrumentation, measuring techniques, and analytical methods used at the XROL for acquisition of surface slope data and optimization of the optic's beamline performance. The high efficacy of the developed experimental methods and data analysis procedures is demonstrated in results of measurements with and performance optimization of hyperbolic and elliptical cylinder mirrors designed and fabricated for the ALS QERLIN beamline.

Multilayer-coated blazed gratings (MBG) are the most promising solution for ultra-high resolution soft X-ray spectroscopy, since they can have very high groove density and provide high-order operation and very high diffraction efficiency. The performance of MBGs however depends critically on the conformal deposition of the multilayer (ML) stack on a saw-tooth substrate and the minimization of roughness. We present an analysis of the roughening and smoothing processes during growth of Mo/Si multilayers deposited over a range of pressures of Ar sputtering gas on flat and saw-tooth substrates. A Linear Continuum Model (LCM) of the film growth was used to understand the interplay between smoothing and roughening of the ML films and to predict the optimum conditions for deposition. The MBG coated under the optimal deposition conditions demonstrated high diffraction efficiency in the EUV and soft X-ray wavelength ranges

Battery function is determined by the efficiency and reversibility of the electrochemical phase transformations at solid electrodes. The microscopic tools available to study the chemical states of matter with the required spatial resolution and chemical specificity are intrinsically limited when studying complex architectures by their reliance on two-dimensional projections of thick material. Here, we report the development of soft X-ray ptychographic tomography, which resolves chemical states in three dimensions at 11 nm spatial resolution. We study an ensemble of nano-plates of lithium iron phosphate extracted from a battery electrode at 50% state of charge. Using a set of nanoscale tomograms, we quantify the electrochemical state and resolve phase boundaries throughout the volume of individual nanoparticles. These observations reveal multiple reaction points, intra-particle heterogeneity, and size effects that highlight the importance of multi-dimensional analytical tools in providing novel insight to the design of the next generation of high-performance devices., Here the authors show the development of soft X-ray ptychographic tomography to quantify the electrochemical state and resolve phase boundaries throughout the volume of individual nano-particles from a composite battery electrode.

A blazed diffraction grating for the EUV lithography Beamline 12.0.1 of the Advanced Light Source has been fabricated using optical direct write lithography and anisotropic wet etching technology. A variable line spacing pattern was recorded on a photoresist layer and transferred to a hard mask layer of the grating substrate by a plasma etch. Then anisotropic wet etching was applied to shape triangular grating grooves with precise control of the ultralow blaze angle. Variation of the groove density along the grating length was measured with a Long Trace Profiler (LTP). Fourier analysis of the LTP data confirmed high groove placement accuracy of the grating. The grating coated with a Ru coating demonstrated diffraction efficiency of 69.6% in the negative first diffraction order which is close to theoretical efficiency at the wavelength of 13.5 nm. This work demonstrates an alternative approach to fabrication of highly efficient and precise x-ray diffraction gratings with ultra-low blaze angles.

High-resolution Resonance Inelastic X-ray Scattering (RIXS) is a technique that allows us to probe the electronic excitations of complex materials with unprecedented precision. However, the RIXS process has a low cross section, compounded by the fact that the optical spectrometers used to analyze the scattered photons can only collect a small solid angle and overall have a small efficiency. Here we present a method to significantly increase the throughput of RIXS systems, by energy multiplexing, so that a complete RIXS map of scattered intensity versus photon energy in and photon energy out can be recorded simultaneously1. This parallel acquisition scheme should provide a gain in throughput of over 100.. A system based on this principle, QERLIN, is under construction at the Advanced Light Source (ALS).

A 2500 lines/mm Multilayer Blazed Grating (MBG) optimized for the soft x-ray wavelength range was fabricated and tested. The grating coated with a W/B4C multilayer demonstrated a record diffraction efficiency in the 2nd blazed diffraction order in the energy range from 500 to 1200 eV. Detailed investigation of the diffraction properties of the grating demonstrated that the diffraction efficiency of high groove density MBGs is not limited by the normal shadowing effects that limits grazing incidence x-ray grating performance. Refraction effects inherent in asymmetrical Bragg diffraction were experimentally confirmed for MBGs. The refraction affects the blazing properties of the MBGs and results in a shift of the resonance wavelength of the gratings and broadening or narrowing of the grating bandwidth depending on diffraction geometry. The true blaze angle of the MBGs is defined by both the real structure of the multilayer stack and by asymmetrical refraction effects. Refraction effects can be used as a powerful tool in providing highly efficient suppression of high order harmonics.

Multilayer coated blazed gratings with high groove density are the most promising candidate for ultra-high resolution soft x-ray spectroscopy. They combine the ability of blazed gratings to concentrate almost all diffraction energy in a desired high diffraction order with high reflectance soft x-ray multilayers. However in order to realize this potential, the grating fabrication process should provide a near perfect groove profile with an extremely smooth surface of the blazed facets. Here we report on successful fabrication and testing of ultra-dense saw-tooth substrates with 5,000 and 10,000 lines/mm.

At the Advanced Light Source (ALS), we are developing broadly applicable, high-accuracy, in-situ, at-wavelength wavefront slope measurement techniques for Kirkpatrick-Baez (KB) mirror nano-focusing. In this paper, we report an initial cross-check of ex-situ and in-situ metrology of a bendable temperature stabilized KB mirror. This cross-check provides a validation of the in-situ shearing interferometry currently under development at the ALS.

We present details of design of elliptically bent Kirkpatrick-Baez mirrors developed and successfully used at the advanced light source for submicron focusing. A distinctive feature of the mirror design is an active temperature stabilization based on a Peltier element attached directly to the mirror body. The design and materials have been carefully optimized to provide high heat conductance between the mirror body and substrate. We describe the experimental procedures used when assembling and precisely shaping the mirrors, with special attention paid to laboratory testing of the mirror-temperature stabilization. For this purpose, the temperature dependence of the surface slope profile of a specially fabricated test mirror placed inside a temperature-controlled container was measured. We demonstrate that with active mirror-temperature stabilization, a change of the surrounding temperature by more than 3 K does not noticeably affect the mirror figure. Without temperature stabilization, the rms slope error is changed by approximately 1.5 μrad (primarily defocus) under the same conditions.

Beamline 12.3.2 at the Advanced Light Source is a newly commissioned beamline dedicated to x-ray microdiffraction. It operates in both monochromatic and polychromatic radiation mode. The facility uses a superconducting bending magnet source to deliver an X-ray spectrum ranging from 5 to 22 keV. The beam is focused down to {approx} 1 um size at the sample position using a pair of elliptically bent Kirkpatrick-Baez mirrors enclosed in a vacuum box. The sample placed on high precision stages can be raster-scanned under the microbeam while a diffraction pattern is taken at each step. The arrays of diffraction patterns are then analyzed to derive distribution maps of phases, strain/stress and/or plastic deformation inside the sample.

The purpose of this document is to outline the Advanced Light Source (ALS) approach for preventing a radiation accident scenario on the ALS experimental floor due to top-off operation. The document will describe the potential risks, the analysis, and the resulting specifications for the controls.

High-resolution Resonant Inelastic X-ray Scattering (RIXS) requires diffraction gratings with very exacting characteristics. The gratings should provide both very high dispersion and high efficiency which are conflicting requirements and extremely challenging to satisfy in the soft x-ray region for a traditional grazing incidence geometry. To achieve high dispersion one should increase the groove density of a grating; this however results in a diffraction angle beyond the critical angle range and results in drastic efficiency loss. The problem can be solved by use of multilayer coated blazed gratings (MBG). In this work we have investigated the diffraction characteristics of MBGs via numerical simulations and have developed a procedure for optimization of grating design for a multiplexed high resolution imaging spectrometer for RIXS spectroscopy to be built in sector 6 at the Advanced Light Source (ALS). We found that highest diffraction efficiency can be achieved for gratings optimized for 4th or 5th ord...

The performance of battery electrode materials is strongly affected by inefficiencies in utilization kinetics and cycle life as well as size effects. Observations of phase transformations in these materials with high chemical and spatial resolution can elucidate the relationship between chemical processes and mechanical degradation. Soft X-ray ptychographic microscopy combined with X-ray absorption spectroscopy and electron microscopy creates a powerful suite of tools that we use to assess the chemical and morphological changes in lithium iron phosphate (LiFePO4) micro- and nanocrystals that occur upon delithiation. All sizes of partly delithiated crystals were found to contain two phases with a complex correlation between crystallographic orientation and phase distribution. However, the lattice mismatch between LiFePO4 and FePO4 led to severe fracturing on microcrystals, whereas no mechanical damage was observed in nanoplates, indicating that mechanics are a principal driver in the outstanding electrode performance of LiFePO4 nanoparticles. These results demonstrate the importance of engineering the active electrode material in next generation electrical energy storage systems, which will achieve theoretical limits of energy density and extended stability. This work establishes soft X-ray ptychographic chemical imaging as an essential tool to build comprehensive relationships between mechanics and chemistry that guide this engineering design.

During the last two decades, scanning transmission x-ray microscopy (STXM) has evolved into a powerful characterization tool. For best performance, STXM's are located at undulator sources at synchrotron facilities. The scarcity and expense of undulator sources and associated heamlines limits the number of available STXMs. We have successfully re-examined the use of bending magnets as a source for a STXM and implemented a interferometer controlled STXM with excellent performance at the beamline 5.3,2, at the Advanced Light Source Near the carbon K-edge, periodic features with 30 nm half-period could be resolved with a zone plate that has a 40 nm outermost zone width with an energy resolution corresponding to 100 meV and an intensity of about 1 MHz The design and perforormance of the microscope are described.

Two new soft X-ray scanning transmission microscopes located at the Advanced Light Source (ALS) have been designed, built and commissioned. Interferometer control implemented in both microscopes allows the precise measurement of the transverse position of the zone plate relative to the sample. Long-term positional stability and compensation for transverse displacement during translations of the zone plate have been achieved. The interferometer also provides low-distortion orthogonal x, y imaging. Two different control systems have been developed: a digital control system using standard VXI components at beamline 7.0, and a custom feedback system based on PC AT boards at beamline 5.3.2. Both microscopes are diffraction limited with the resolution set by the quality of the zone plates. Periodic features with 30 nm half period can be resolved with a zone plate that has a 40 nm outermost zone width. One microscope is operating at an undulator beamline (7.0), while the other is operating at a novel dedicated bending-magnet beamline (5.3.2), which is designed specifically to illuminate the microscope. The undulator beamline provides count rates of the order of tens of MHz at high-energy resolution with photon energies of up to about 1000 eV. Although the brightness of a bending-magnet source is about four orders of magnitude smaller than that of an undulator source, photon statistics limited operation with intensities in excess of 3 MHz has been achieved at high energy resolution and high spatial resolution. The design and performance of these microscopes are described.

Morphological details of calcium silicate hydrate (C–S–H) stemming from the hydration process of Portland cement (PC) phases are crucial for understanding the PC-based systems but are still only partially known. Here we introduce the first soft X-ray ptychographic imaging of tricalcium silicate (C3S) hydration products. The results are compared using both scanning transmission X-ray and electron transmission microscopy data. The evidence shows that ptychography is a powerful method to visualize the details of outer and inner product C–S–H of fully hydrated C3S, which have fibrillar and an interglobular structure with average void sizes of 20 nm, respectively. The high-resolution ptychrography image enables us to perform morphological quantification of C–S–H, and, for the first time, to possibly distinguish the contributions of inner and outer product C–S–H to the small angle scattering of cement paste. The results indicate that the outer product C–S–H is mainly responsible for the q−3 regime, whereas the inner product C–S–H transitions to a q−2 regime. Various hypotheses are discussed to explain these regimes.

The high brightness of the bend magnets at the Advanced Light Source has been exploited to illuminate a scanning transmission X-ray microscope (STXM). This is the first diffraction-limited scanning X-ray microscope to operate with a useful count rate on a synchrotron bend-magnet source. A simple dedicated beamline has been built covering the range of photon energy from 250 eV to 600 eV. The beamline is always available and needs little adjustment. Use of this facility is much easier than that of installations that share undulator beams. This facility provides radiation for C 1s, N 1s and O 1s near-edge X-ray absorption spectromicroscopy with STXM count rates in excess of 1 MHz and with spectral resolution typically 1:2000, limited to about 1:5000.

We present a new ptychographic x-ray microscope dedicated to soft x-ray tomography and spectromicroscopy of nano-materials at the Advanced Light Source. The microscope utilizes an ultra-stable, high performance scanning mechanism with laser interferometer feedback for sample positioning and a fast frame rate charge-coupled device detector for soft x-ray diffraction measurements. The microscope can achieve point scan rates of 120 Hz with 1 nm RMS positioning accuracy. A high performance data pipeline has been developed which enables real time ptychographic reconstructions and user-friendly operation. This instrument, called The Nanosurveyor, can achieve a spatial resolution at least 10 times finer than the x-ray spot size in both two and three dimensions with sensitivity to electronicand magnetic states of nano-materials. In this paper we demonstrate the tomographic and spectromicroscopic capability of the Nanosurveyor instrument. At high brightness x-ray sources this instrument will enable spectromicroscopy and tomography of materials with diffraction limited spatial resolution.

At the Advanced Light Source (ALS), we are developing broadly applicable, high-accuracy, in situ, at-wavelength wavefront slope measurement techniques for Kirkpatrick-Baez (KB) mirror nano-focusing. We describe here details of the metrology beamline endstation, the at-wavelength tests, and an original alignment method that have already allowed us to precisely set a bendable KB mirror to achieve a FWHM focused spot size of ~;;120 nm, at 1-nm soft x-ray wavelength.

A grand challenge in soft x-ray spectroscopy is to drive the resolving power of monochromators and spectrometers from the 10(4) achieved routinely today to well above 10(5). This need is driven mainly by the requirements of a new technique that is set to have enormous impact in condensed matter physics, Resonant Inelastic X-ray Scattering (RIXS). Unlike x-ray absorption spectroscopy, RIXS is not limited by an energy resolution dictated by the core-hole lifetime in the excitation process. Using much higher resolving power than used for normal x-ray absorption spectroscopy enables access to the energy scale of soft excitations in matter. These excitations such as magnons and phonons drive the collective phenomena seen in correlated electronic materials such as high temperature superconductors. RIXS opens a new path to study these excitations at a level of detail not formerly possible. However, as the process involves resonant excitation at an energy of around 1 keV, and the energy scale of the excitations one would like to see are at the meV level, to fully utilize the technique requires the development of monochromators and spectrometers with one to two orders of magnitude higher energy resolution than has been conventionally possible. Here we investigate the detailed diffraction characteristics of multilayer blazed gratings. These elements offer potentially revolutionary performance as the dispersive element in ultra-high resolution x-ray spectroscopy. In doing so, we have established a roadmap for the complete optimization of the grating design. Traditionally 1st order gratings are used in the soft x-ray region, but we show that as in the optical domain, one can work in very high spectral orders and thus dramatically improve resolution without significant loss in efficiency.

The blazing ability of multilayer-coated blazed gratings (MBGs) was systematically investigated via numerical calculation of the diffraction efficiency with a rigorous electromagnetic simulation code. It was found that the blazing condition is not exact and allows significant deviation from the ideal situation for ultra-dense MBGs. A mismatch of the interfaces of the multilayer (ML) stacks of adjacent grooves results in a modified effective blaze angle, which gives the opportunity to control and tune precisely the blaze angle via a proper choice of ML d-spacing. Also this allows a new kind of x-ray gratings that have a variable line spacing (VLS) as well as a variable blaze angle. Precise adjustment of a local blaze angle of a VLS MBG can be achieved with a laterally graded ML, providing very high diffraction efficiency for the whole area of the grating.

X-ray microscopy is powerful in that it can probe large volumes of material at high spatial resolution with exquisite chemical, electronic and bond orientation contrast. The development of diffraction-based methods such as ptychography has, in principle, removed the resolution limit imposed by the characteristics of the X-ray optics. Here, using soft X-ray ptychography, we demonstrate the highest-resolution X-ray microscopy ever achieved by imaging 5â €..nm structures. We quantify the performance of our microscope and apply the method to the study of delithiation in a nanoplate of LiFePO 4, a material of broad interest in electrochemical energy storage. We calculate chemical component distributions using the full complex refractive index and demonstrate enhanced contrast, which elucidates a strong correlation between structural defects and chemical phase propagation. The ability to visualize the coupling of the kinetics of a phase transformation with the mechanical consequences is critical to designing materials with ultimate durability.

A Variable Line Spacing (VLS) diffraction grating has been fabricated using an optical direct write technique. This grating is now in use at the Advanced Light Source, in beamline 12.0.1, delivering light for EUV lithography. Direct Write Lithography (DWL) with focused light at λ = 442 nm was used for the first time to record a VLS grating pattern on a substrate coated with a photoresist. The pattern was transferred to the Si substrate surface using reactive plasma etch. Precision of groove placement was verified by wavefront measurements of a witness grating recorded simultaneously with the VLS pattern. Atomic force microscope measurements confirmed near ideal groove shape and high smoothness of the grating grooves. The grating coated with a Ru coating demonstrated diffraction efficiency of 39.5% in the negative first diffraction order which corresponds to theoretical efficiency at the wavelength of 13.5 nm. This work validates the DWL approach as a promising technique for advanced grating fabrication.

Imperfections in the multilayer stack deposited on a saw-tooth substrate are the main factor limiting the diffraction efficiency of extreme ultraviolet and soft x-ray multilayer-coated blazed gratings (MBGs). Since the multilayer perturbations occur in the vicinity of antiblazed facets of the substrates, reduction of the groove density of MBGs is expected to enlarge the area of unperturbed multilayer and result in higher diffraction efficiency. At the same time the grating should be optimized for higher-order operation in order to keep high dispersion and spectral resolution. In this work we show the validity of this approach and demonstrate significant enhancement of diffraction efficiency of MBGs using higher-order diffraction. A new record for diffraction efficiency of 52% in the second diffraction order was achieved for an optimized MBG with groove density of 2525 lines/mm at the wavelength of 13.4 nm.

A new beam line (beam line 11.0) at the Advanced Light Source has been designed to employ an SX700 (Peterson, Opt. Commun. 40 (1982) 402) style variable-included-angle plane-grating-monochromator. The extended range available from a specific grating is exploited to cover energies from the carbon 1 s absorption edge to the oxygen 1 s absorption edge with two different gratings (150 and 1200 lines/mm) with dispersion different by a factor of three. The phase space of a zone plate microscope can then be efficiently filled either at low or high resolution (R=2500 and 7500). At the same time the monochromator is designed to cover the energy range from 75 to 1500 eV using the same two gratings at high resolution for spectroscopy. A deformable mirror pair will re-focus to a monochromatic spot 5×10 μm, matched into the acceptance of a fluorescence spectrometer. The monochromator will operate in vertically collimated light and the free choice of focussing parameter provides a guarantee of high resolution even when the power loading is high. However, we will provide a thermally engineered pre-mirror so that the high resolution requirement at low photon energy can be met without loss of efficiency.

The electronic structure of C 60 and potassium doped C 60 has been studied by soft X-ray absorption and emission spectroscopies. The C Kα emission spectrum of doped C 60 shows a resolved filled lowest unoccupied molecular orbitals (LUMO) ( t 1 u ) -derived valence band. The intensity ratio of the highest occupied molecular orbitals (HOMO)-derived band to LUMO-derived band is 2, indicating that a K 6 C 60 phase is forming the potassium doped C 60 film. Small variations with excitation energy in the spectral shape compared to solid C 60 suggest that resonant inelastic X-ray scattering becomes less prominent due to the formation of solid-state system upon potassium doping.

Interfaces between minerals and water, and minerals and microbes, are chemically complex and traditionally have been considered beyond the capabilities of surface science techniques, except for model systems under controlled laboratory conditions. We report on some advances in soft x-ray spectroscopy and imaging that make it possible to extract meaningful chemical information about interfaces of specimens that have complex histories, involving environmental exposure. These measurements utilize x-ray absorption spectroscopy, in combination with spatial resolution, in a technique called x-ray spectromicroscopy. Examples are drawn from attempts at Mn and Fe speciation of biologically produced minerals, bio-corrosion deposits and clays.

Chemical state analyses of heat-treated polyacrylonitrile (PAN) fibers with a spatial resolution of 200 nm have been performed using scanning transmission X-ray microscopy (STXM) at a third generation synchrotron radiation facility. Near-edge X-ray absorption fine structure (NEXAFS) spectra and chemical state images have been obtained on the cross-sectioned fiber specimens. A clear `core–rim' structure has been observed in the heat-treated fibers. The spectral characteristics show that the fiber has less nitrile group in the core region, suggesting that, contrary to the model widely believed, the conversion of the nitrile to other chemical species proceeds faster in the core of the fibers.

The structures of a series of (TiSe2)n(NbSe2)m superlattices grown through controlled crystallization of designed multilayer reactants have been studied. X-ray diffraction of the data of the superlattices after crystallization show considerable preferred orientation, with the basal plane of the dichalcogenide structure parallel to the substrate to within 0.1°. Lattice refinement using the observed (00l) diffraction maxima yields lattice parameters along the c axis that are consistent with those expected based on the target superlattices and lattice parameters of the binary constituents. These (00l) diffraction data, however, contain no information about the crystalline structure in the ab plane of the superlattice associated with the preferred c-axis orientation. Off-specular x-ray diffraction (XRD), scanning electron microscopy, and scanning transmission x-ray microscopy (STXM) were used to explore the structure and homogeneity of the superlattices in the ab plane. XRD results rule out preferred long-ran...

Several third generation synchrotron radiation facilities are now operational, and the high brightness of these photon sources offers new opportunities for X-ray microscopy. Well developed synchrotron radiation spectroscopy techniques are being applied in new instruments capable of imaging the surface of a material with a spatial resolution smaller than 1 μm. There are two aspects to this. One is to further the field of surface science by exploring the effects of spatial variations across a surface on a scale not previously accessible to X-ray measurements. The other is to open up new analytical techniques in materials science using X-rays on a spatial scale comparable with that of the processes or devices to be studied. The development of the spectromicroscopy program at the Advanced Light Source will employ a variety of instruments, some of which are already operational. Their development and use will be discussed, and recent results will be presented to illustrate their capabilities.

MAESTRO, the Microscopic and Electronic STRucture Observatory, currently under construction at the Advanced Light Source (ALS), will be a world premier facility for the study of electronic and structural properties of in situ grown crystals. The new facility will be comprised of several end-stations, including angle-resolved photoemission spectroscopy, μARPES and nARPES end-stations, and a photoemission electron microscope combined with a lowenergy electron microscope (PEEM/LEEM). Redirection of the x-ray beam between the μARPES and PEEM/LEEM end-stations, which are longitudinally separated by 2.5 meters, uses a system of two bendable mirrors, placed in Kirkpatrick-Baez configuration designed for two foci. Here we present the details of the mirrors’ design and report on the characterization of the mirrors carried out at the ALS X-ray optical laboratory (XROL). Optimal tuning and calibration of the mirrors was performed using a technique recently developed at the OML [Opt. Eng. 48(8), 083601 (2009)]. The technique is based on regression analysis of surface slope data obtained with a long trace profiler (LTP). We provide results of tests of temporal and temperature stabilities of the shape of the mirrors. High reliability of the optical metrology with the mirrors has become possible due to a modification of the tuning procedure described in the present article. The modification allows accounting for the gravity sag effect, as well as the LTP systematic error in measurements with significantly curved x-ray optics.

Fabrication of diffraction grating for x-rays is a very challenging problem due to the exacting requirements of surface quality, groove position, and groove profile. Traditional fabrication techniques have significant limitations and do not cover all the necessary requirements. For example, classical holographic recording is limited in the type of groove patterns that can be produced. This is particularly important in the design of wide aperture high resolution spectrometers, where aberration correction using complex groove patterns is necessary. We are pioneering the use of direct-write mask-less optical lithography to make grating patterns of arbitrary complexity. In this work we report on the first results from our direct-write mask-less approach, including quality assessment of the patterns using interferometric techniques.

The advent of third generation synchrotron soft X-ray radiation sources has opened up many new opportunities for the use of spectroscopy and microscopy to study the structure of complex materials. The ultra-high brightness of these sources offers the possibility of combining the two techniques so that the spectroscopy of microscopic areas of a material may be studied (spectromicroscopy), and in addition offers tremendous flux and resolution enhancements for traditional macroscopic surface studies. The optical properties of both bending magnet and undulator sources for use in third generation soft X-ray sources offer significant possibilities for improving the performance of optical systems compared with traditional designs. We will describe two recent such advances in beamline optical system design at the advanced light source (ALS) and review the performance of a current generation of undulator based beamlines at the ALS.

X-ray fluorescence of condensed ${\mathrm{C}}_{60}$ has been recorded in high resolution using monochromatic synchrotron radiation excitation. Strong intensity modulation of constituent spectral features is observed with varying excitation energy up to 10 eV above threshold. The energy dependence is interpreted as due to resonant inelastic x-ray scattering, leading to symmetry selection rules governing the two-photon process in the fully symmetric molecule.

Realizing the experimental potential of high-brightness, next generation synchrotron and free-electron laser light sources requires the development of reflecting x-ray optics capable of wavefront preservation and high-resolution nano-focusing. At the Advanced Light Source (ALS) beamline 5.3.1, we are developing broadly applicable, high-accuracy, in situ, at-wavelength wavefront measurement techniques to surpass 100-nrad slope measurement accuracy for diffraction-limited Kirkpatrick-Baez (KB) mirrors. The at-wavelength methodology we are developing relies on a series of wavefront-sensing tests with increasing accuracy and sensitivity, including scanning-slit Hartmann tests, grating-based lateral shearing interferometry, and quantitative knife-edge testing. We describe the original experimental techniques and alignment methodology that have enabled us to optimally set a bendable KB mirror to achieve a focused, FWHM spot size of 150 nm, with 1 nm (1.24 keV) photons at 3.7 mrad numerical aperture. The predictions of wavefront measurement are confirmed by the knife-edge testing. The side-profiled elliptically bent mirror used in these one-dimensional focusing experiments was originally designed for a much different glancing angle and conjugate distances. Visible-light long-trace profilometry was used to pre-align the mirror before installation at the beamline. This work demonstrates that high-accuracy, at-wavelength wavefront-slope feedback can be used to optimize the pitch, roll, and mirror-bending forces in situ, using procedures that are deterministic and repeatable.

Diffraction gratings with high efficiency and high groove density are required for EUV and soft x-ray spectroscopy techniques (such as Resonant Inelastic X-ray Scattering, RIXS) designed for state-of-the-art spectral resolution and throughput. A multilayer coated blazed grating (MBG) fabricated by deposition of a multilayer on a saw-tooth substrate could address these challenges. In order to obtain high diffraction efficiency one should provide perfect triangular grooves on a substrate and perfect replication of the groove profile during the multilayer deposition. However, multilayers trend to smooth out the corrugated surface of the substrates, resulting in the main limiting factor for efficiency of ultra-dense MBGs. Understanding of the growth of multilayers on saw-tooth substrates is a key for further grating improvement. In this work we investigate growth behavior of Al/Zr multilayers on saw-tooth substrates with a groove density of 10,000 lines/mm. We apply existing growth models to describe an evolution of Power Spectral Density functions of a grating surface during the multilayer deposition, and identify a main smoothing mechanism. We found that growth of flat multilayers is well modeled with surface diffusion caused by surface curvature as a main relaxation mechanism, while growth of the multilayer on saw-tooth substrates obeys different kinetics. Limitations of the linear approach and possible model improvements by accounting for an additional component of the surface diffusion flux, caused by a gradient of adatom concentration on a corrugated surface are discussed.

Ultra-high spectral resolution in the EUV and soft x-ray energy ranges requires the use of very high line density gratings with optimal design resulting in use of a Blazed Multilayer Grating (BMG) structure. Here we demonstrate the production of near-atomically perfect Si blazed substrates with an ultra-high groove density (10,000 l/mm) together with the measured and theoretical performance of an Al/Zr multilayer coating on the grating. A 1st order absolute efficiency of 13percent and 24.6percent was achieved at incidence angles of 11o and 36o respectively. Cross-sectional TEM shows the effect of smoothing caused by the surface mobility of deposited atoms and we correlate this effect with a reduction in peak diffraction efficiency. This work shows the high performance that can be achieved with BMGs based on small-period anisotropic etched Si substrates, but also the constraints imposed by the surface mobility of deposited species.

Multilayer coated blazed gratings with high groove density are the best candidates for use in high resolution EUV and soft x-ray spectroscopy. Theoretical analysis shows that such a grating can be potentially optimized for high dispersion and spectral resolution in a desired high diffraction order without significant loss of diffraction efficiency. In order to realize this potential, the grating fabrication process should provide a perfect triangular groove profile and an extremely smooth surface of the blazed facets. Here we report on recent progress achieved at the Advanced Light Source (ALS) in fabrication of high quality multilayer coated blazed gratings. The blazed gratings were fabricated using scanning beam interference lithography followed by wet anisotropic etching of silicon. A 200 nm period grating coated with a Mo/Si multilayer composed with 30 bi-layers demonstrated an absolute efficiency of 37.6% in the 3rd diffraction order at 13.6 nm wavelength. The groove profile of the grating was thoroughly characterized with atomic force microscopy before and after the multilayer deposition. The obtained metrology data were used for simulation of the grating efficiency with the vector electromagnetic PCGrate-6.1 code. The simulations showed that smoothing of the grating profile during the multilayer deposition is the main reason for efficiency losses compared to the theoretical maximum. Investigation of the grating with cross-sectional transmission electron microscopy revealed a complex evolution of the groove profile in the course of the multilayer deposition. Impact of the shadowing and smoothing processes on growth of the multilayer on the surface of the sawtooth substrate is discussed.

Nano-focusing and brightness preservation for ever brighter synchrotron radiation and free electron laser beamlines require surface slope tolerances of x-ray optics on the order of 100 nrad. While the accuracy of fabrication and ex situ metrology of x-ray mirrors has improved over time, beamline in situ performance of the optics is often limited by application specific factors such as x-ray beam heat loading, temperature drift, alignment, vibration, etc. In the present work, we discuss the recent results from the Advanced Light Source developing high accuracy, in situ, at-wavelength wavefront measurement techniques to surpass 100-nrad accuracy surface slope measurements with reflecting x-ray optics. The techniques will ultimately allow closed-loop feedback systems to be implemented for x-ray nano-focusing. In addition, we present a dedicated metrology beamline endstation, applicable to a wide range of in situ metrology and test experiments. The design and performance of a bendable Kirkpatrick-Baez (KB) mirror with active temperature stabilization will also be presented. The mirror is currently used to study, refine, and optimize in situ mirror alignment, bending and metrology methods essential for nano-focusing application.

Volume x-ray gratings consisting of a multilayer coating deposited on a blazed substrate can diffract with very high efficiency, even in high orders if diffraction conditions in-plane (grating) and out-of-plane (Bragg multilayer) are met simultaneously. This remarkable property, however, depends critically on the ability to create a structure with near atomic perfection. In this Letter we report on a method to produce these structures. We report measurements that show, for a 5000l/mm grating diffracting in the third order, a diffraction efficiency of 37.6% at a wavelength of 13.6nm. This work now shows a direct route to achieving high diffraction efficiency in high order at wavelengths throughout the soft x-ray energy range.

We report on the design and construction of a higher energy Scanning Transmission X‐ray Microscope on a new bend magnet beam line at the Advanced Light Source. Previously we have operated such an instrument on a bend magnet for C, N and O 1s NEXAFS spectroscopy. The new instrument will have similar performance at higher energies up to and including the S 1s edge at 2472eV. A new microscope configuration is planned. A more open geometry will allow a fluorescence detector to count emitted photons from the front surface of the sample. There will be a capability for zone plate scanning in addition to the more conventional sample scanning mode. This will add the capability for imaging a massive sample at high resolution over a limited field of view, so that heavy reaction cells may be used to study processes in‐situ, exploiting the longer photon attenuation length and the longer zone plate working distances available at higher photon energy. The energy range will extend down to include the C1s edge at 300eV, to allow high energy NEXAFS microscopic studies to correlate with the imaging of organics in the same sample region of interest.