Nobumichi Tamura

Submicron X-ray diffraction and its applications to problems in materials and environmental science.

The availability of high brilliance third generation synchrotron sources together with progress in achromatic focusing optics allows us to add submicron spatial resolution to the conventional century-old x-ray diffraction technique. The new capabilities include the possibility to map in situ, grain orientations, crystalline phase distribution, and full strain/stress tensors at a very local level, by combining white and monochromatic x-ray microbeam diffraction. This is particularly relevant for high technology industry where the understanding of material properties at a microstructural level becomes increasingly important. After describing the latest advances in the submicron x-ray diffraction techniques at the Advanced Light Source, we will give some examples of its application in material science for the measurement of strain/stress in metallic thin films and interconnects. Its use in the field of environmental science will also be discussed.

Learning from the past: Rare ε-Fe2O3 in the ancient black-glazed Jian (Tenmoku) wares

Ancient Jian wares are famous for their lustrous black glaze that exhibits unique colored patterns. Some striking examples include the brownish colored “Hares Fur” (HF) strips and the silvery “Oil Spot” (OS) patterns. Herein, we investigated the glaze surface of HF and OS samples using a variety of characterization methods. Contrary to the commonly accepted theory, we identified the presence of ε-Fe2O3, a rare metastable polymorph of Fe2O3 with unique magnetic properties, in both HF and OS samples. We found that surface crystals of OS samples are up to several micrometers in size and exclusively made of ε-Fe2O3. Interestingly, these ε-Fe2O3 crystals on the OS sample surface are organized in a periodic two dimensional fashion. These results shed new lights on the actual mechanisms and kinetics of polymorphous transitions of Fe2O3. Deciphering technologies behind the fabrication of ancient Jian wares can thus potentially help researchers improve the ε-Fe2O3 synthesis.

A dedicated superbend x-ray microdiffraction beamline for materials, geo-, and environmental sciences at the advanced light source

A new facility for microdiffraction strain measurements and microfluorescence mapping has been built on beamline 12.3.2 at the advanced light source of the Lawrence Berkeley National Laboratory. This beamline benefits from the hard x-radiation generated by a 6 T superconducting bending magnet (superbend). This provides a hard x-ray spectrum from 5 to 22 keV and a flux within a 1 microm spot of approximately 5x10(9) photons/s (0.1% bandwidth at 8 keV). The radiation is relayed from the superbend source to a focus in the experimental hutch by a toroidal mirror. The focus spot is tailored by two pairs of adjustable slits, which serve as secondary source point. Inside the lead hutch, a pair of Kirkpatrick-Baez (KB) mirrors placed in a vacuum tank refocuses the secondary slit source onto the sample position. A new KB-bending mechanism with active temperature stabilization allows for more reproducible and stable mirror bending and thus mirror focusing. Focus spots around 1 microm are routinely achieved and allow a variety of experiments, which have in common the need of spatial resolution. The effective spatial resolution (approximately 0.2 microm) is limited by a convolution of beam size, scan-stage resolution, and stage stability. A four-bounce monochromator consisting of two channel-cut Si(111) crystals placed between the secondary source and KB-mirrors allows for easy changes between white-beam and monochromatic experiments while maintaining a fixed beam position. High resolution stage scans are performed while recording a fluorescence emission signal or an x-ray diffraction signal coming from either a monochromatic or a white focused beam. The former allows for elemental mapping, whereas the latter is used to produce two-dimensional maps of crystal-phases, -orientation, -texture, and -strain/stress. Typically achieved strain resolution is in the order of 5x10(-5) strain units. Accurate sample positioning in the x-ray focus spot is achieved with a commercial laser-triangulation unit. A Si-drift detector serves as a high-energy-resolution (approximately 150 eV full width at half maximum) fluorescence detector. Fluorescence scans can be collected in continuous scan mode with up to 300 pixels/s scan speed. A charge coupled device area detector is utilized as diffraction detector. Diffraction can be performed in reflecting or transmitting geometry. Diffraction data are processed using XMAS, an in-house written software package for Laue and monochromatic microdiffraction analysis.

Deciphering Ni sequestration in soil ferromanganese nodules by combining X-ray fluorescence, absorption, and diffraction at micrometer scales of resolution

Abstract X-ray microprobes are among the most important new analytical techniques to emerge from third generation synchrotron facilities. Here we show how X-ray fluorescence, diffraction, and absorption can be used in parallel to determine the structural form of trace elements in heterogeneous matrices at the micrometer-scale of resolution. Scanning X-ray microfluorescence (μSXRF) and microdiffraction (μSXRD) first are used to identify the host solid phase by mapping the distributions of elements and solid species, respectively. Micro-extended X-ray absorption fine structure (μEXAFS) spectroscopy is then used to determine the mechanism of trace element binding by the host phase at the molecular scale. To illustrate the complementary application of these three techniques, we studied how nickel is sequestered in soil ferromanganese nodules, an overwhelmingly complex natural matrix consisting of submicrometer to nanometer sized particles with varying structures and chemical compositions. We show that nickel substitutes for Mn3+ in the manganese layer of the MnO2- Al(OH)3 mixed-layer oxide lithiophorite. The affinity of Ni for lithiophorite was characteristic of micronodules sampled from soils across the U.S.A. and Europe. Since many natural and synthetic materials are heterogeneous at nanometer to micrometer scales, the synergistic use of μSXRF, μSXRD, and μEXAFS is expected to have broad applications to earth and materials science.

Effect of surface microstructure on electrochemical performance of garnet solid electrolytes.

Cubic garnet phases based on Al-substituted Li7La3Zr2O12 (LLZO) have high ionic conductivities and exhibit good stability versus metallic lithium, making them of particular interest for use in next-generation rechargeable battery systems. However, high interfacial impedances have precluded their successful utilization in such devices until the present. Careful engineering of the surface microstructure, especially the grain boundaries, is critical to achieving low interfacial resistances and enabling long-term stable cycling with lithium metal. This study presents the fabrication of LLZO heterostructured solid electrolytes, which allowed direct correlation of surface microstructure with the electrochemical characteristics of the interface. Grain orientations and grain boundary distributions of samples with differing microstructures were mapped using high-resolution synchrotron polychromatic X-ray Laue microdiffraction. The electrochemical characteristics are strongly dependent upon surface microstructure, with small grained samples exhibiting much lower interfacial resistances and better cycling behavior than those with larger grain sizes. Low area specific resistances of 37 Ω cm(2) were achieved; low enough to ensure stable cycling with minimal polarization losses, thus removing a significant obstacle toward practical implementation of solid electrolytes in high energy density batteries.

Measurement of stresses in Cu and Si around through-silicon via by synchrotron X-ray microdiffraction for 3-dimensional integrated circuits

Through-silicon via (TSV) has been used for 3-dimentional integrated circuits. Mechanical stresses in Cu and Si around the TSV were measured using synchrotron X-ray microdiffraction. The hydrostatic stress in Cu TSV went from high tensile of 234 MPa in the as-fabricated state, to � 196 MPa (compressive) during thermal annealing (in situ measurement), to 167 MPa in the post-annealed state. Due to this stress, the keep-away distance in Si was determined to be about 17 lm. Our results suggest that Cu stress may lead to reliability as well as integration issues, while Si stress may lead to device performance concerns.

Submicron X-ray diffraction

Abstract At the Advanced Light Source in Berkeley we have instrumented a beam line that is devoted exclusively to X-ray micro-diffraction problems. By micro-diffraction we mean those classes of problems in Physics and Materials Science that require X-ray beam sizes in the sub-micron range. The instrument is for instance, capable of probing a sub-micron size volume inside micron-sized aluminum metal grains buried under a silicon dioxide insulating layer. The resulting Laue pattern is collected on a large area CCD detector and automatically indexed to yield the grain orientation and deviatoric (distortional) strain tensor of this sub-micron volume. A four-crystal monochromator is then inserted into the beam, which allows monochromatic light to illuminate the same part of the sample. Measurement of the diffracted photon energy allows for the determination of d spacings. The combination of white and monochromatic beam measurements allow for the determination of the total strain/stress tensor (6 components) inside each sub-micron-sized illuminated volume of the sample.

Crystal plasticity in Cu damascene interconnect lines undergoing electromigration as revealed by synchrotron x-ray microdiffraction

Plastic deformation was observed in damascene Cu interconnect test structures during an in situ electromigration experiment and before the onset of visible microstructural damage (voiding, hillock formation). We show here, using a synchrotron technique of white beam x-ray microdiffraction, that the extent of this electromigration-induced plasticity is dependent on the linewidth. In wide lines, plastic deformation manifests itself as grain bending and the formation of subgrain structures, while only grain rotation is observed in the narrower lines. The deformation geometry leads us to conclude that dislocations introduced by plastic flow lie predominantly in the direction of electron flow and may provide additional easy paths for the transport of point defects. Since these findings occur long before any observable voids or hillocks are formed, they may have direct bearing on the final failure stages of electromigration.

Dramatic morphological change of scallop-type Cu6Sn5 formed on (001) single crystal copper in reaction between molten SnPb solder and Cu

Wetting reaction between molten Sn-based solders and Cu produces scallop-type Cu6Sn5. In the present wetting study, a (001) single crystal Cu is used as substrate and a dramatic change in the morphology of Cu6Sn5 is observed: instead of scallop type, the authors observed a rooftop-type Cu6Sn5 grains, elongated along two preferred orientation directions. This was confirmed by electron beam backscattered diffraction and white beam synchrotron x-ray microdiffraction. The results indicate that the nucleation, growth, and ripening behavior of Cu6Sn5 on single crystal substrate can be quite different from the conventional case of wetting on randomly oriented polycrystalline Cu substrates.

Electromigration-induced microstructure evolution in tin studied by synchrotron x-ray microdiffraction

Under constant current electromigration, white tin exhibited a resistance drop of up to 10%. It has a body-centered-tetragonal structure, and the resistivity along the a and b axes is 35% smaller than along the c axis. Microstructure evolution under electromigration could be responsible for the resistance drop. Synchrotron radiation white beam x-ray microdiffraction was used to study this evolution. Grain-by-grain analysis was obtained from the diffracted Laue patterns about the changes of grain orientation before and after electromigration. We observed that high-resistance grains reorient with respect to the neighboring low-resistance grains, most likely by grain growth of the latter. A different mechanism of grain growth under electromigration from the normal grain growth is proposed and discussed.