Nanoscale Three-Dimensional Imaging of Integrated Circuits Using a Scanning Electron Microscope and Transition-Edge Sensor Spectrometer.

X-ray nanotomography is a powerful tool for the characterization of nanoscale materials and structures, but it is difficult to implement due to the competing requirements of X-ray flux and spot size. Due to this constraint, state-of-the-art nanotomography is predominantly performed at large synchrotron facilities. We present a laboratory-scale nanotomography instrument that achieves nanoscale spatial resolution while addressing the limitations of conventional tomography tools. The instrument combines the electron beam of a scanning electron microscope (SEM) with the precise, broadband X-ray detection of a superconducting transition-edge sensor (TES) microcalorimeter. The electron beam generates a highly focused X-ray spot on a metal target held micrometers away from the sample of interest, while the TES spectrometer isolates target photons with a high signal-to-noise ratio. This combination of a focused X-ray spot, energy-resolved X-ray detection, and unique system geometry enables nanoscale, element-specific X-ray imaging in a compact footprint. The proof of concept for this approach to X-ray nanotomography is demonstrated by imaging 160 nm features in three dimensions in six layers of a Cu-SiO2 integrated circuit, and a path toward finer resolution and enhanced imaging capabilities is discussed.

Design of a 3000-Pixel Transition-Edge Sensor X-Ray Spectrometer for Microcircuit Tomography.

Feature sizes in integrated circuits have decreased substantially over time, and it has become increasingly difficult to three-dimensionally image these complex circuits after fabrication. This can be important for process development, defect analysis, and detection of unexpected structures in externally sourced chips, among other applications. Here, we report on a non-destructive, tabletop approach that addresses this imaging problem through x-ray tomography, which we uniquely realize with an instrument that combines a scanning electron microscope (SEM) with a transition-edge sensor (TES) x-ray spectrometer. Our approach uses the highly focused SEM electron beam to generate a small x-ray generation region in a carefully designed target layer that is placed over the sample being tested. With the high collection efficiency and resolving power of a TES spectrometer, we can isolate x-rays generated in the target from background and trace their paths through regions of interest in the sample layers, providing information about the various materials along the x-ray paths through their attenuation functions. We have recently demonstrated our approach using a 240 Mo/Cu bilayer TES prototype instrument on a simplified test sample containing features with sizes of ∼ 1 µm. Currently, we are designing and building a 3000 Mo/Au bilayer TES spectrometer upgrade, which is expected to improve the imaging speed by factor of up to 60 through a combination of increased detector number and detector speed.

Gamma and Decay Energy Spectroscopy Measurements of Trinitite.

We report gamma ray spectroscopy measurements of trinitite samples and analogous samples obtained from detonation sites in Nevada and Semipalatinsk, as well as in situ measurements of topsoil at the Trinity site. We also report the first isotopic composition measurements of trinitite using the novel forensics technique of decay energy spectroscopy (DES) as a complement to traditional forensics techniques. Our gamma spectroscopy and DES measurements are compared to other published results.

Surface-to-Bulk Redox Coupling through Thermally Driven Li Redistribution in Li- and Mn-Rich Layered Cathode Materials.

Li- and Mn-rich (LMR) layered cathode materials have demonstrated impressive capacity and specific energy density thanks to their intertwined redox centers including transition metal cations and oxygen anions. Although tremendous efforts have been devoted to the investigation of the electrochemically driven redox evolution in LMR cathode at ambient temperature, their behavior under a mildly elevated temperature (up to ∼100 °C), with or without electrochemical driving force, remains largely unexplored. Here we show a systematic study of the thermally driven surface-to-bulk redox coupling effect in charged Li1.2Ni0.15Co0.1Mn0.55O2. We for the first time observed a charge transfer between the bulk oxygen anions and the surface transition metal cations under ∼100 °C, which is attributed to the thermally driven redistribution of Li ions. This finding highlights the nonequilibrium state and dynamic nature of the LMR material at deeply delithiated state upon a mild temperature perturbation.

Use of Transition Models to Design High Performance TESs for the LCLS-II Soft X-Ray Spectrometer.

We are designing an array of transition-edge sensor (TES) microcalorimeters for a soft X-ray spectrometer at the Linac Coherent Light Source at SLAC National Accelerator Laboratory to coincide with upgrades to the free electron laser facility. The complete spectrometer will have 1000 TES pixels with energy resolution of 0.5 eV full-width at half-maximum (FWHM) for incident energies below 1 keV while maintaining pulse decay-time constants shorter than 100 µs. Historically, TES pixels have often been designed for a particular scientific application via a combination of simple scaling relations and trial-and-error experimentation with device geometry. We have improved upon this process by using our understanding of transition physics to guide TES design. Using the two-fluid approximation of the phase-slip line model for TES resistance, we determine how the geometry and critical temperature of a TES will affect the shape of the transition. We have used these techniques to design sensors with a critical temperature of 55 mK. The best sensors achieve an energy resolution of 0.75 eV FWHM at 1.25 keV. Building upon this result, we show how the next generation of sensors can be designed to reach our goal of 0.5 eV resolution.

L-edge spectroscopy of dilute, radiation-sensitive systems using a transition-edge-sensor array.

We present X-ray absorption spectroscopy and resonant inelastic X-ray scattering (RIXS) measurements on the iron L-edge of 0.5 mM aqueous ferricyanide. These measurements demonstrate the ability of high-throughput transition-edge-sensor (TES) spectrometers to access the rich soft X-ray (100-2000 eV) spectroscopy regime for dilute and radiation-sensitive samples. Our low-concentration data are in agreement with high-concentration measurements recorded by grating spectrometers. These results show that soft-X-ray RIXS spectroscopy acquired by high-throughput TES spectrometers can be used to study the local electronic structure of dilute metal-centered complexes relevant to biology, chemistry, and catalysis. In particular, TES spectrometers have a unique ability to characterize frozen solutions of radiation- and temperature-sensitive samples.

Measurement of the 240Pu/239Pu mass ratio using a transition-edge-sensor microcalorimeter for total decay energy spectroscopy.

We have developed a new category of sensor for measurement of the (240)Pu/(239)Pu mass ratio from aqueous solution samples with advantages over existing methods. Aqueous solution plutonium samples were evaporated and encapsulated inside of a gold foil absorber, and a superconducting transition-edge-sensor microcalorimeter detector was used to measure the total reaction energy (Q-value) of nuclear decays via heat generated when the energy is thermalized. Since all of the decay energy is contained in the absorber, we measure a single spectral peak for each isotope, resulting in a simple spectral analysis problem with minimal peak overlap. We found that mechanical kneading of the absorber dramatically improves spectral quality by reducing the size of radioactive inclusions within the absorber to scales below 50 nm such that decay products primarily interact with atoms of the host material. Due to the low noise performance of the microcalorimeter detector, energy resolution values of 1 keV fwhm (full width at half-maximum) at 5.5 MeV have been achieved, an order of magnitude improvement over α-spectroscopy with conventional silicon detectors. We measured the (240)Pu/(239)Pu mass ratio of two samples and confirmed the results by comparison to mass spectrometry values. These results have implications for future measurements of trace samples of nuclear material.

A tabletop X-ray tomography instrument for nanometer-scale imaging: reconstructions.

We show three-dimensional reconstructions of a region of an integrated circuit from a 130 nm copper process. The reconstructions employ x-ray computed tomography, measured with a new and innovative high-magnification x-ray microscope. The instrument uses a focused electron beam to generate x-rays in a 100 nm spot and energy-resolving x-ray detectors that minimize backgrounds and hold promise for the identification of materials within the sample. The x-ray generation target, a layer of platinum, is fabricated on the circuit wafer itself. A region of interest is imaged from a limited range of angles and without physically removing the region from the larger circuit. The reconstruction is consistent with the circuit's design file.

Metastable Brominated Nanodiamond Surface Enables Room Temperature and Catalysis-Free Amine Chemistry.

Bromination of high-pressure, high-temperature (HPHT) nanodiamond (ND) surfaces has not been explored and can open new avenues for increased chemical reactivity and diamond lattice covalent bond formation. The large bond dissociation energy of the diamond lattice-oxygen bond is a challenge that prevents new bonds from forming, and most researchers simply use oxygen-terminated NDs (alcohols and acids) as reactive species. In this work, we transformed a tertiary-alcohol-rich ND surface to an amine surface with ∼50% surface coverage and was limited by the initial rate of bromination. We observed that alkyl bromide moieties are highly labile on HPHT NDs and are metastable as previously found using density functional theory. The strong leaving group properties of the alkyl bromide intermediate were found to form diamond-nitrogen bonds at room temperature and without catalysts. This robust pathway to activate a chemically inert ND surface broadens the modalities for surface termination, and the unique surface properties of brominated and aminated NDs are impactful to researchers for chemically tuning diamond for quantum sensing or biolabeling applications.

Insensitivity of sub-Kelvin electron-phonon coupling to substrate properties.

We have examined the role of the substrate on electron-phonon coupling in normal-metal films of Mn-doped Al at temperatures below 1 K. Normal metal-insulator-superconductor junctions were used to measure the electron temperature in the films as a function of Joule heating power and phonon temperature. Theory suggests that the distribution of phonons available for interaction with electrons in metal films may depend on the acoustic properties of the substrate, namely, that the electron-phonon coupling constant Σ would be larger on the substrate with smaller sound speed. In contrast, our results indicate that within experimental error (typically ±10%), Σ is unchanged among the two acoustically distinct substrates used in our investigation.

A model for excess Johnson noise in superconducting transition-edge sensors.

Transition-edge sensors (TESs) are two-dimensional superconducting films utilized as highly sensitive detectors of energy or power. These detectors are voltage biased in the superconducting-normal transition where the film resistance is both finite and a strong function of temperature. Unfortunately, the amount of electrical noise observed in TESs exceeds the predictions of existing noise theories. We describe a possible mechanism for the unexplained excess noise, which we term "mixed-down noise." The source is Johnson noise, which is mixed down to low frequencies by Josephson oscillations in devices with a nonlinear current-voltage relationship. We derive an expression for the power spectral density of this noise and show that its predictions agree with measured data.

Valence-to-core X-ray emission spectroscopy of titanium compounds using energy dispersive detectors.

X-ray emission spectroscopy (XES) of transition metal compounds is a powerful tool for investigating the spin and oxidation state of the metal centers. Valence-to-core (vtc) XES is of special interest, as it contains information on the ligand nature, hybridization, and protonation. To date, most vtc-XES studies have been performed with high-brightness sources, such as synchrotrons, due to the weak fluorescence lines from vtc transitions. Here, we present a systematic study of the vtc-XES for different titanium compounds in a laboratory setting using an X-ray tube source and energy dispersive microcalorimeter sensors. With a full-width at half-maximum energy resolution of approximately 4 eV at the Ti Kß lines, we measure the XES features of different titanium compounds and compare our results for the vtc line shapes and energies to previously published and newly acquired synchrotron data as well as to new theoretical calculations. Finally, we report simulations of the feasibility of performing time-resolved vtc-XES studies with a laser-based plasma source in a laboratory setting. Our results show that microcalorimeter sensors can already perform high-quality measurements of vtc-XES features in a laboratory setting under static conditions and that dynamic measurements will be possible in the future after reasonable technological developments.

Chemical control of competing electron transfer pathways in iron tetracyano-polypyridyl photosensitizers.

Photoinduced intramolecular electron transfer dynamics following metal-to-ligand charge-transfer (MLCT) excitation of [Fe(CN)4(2,2'-bipyridine)]2- (1), [Fe(CN)4(2,3-bis(2-pyridyl)pyrazine)]2- (2) and [Fe(CN)4(2,2'-bipyrimidine)]2- (3) were investigated in various solvents with static and time-resolved UV-Visible absorption spectroscopy and Fe 2p3d resonant inelastic X-ray scattering (RIXS). This series of polypyridyl ligands, combined with the strong solvatochromism of the complexes, enables the 1MLCT vertical energy to be varied from 1.64 eV to 2.64 eV and the 3MLCT lifetime to range from 180 fs to 67 ps. The 3MLCT lifetimes in 1 and 2 decrease exponentially as the MLCT energy increases, consistent with electron transfer to the lowest energy triplet metal-centred (3MC) excited state, as established by the Tanabe-Sugano analysis of the Fe 2p3d RIXS data. In contrast, the 3MLCT lifetime in 3 changes non-monotonically with MLCT energy, exhibiting a maximum. This qualitatively distinct behaviour results from a competing 3MLCT → ground state (GS) electron transfer pathway that exhibits energy gap law behaviour. The 3MLCT → GS pathway involves nuclear tunnelling for the high-frequency polypyridyl breathing mode (hν = 1530 cm-1), which is most displaced for complex 3, making this pathway significantly more efficient. Our study demonstrates that the excited state relaxation mechanism of Fe polypyridyl photosensitizers can be readily tuned by ligand and solvent environment. Furthermore, our study reveals that extending charge transfer lifetimes requires control of the relative energies of the 3MLCT and the 3MC states and suppression of the intramolecular distortion of the acceptor ligand in the 3MLCT excited state.

Tile-and-trim micro-resonator array fabrication optimized for high multiplexing factors.

We present a superconducting micro-resonator array fabrication method that is scalable and reconfigurable and has been optimized for high multiplexing factors. The method uses uniformly sized tiles patterned on stepper photolithography reticles as the building blocks of an array. We demonstrate this technique on a 101-element microwave kinetic inductance detector (MKID) array made from a titanium-nitride superconducting film. Characterization reveals 1.5% maximum fractional frequency spacing deviations caused primarily by material parameters that vary smoothly across the wafer. However, local deviations exhibit a Gaussian distribution in fractional frequency spacing with a standard deviation of 2.7 × 10-3. We exploit this finding to increase the yield of the BLAST-TNG 250 µm production wafer by placing resonators in the array close in both physical and frequency space. This array consists of 1836 polarization-sensitive MKIDs wired in three multiplexing groups. We present the array design and show that the achieved yield is consistent with our model of frequency collisions and is comparable to what has been achieved in other low temperature detector technologies.

Configurable error correction of code-division multiplexed TES detectors with a cryotron switch.

The development of a superconducting analog to the transistor with extremely low power dissipation will accelerate the proliferation of low-temperature circuitry operating in the milliKelvin regime. The thin-film, magnetically actuated cryotron switch is a candidate building block for more complicated and flexible milliKelvin circuitry. We demonstrate its utility for implementing reconfigurable circuitry by integrating a cryotron switch into flux-summed code-division SQUID multiplexed readout for large arrays of transition-edge-sensor (TES) microcalorimeters. Code-division multiplexing eliminates the noise penalty of time-division multiplexing while being drop-in compatible with the latter's control electronics. However, code-division multiplexing is susceptible to single-point failure mechanisms which can result in an unconstrained demodulation matrix and the loss of information from many sensing elements. In the event of a failure, the integrated cryotron switch provides a zero-signal output from a single TES, enabling the demodulation matrix used to compute TES signals from SQUID signals to be constrained and data recovered from the remaining sensors. This demonstration of configurable error correction provides both a realworld application of the cryotron switch and a foundation for more complex circuitry at milliKelvin temperatures.

Lynx x-ray microcalorimeter.

Lynx is an x-ray telescope, one of four large satellite mission concepts currently being studied by NASA to be a flagship mission. One of Lynx's three instruments is an imaging spectrometer called the Lynx x-ray microcalorimeter (LXM), an x-ray microcalorimeter behind an x-ray optic with an angular resolution of 0.5 arc sec and ∼2 m2 of area at 1 keV. The LXM will provide unparalleled diagnostics of distant extended structures and, in particular, will allow the detailed study of the role of cosmic feedback in the evolution of the Universe. We discuss the baseline design of LXM and some parallel approaches for some of the key technologies. The baseline sensor technology uses transition-edge sensors, but we also consider an alternative approach using metallic magnetic calorimeters. We discuss the requirements for the instrument, the pixel layout, and the baseline readout design, which uses microwave superconducting quantum interference devices and high-electron mobility transistor amplifiers and the cryogenic cooling requirements and strategy for meeting these requirements. For each of these technologies, we discuss the current technology readiness level and our strategy for advancing them to be ready for flight. We also describe the current system design, including the block diagram, and our estimate for the mass, power, and data rate of the instrument.

Soft X-ray spectroscopy with transition-edge sensors at Stanford Synchrotron Radiation Lightsource beamline 10-1.

We present results obtained with a new soft X-ray spectrometer based on transition-edge sensors (TESs) composed of Mo/Cu bilayers coupled to bismuth absorbers. This spectrometer simultaneously provides excellent energy resolution, high detection efficiency, and broadband spectral coverage. The new spectrometer is optimized for incident X-ray energies below 2 keV. Each pixel serves as both a highly sensitive calorimeter and an X-ray absorber with near unity quantum efficiency. We have commissioned this 240-pixel TES spectrometer at the Stanford Synchrotron Radiation Lightsource beamline 10-1 (BL 10-1) and used it to probe the local electronic structure of sample materials with unprecedented sensitivity in the soft X-ray regime. As mounted, the TES spectrometer has a maximum detection solid angle of 2 × 10-3 sr. The energy resolution of all pixels combined is 1.5 eV full width at half maximum at 500 eV. We describe the performance of the TES spectrometer in terms of its energy resolution and count-rate capability and demonstrate its utility as a high throughput detector for synchrotron-based X-ray spectroscopy. Results from initial X-ray emission spectroscopy and resonant inelastic X-ray scattering experiments obtained with the spectrometer are presented.

Electrical and optical measurements on the first SCUBA-2 prototype 1280 pixel submillimeter superconducting bolometer array.

SCUBA-2 is a submillimeter camera being built for the James Clerk Maxwell Telescope in Hawaii. Bringing CCD style imaging to the submillimeter for the first time, with over 10000 pixels, it will provide a revolutionary improvement in sensitivity and mapping speed. We present results of the first tests on a prototype 1280 pixel SCUBA-2 subarray; the full instrument will be made up of eight such subarrays. The array is made up of transition edge sensor (TES) detectors, with Mo/Cu bilayers as the sensing element. To keep the number of wires reasonable, a multiplexed readout is used. Unlike previous TES arrays, an in-focal plane multiplexer configuration is used, in which the multiplexing elements are located beneath each pixel. To achieve the required performance, the detectors are operated at a temperature of approximately 120 mK. We describe the results of a basic electrical and optical characterization of the array, demonstrating that it is fully operational. Noise measurements were made on several pixels and gave a noise equivalent power below 2.5 x 10(-17) W HZ(-0.5), within the requirements for SCUBA-2. The construction of the testbed used to carry out these measurements is also described.

Beating Darwin-Bragg losses in lab-based ultrafast x-ray experiments.

The use of low temperature thermal detectors for avoiding Darwin-Bragg losses in lab-based ultrafast experiments has begun. An outline of the background of this new development is offered, showing the relevant history and initiative taken by this work.

Ultrafast Time-Resolved X-ray Absorption Spectroscopy of Ferrioxalate Photolysis with a Laser Plasma X-ray Source and Microcalorimeter Array.

The detailed pathways of photoactivity on ultrafast time scales are a topic of contemporary interest. Using a tabletop apparatus based on a laser plasma X-ray source and an array of cryogenic microcalorimeter X-ray detectors, we measured a transient X-ray absorption spectrum during the ferrioxalate photoreduction reaction. With these high-efficiency detectors, we observe the Fe K edge move to lower energies and the amplitude of the extended X-ray absorption fine structure reduce, consistent with a photoreduction mechanism in which electron transfer precedes disassociation. These results are compared to previously published transient X-ray absorption measurements on the same reaction and found to be consistent with the results from Ogi et al. and inconsistent with the results of Chen et al. ( Ogi , Y. ; et al. Struct. Dyn. 2015 , 2 , 034901 ; Chen , J. ; Zhang , H. ; Tomov , I. V. ; Ding , X. ; Rentzepis , P. M. Chem. Phys. Lett. 2007 , 437 , 50 - 55 ). We provide quantitative limits on the Fe-O bond length change. Finally, we review potential improvements to our measurement technique, highlighting the future potential of tabletop X-ray science using microcalorimeter sensors.