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Block polymer self-assembly typically translates molecular chain connectivity into mesoscale structure by exploiting incompatible blocks with large interaction parameters (χ ij ). In this article, we demonstrate that the converse approach, encoding low-χ interactions in ABC bottlebrush triblock terpolymers (χ AC ≲ 0), promotes organization into a unique mixed-domain lamellar morphology, which we designate LAM P . Transmission electron microscopy indicates that LAM P exhibits ACBC domain connectivity, in contrast to conventional three-domain lamellae (LAM 3 ) with ABCB periods. Complementary small-angle X-ray scattering experiments reveal a strongly decreasing domain spacing with increasing total molar mass. Self-consistent field theory reinforces these observations and predicts that LAM P is thermodynamically stable below a critical χ AC , above which LAM 3 emerges. Both experiments and theory expose close analogies to ABA′ triblock copolymer phase behavior, collectively suggesting that low-χ interactions between chemically similar or distinct blocks intimately influence self-assembly. These conclusions provide fresh opportunities for block polymer design with potential consequences spanning all self-assembling soft materials.block polymer | self-assembly | polymer nanostructure | domain spacing | LAM P B lock polymers are a diverse class of soft materials capable of self-assembling into complex periodic nanostructures. Synthetic command over composition, dispersity, sequence, and molecular architecture enables control over the mesoscopic order and macroscopic thermal, mechanical, rheological, and transport properties (1-4). The phase behavior of "simple" linear AB diblock copolymers is universally parameterized by the segregation strength χ AB N and relative volume fraction f, where χ AB represents the effective Flory-Huggins binary interaction parameter and N is the total volume-averaged degree of polymerization. Mixing behavior, captured through the mean-field concept of χ AB , is central to block polymer self-assembly: the competing demands of minimizing interfacial energy and maximizing configurational entropy only favor microphase separation when A-B interactions are repulsive (χ AB > 0) (5, 6). Extension to higher-order multiblock polymers introduces additional interaction parameters (χ ij ) that impact self-assembly and properties (7). For example, introducing a mutually incompatible C block (χ AC > 0, χ BC > 0) generates a host of new morphologies dictated by the chain connectivity (ABC, ACB, or BAC) and intrinsic χ ij -values (8, 9). In this rich phase space, designing multiblock polymers with a combination of miscible and immiscible blocks can also access new structures and impart useful functions (10, 11). Perhaps the best-known examples of such systems are linear ABA′ triblock copolymers (χ AB > 0, χ AA′ ≈ 0): their high-value industrial applications as thermoplastic elastomers are entirely enabled by A/A′ mixing and chain connectivity, which together create physically cross-linked materials with ex...

M-Si-N and M-Si ͑MϭMo, Ta, or W͒ thin films, reactively sputtered from M 5 Si 3 and WSi 2 targets, are examined as diffusion barriers for aluminum metallizations of silicon. Methods of analysis include electrical tests of shallow-junction diodes, 4 He ϩϩ backscattering spectrometry, x-ray diffraction, transmission electron microscopy, scanning electron microscopy, and secondary-ion-mass spectrometry. At the proper compositions, the M-Si-N films prevent Al overlayers from electrically degrading shallow-junction diodes after 10 min anneals above the melting point of aluminum. Secondary-ion-mass spectrometry indicates virtually no diffusivity of Al into the M-Si-N films during a 700°C/10 h treatment. The stability can be partially attributed to a self-sealing 3-nm-thick AlN layer that grows at the M-Si-N/Al interface, as seen by transmission electron microscopy.

The impact of hydration on the transport properties of microcrystalline Sm 0.15 Ce 0.85 O 1.925 has been examined. Dense, polycrystalline samples were obtained by conventional ceramic processing and the grain boundary regions were found, by high resolution transmission electron microscopy, to be free of impurity phases. Impedance spectroscopy measurements were performed over the temperature range 250 to 650 1C under dry, H 2 O-saturated, and D 2 O-saturated synthetic air; and over the temperature range 575 to 650 1C under H 2 -H 2 O atmospheres. Under oxidizing conditions humidification by either H 2 O or D 2 O caused a substantial increase in the grain boundary resistivity, while leaving the bulk (or grain interior) properties unchanged. This unusual behavior, which was found to be both reversible and reproducible, is interpreted in terms of the space-charge model, which adequately explains all the features of the measured data. It is found that the space-charge potential increases by 5-7 mV under humidification, in turn, exacerbating oxygen vacancy depletion in the space-charge regions and leading to the observed reduction in grain boundary conductivity. It is proposed that the heightened space-charge potential reflects a change in the relative energetics of vacancy creation in the bulk and at the grain boundary interfaces as a result of water uptake into the grain boundary core. Negligible bulk water uptake is detected under both oxidizing and reducing conditions.

We investigated through X- ray diffraction and transmission electron microscopy the crystal refinement of the intermetallic compound AIRu by high- energy ball milling. The deformation process causes a decrease of crystal size to 5–7 rum and an increase of atomic level strain. This deformation is localized in shear bands with a thickness of 0.5 to 1 micron. Within these bands the crystal lattice breaks into small grains with a typical size of 8–14 rum. Further deformation leads to a final nanocrystalline structure with randomly oriented crystallite grains separated by high- angle grain boundaries.

Gallium oxide films 20 Å in thickness were deposited onto GaAs substrates in ultra high vacuum ͑UHV͒ via e-beam evaporation from a monolithic high-purity source. The substrates were prepared by molecular-beam epitaxy and transferred to the oxide film deposition site in a wholly UHV environment. The Ga 2 O 3Ϫx films were probed by x-ray photoelectron spectroscopy ͑XPS͒. Chemical states were identified and stoichiometry was estimated. Metallic layers were deposited by e-beam evaporation in UHV after XPS analysis as caps and for future work. Film morphology and structure were probed by cross-sectional high-resolution transmission electron microscopy. The films were found to have xр0.3 and a metal/oxide interface roughness Ͻ1 Å.

Films of chemically disordered fcc Ni3Al were synthesized by the vacuum evaporation of Ni3Al onto room temperature and liquid nitrogen temperature substrates. X-ray diffractometry and transmission electron microscopy showed the material to be single phase with an average grain size of about 4 nm. The formation of the equilibrium L12 ordered phase occurred simultaneously with grain growth at temperatures above 350°C. Differential scanning calorimetry provided ordering enthalpies of 7 kJ/mole and 9 kJ/mole for material evaporated onto room temperature and liquid nitrogen temperature substrates, respectively.