Exploding and weeping ceramics.

The systematic tuning of crystal lattice parameters to achieve improved kinematic compatibility between different phases is a broadly effective strategy for improving the reversibility, and lowering the hysteresis, of solid-solid phase transformations1-11. (Kinematic compatibility refers to the fitting together of the phases.) Here we present an apparently paradoxical example in which tuning to near perfect kinematic compatibility results in an unusually high degree of irreversibility. Specifically, when cooling the kinematically compatible ceramic (Zr/Hf)O2(YNb)O4 through its tetragonal-to-monoclinic phase transformation, the polycrystal slowly and steadily falls apart at its grain boundaries (a process we term weeping) or even explosively disintegrates. If instead we tune the lattice parameters to satisfy a stronger 'equidistance' condition (which additionally takes into account sample shape), the resulting material exhibits reversible behaviour with low hysteresis. These results show that a diversity of behaviours-from reversible at one extreme to explosive at the other-is possible in a chemically homogeneous ceramic system by manipulating conditions of compatibility in unexpected ways. These concepts could prove critical in the current search for a shape-memory oxide ceramic9-12.

Epitaxial SrTiO3 films with dielectric constants exceeding 25,000.

SignificanceSemiconductor interfaces are among the most important in use in modern technology. The properties they exhibit can either enable or disable the characteristics of the materials they connect for functional performance. While much is known about important junctions involving conventional semiconductors such as Si and GaAs, there are several unsolved mysteries surrounding interfaces between oxide semiconductors. Here we resolve a long-standing issue concerning the measurement of anomalously low dielectric constants in SrTiO3 films with record high electron mobilities. We show that the junction between doped and undoped SrTiO3 required to make dielectric constant measurements masks the dielectric properties of the undoped film. Through modeling, we extract the latter and show that it is much higher than previously measured.

Self-Assembled Periodic Nanostructures Using Martensitic Phase Transformations.

We describe a novel approach for the rational design and synthesis of self-assembled periodic nanostructures using martensitic phase transformations. We demonstrate this approach in a thin film of perovskite SrSnO3 with reconfigurable periodic nanostructures consisting of regularly spaced regions of sharply contrasted dielectric properties. The films can be designed to have different periodicities and relative phase fractions via chemical doping or strain engineering. The dielectric contrast within a single film can be tuned using temperature and laser wavelength, effectively creating a variable photonic crystal. Our results show the realistic possibility of designing large-area self-assembled periodic structures using martensitic phase transformations with the potential of implementing "built-to-order" nanostructures for tailored optoelectronic functionalities.

Quantitative analysis of compatible microstructure by electron backscatter diffraction.

We propose a scheme for assigning the martensite variant using electron backscatter diffraction in a martensite material that undergoes a solid-solid phase transformation. Based on the solutions of the crystallographic equations of martensite, we provide an algorithm to assign martensite variants to a particular microscopic region, and to check the elastic compatibility of the microstructure corresponding to low hysteresis and high reversibility in shape memory alloys. This article is part of the theme issue 'Topics in mathematical design of complex materials'.

Enhanced reversibility and unusual microstructure of a phase-transforming material.

Materials undergoing reversible solid-to-solid martensitic phase transformations are desirable for applications in medical sensors and actuators, eco-friendly refrigerators and energy conversion devices. The ability to pass back and forth through the phase transformation many times without degradation of properties (termed 'reversibility') is critical for these applications. Materials tuned to satisfy a certain geometric compatibility condition have been shown to exhibit high reversibility, measured by low hysteresis and small migration of transformation temperature under cycling. Recently, stronger compatibility conditions called the 'cofactor conditions' have been proposed theoretically to achieve even better reversibility. Here we report the enhanced reversibility and unusual microstructure of the first martensitic material, Zn45Au30Cu25, that closely satisfies the cofactor conditions. We observe four striking properties of this material. (1) Despite a transformation strain of 8%, the transformation temperature shifts less than 0.5 °C after more than 16,000 thermal cycles. For comparison, the transformation temperature of the ubiquitous NiTi alloy shifts up to 20 °C in the first 20 cycles. (2) The hysteresis remains approximately 2 °C during this cycling. For comparison, the hysteresis of the NiTi alloy is up to 70 °C (refs 9, 12). (3) The alloy exhibits an unusual riverine microstructure of martensite not seen in other martensites. (4) Unlike that of typical polycrystal martensites, its microstructure changes drastically in consecutive transformation cycles, whereas macroscopic properties such as transformation temperature and latent heat are nearly reproducible. These results promise a concrete strategy for seeking ultra-reliable martensitic materials.

Exceptional Resilience of Small-Scale Au30Cu25Zn45 under Cyclic Stress-Induced Phase Transformation.

Shape memory alloys that produce and recover from large deformation driven by martensitic transformation are widely exploited in biomedical devices and microactuators. Generally their actuation work degrades significantly within first a few cycles and is reduced at smaller dimensions. Further, alloys exhibiting unprecedented reversibility have relatively small superelastic strain, 0.7%. These raise the questions of whether high reversibility is necessarily accompanied by small work and strain and whether high work and strain is necessarily diminished at small scale. Here we conclusively demonstrate that these are not true by showing that Au30Cu25Zn45 pillars exhibit 12 MJ m-3 work and 3.5% superelastic strain even after 100 000 phase transformation cycles. Our findings confirm that the lattice compatibility dominates the mechanical behavior of phase-changing materials at nano to micron scales and points a way for smart microactuators design having the mutual benefits of high actuation work and long lifetime.

Zig-zag twins and helical phase transformations.

We demonstrate the large bending deformation induced by an array of permanent magnets (applied field ∼0.02 T) designed to minimize poles in the bent state of the crystal. Planar cantilevers of NiMnGa (5M modulated martensite) ferromagnetic shape memory alloy deform into an arched shape according to theory, with a zig-zag microstructure that complies with the kinematic and magnetic compatibility between adjacent twin variants. A general theory of bent and twisted states is given, applicable to both twinning and austenite/martensite transformations. Some of these configurations achieve order-of-magnitude amplification of rotation and axial strain. We investigate also atomistic analogues of these bent and twisted configurations with perfect interfaces between phases. These mechanisms of large deformation, induced by small magnetic fields or temperature changes, have potential application to the development of new actuation technologies for micro-robotic systems.

Betanin dye extracted from ayrampo (Opuntia soehrensii) seeds to develop dye-sensitized solar cells.

Pigments extracted from ayrampo seeds of the Peruvian-native prickly pear (Opuntia soehrensii) were used in dye-sensitized solar cells with promising efficiencies. The performance of the solar cells was then improved via the addition of citric acid to stabilise the photosensitive dye, and an efficiency of 1.41% was achieved with current output remaining stable after 7 days. Upon testing in low-light conditions, the solar conversion efficiency of devices increased to 4%. This paper not only highlights the potential of natural sensitizers in DSSCs but also shows that simple extraction and gentle handling methods can contribute to the device performance.

Adsorption-Controlled Growth and Magnetism in Epitaxial SrRuO3 Films.

Controlling defect densities in SrRuO3 films is the cornerstone for probing the intricate relationship among its structural, electrical, and magnetic properties. We combine film growth, electrical transport, and magnetometry to demonstrate the adsorption-controlled growth of phase-pure, epitaxial, and stoichiometric SrRuO3 films on SrTiO3 (001) substrates using solid source metal-organic molecular beam epitaxy. Across the growth window, we show that the anomalous Hall curves arise from two distinct magnetic domains. Domains with similar anomalous Hall polarities generate the stepped feature observed within the growth window, and those with opposite polarities produce the hump-like feature present exclusively in the highly Ru-poor film. We achieve a residual resistivity ratio (RRR = ρ300K/ρ2K) of 87 in a 50 nm-thick, coherently strained, and stoichiometric SrRuO3 film, the highest reported value to date on SrTiO3 (001) substrates. We hypothesize further improvements in the RRR through strain engineering to control the tetragonal-to-orthorhombic phase transformation and the domain structure of SrRuO3 films.

Pentafluorosulfanyl-functionalised BODIPY push-pull dyes for p-type dye-sensitized solar cells.

We report a push-pull BODIPY-based dye functionalised with an electronegative SF5 group at the meso position for applications in photocathodes in tandem dye-sensitized solar cells (DSSCs). The push-pull character enhances charge-transfer from the mesoporous NiO cathode surface towards the redox mediator. A Knoevenagel condensation reaction was used to introduce the carboxylic acid to anchor the dye to the oxide surface, via a styryl linker which increases the conjugation in the molecule and shifts the absorption to the red. The room-temperature synthesis and high yields, make the dye promising for manufacture on a large scale. The dye was applied in p-DSSCs giving a power conversion efficiency (0.066%), a short circuit photocurrent (J SC) of 3.84 mA cm-2, open circuit voltage (V OC) of 58 mV and fill factor of 30%.

Origami-inspired thin-film shape memory alloy devices.

We describe the design and fabrication of miniaturized origami structures based on thin-film shape memory alloys. These devices are attractive for medical implants, as they overcome the opposing requirements of crimping the implant for insertion into an artery while keeping sensitive parts of the implant nearly stress-free. The designs are based on a group theory approach in which compatibility at a few creases implies the foldability of the whole structure. Importantly, this approach is versatile and thus provides a pathway for patient-specific treatment of brain aneurysms of differing shapes and sizes. The wafer-based monolithic fabrication method demonstrated here, which comprises thin-film deposition, lithography, and etching using sacrificial layers, is a prerequisite for any integrated self-folding mechanism or sensors and will revolutionize the availability of miniaturized implants, allowing for new and safer medical treatments.

Helical Miura origami.

We characterize the phase space of all helical Miura origami. These structures are obtained by taking a partially folded Miura parallelogram as the unit cell, applying a generic helical or rod group to the cell, and characterizing all the parameters that lead to a globally compatible origami structure. When such compatibility is achieved, the result is cylindrical-type origami that can be manufactured from a suitably designed flat tessellation and "rolled up" by a rigidly foldable motion into a cylinder. We find that the closed helical Miura origami are generically rigid to deformations that preserve cylindrical symmetry but are multistable. We are inspired by the ways atomic structures deform to develop two broad strategies for reconfigurability: motion by slip, which involves relaxing the closure condition, and motion by phase transformation, which exploits multistability. Taken together, these results provide a comprehensive description of the phase space of cylindrical origami, as well as quantitative design guidance for their use as actuators or metamaterials that exploit twist, axial extension, radial expansion, and symmetry.

Correlation between phase compatibility and efficient energy conversion in Zr-doped Barium Titanate.

Recent demonstrations of both heat-to-electricity energy conversion devices and electrocaloric devices based on first-order ferroelectric phase transformations identify the lowering of hysteresis and cyclic reversibility of the transformation as enabling criteria for the advancement of this technology. These demonstrations, and recent studies of the hysteresis of phase transformations in oxides, show that satisfying conditions of supercompatibility can be useful for lowering hysteresis, but with limitations for systems with only a few variants of the lower symmetry phase. In particular, it is widely accepted that in a classic cubic-to-tetragonal phase transformation, with only three tetragonal variants having only six twin systems, tuning for improved crystallographic compatibility will be of limited value. This work shows that, on the contrary, the tuning of lattice parameters in Ba(Ti1-xZrx)O3 for improved crystallographic compatibility, even at low doping levels of Zr (x ≤ 0.027), give significant improvement of transformation and ferroelectric energy conversion properties. Specifically, the transformation hysteresis is lowered by 25%, and the maximum value of the polarization/temperature ratio dP/dT at the phase transformation is increased by 10%.

Elasticity theory for self-assembled protein lattices with application to the martensitic phase transition in bacteriophage T4 tail sheath.

We propose an elasticity theory for one- and two-dimensional arrays of globular proteins for which the free energy is affected by relative position and relative rotation between neighboring molecules. The kinematics of such assemblies is described, the conditions of compatibility are found, a form of the free energy is given, and formulas for applied forces and moments are developed. It is shown that fully relaxed states of sheets consist of helically deformed sheets which themselves are composed of helical chains of molecules in rational directions. We apply the theory to the fascinating contractile deformation that occurs in the tail sheath of the virus bacteriophage T4, which aids its invasion of its bacterial host. Using electron density maps of extended and contracted sheaths, we approximate the domains of each molecule by ellipsoids and then evaluate our formulas for the position and orientation of each molecule. We show that, with the resulting kinematic description, the configurations of extended and contracted tail sheaths are generated by a simple formula. We proposed a constrained version of the theory based on measurements on extended and contracted sheath. Following a suggestion of Pauling [Discuss. Faraday Soc. 13, 170 (1953)], we develop a simple model of the molecular interaction. The resulting free energy is found to have a double-well structure. Certain simple deformations are studied (tension, torsion inflation); the theory predicts a first-order Poynting effect and some unexpected relations among moduli. Finally, the force of penetration is given, and a possibly interesting program of epitaxial growth and patterning of such sheets is suggested.

Bragg-von Laue diffraction generalized to twisted X-rays.

A pervasive limitation of nearly all practical X-ray methods for the determination of the atomic scale structure of matter is the need to crystallize the molecule, compound or alloy in a sufficiently large (∼ 10 × 10 × 10 µm) periodic array. In this paper an X-ray method applicable to structure determination of some important noncrystalline structures is proposed. It is designed according to a strict mathematical analog of von Laue's method, but replacing the translation group by another symmetry group, and simultaneously replacing plane waves by different exact closed-form solutions of Maxwell's equations. Details are presented for helical structures like carbon nanotubes or filamentous viruses. In computer simulations the accuracy of the determination of structure is shown to be comparable to the periodic case.

Combinatorial search of thermoelastic shape-memory alloys with extremely small hysteresis width.

Reversibility of structural phase transformations has profound technological implications in a wide range of applications from fatigue life in shape-memory alloys (SMAs) to magnetism in multiferroic oxides. The geometric nonlinear theory of martensite universally applicable to all structural transitions has been developed. It predicts the reversibility of the transitions as manifested in the hysteresis behaviour based solely on crystal symmetry and geometric compatibilities between phases. In this article, we report on the verification of the theory using the high-throughput approach. The thin-film composition-spread technique was devised to rapidly map the lattice parameters and the thermal hysteresis of ternary alloy systems. A clear relationship between the hysteresis and the middle eigenvalue of the transformation stretch tensor as predicted by the theory was observed for the first time. We have also identified a new composition region of titanium-rich SMAs with potential for improved control of SMA properties.