Reverse and forward engineering of Drosophila corneal nanocoatings.

Insect eyes have an anti-reflective coating, owing to nanostructures on the corneal surface creating a gradient of refractive index between that of air and that of the lens material1,2. These nanocoatings have also been shown to provide anti-adhesive functionality3. The morphology of corneal nanocoatings are very diverse in arthropods, with nipple-like structures that can be organized into arrays or fused into ridge-like structures4. This diversity can be attributed to a reaction-diffusion mechanism4 and patterning principles developed by Alan Turing5, which have applications in numerous biological settings6. The nanocoatings on insect corneas are one example of such Turing patterns, and the first known example of nanoscale Turing patterns4. Here we demonstrate a clear link between the morphology and function of the nanocoatings on Drosophila corneas. We find that nanocoatings that consist of individual protrusions have better anti-reflective properties, whereas partially merged structures have better anti-adhesion properties. We use biochemical analysis and genetic modification techniques to reverse engineer the protein Retinin and corneal waxes as the building blocks of the nanostructures. In the context of Turing patterns, these building blocks fulfil the roles of activator and inhibitor, respectively. We then establish low-cost production of Retinin, and mix this synthetic protein with waxes to forward engineer various artificial nanocoatings with insect-like morphology and anti-adhesive or anti-reflective function. Our combined reverse- and forward-engineering approach thus provides a way to economically produce functional nanostructured coatings from biodegradable materials.

Defeating depolarizing fields with artificial flux closure in ultrathin ferroelectrics.

Material surfaces encompass structural and chemical discontinuities that often lead to the loss of the property of interest in so-called dead layers. It is particularly problematic in nanoscale oxide electronics, where the integration of strongly correlated materials into devices is obstructed by the thickness threshold required for the emergence of their functionality. Here we report the stabilization of ultrathin out-of-plane ferroelectricity in oxide heterostructures through the design of an artificial flux-closure architecture. Inserting an in-plane-polarized ferroelectric epitaxial buffer provides the continuity of polarization at the interface; despite its insulating nature, we observe the emergence of polarization in our out-of-plane-polarized model of ferroelectric BaTiO3 from the very first unit cell. In BiFeO3, the flux-closure approach stabilizes a 251° domain wall. Its unusual chirality is probably associated with the ferroelectric analogue to the Dzyaloshinskii-Moriya interaction. We, thus, see that in an adaptively engineered geometry, the depolarizing-field-screening properties of an insulator can even surpass those of a metal and be a source of functionality. This could be a useful insight on the road towards the next generation of oxide electronics.

Non-volatile electric-field control of inversion symmetry.

Competition between ground states at phase boundaries can lead to significant changes in properties under stimuli, particularly when these ground states have different crystal symmetries. A key challenge is to stabilize and control the coexistence of symmetry-distinct phases. Using BiFeO3 layers confined between layers of dielectric TbScO3 as a model system, we stabilize the mixed-phase coexistence of centrosymmetric and non-centrosymmetric BiFeO3 phases at room temperature with antipolar, insulating and polar semiconducting behaviour, respectively. Application of orthogonal in-plane electric (polar) fields results in reversible non-volatile interconversion between the two phases, hence removing and introducing centrosymmetry. Counterintuitively, we find that an electric field 'erases' polarization, resulting from the anisotropy in octahedral tilts introduced by the interweaving TbScO3 layers. Consequently, this interconversion between centrosymmetric and non-centrosymmetric phases generates changes in the non-linear optical response of over three orders of magnitude, resistivity of over five orders of magnitude and control of microscopic polar order. Our work establishes a platform for cross-functional devices that take advantage of changes in optical, electrical and ferroic responses, and demonstrates octahedral tilts as an important order parameter in materials interface design.

Pressure Control of Nonferroelastic Ferroelectric Domains in ErMnO3.

Mechanical pressure controls the structural, electric, and magnetic order in solid-state systems, allowing tailoring of their physical properties. A well-established example is ferroelastic ferroelectrics, where the coupling between pressure and the primary symmetry-breaking order parameter enables hysteretic switching of the strain state and ferroelectric domain engineering. Here, we study the pressure-driven response in a nonferroelastic ferroelectric, ErMnO3, where the classical stress-strain coupling is absent and the domain formation is governed by creation-annihilation processes of topological defects. By annealing ErMnO3 polycrystals under variable pressures in the MPa regime, we transform nonferroelastic vortex-like domains into stripe-like domains. The width of the stripe-like domains is determined by the applied pressure as we confirm by three-dimensional phase field simulations, showing that pressure leads to oriented layer-like periodic domains. Our work demonstrates the possibility to utilize mechanical pressure for domain engineering in nonferroelastic ferroelectrics, providing a lever to control their dielectric and piezoelectric responses.

Interface and surface stabilization of the polarization in ferroelectric thin films.

Ferroelectric perovskites present a switchable spontaneous polarization and are promising energy-efficient device components for digital information storage. Full control of the ferroelectric polarization in ultrathin films of ferroelectric perovskites needs to be achieved in order to apply this class of materials in modern devices. However, ferroelectricity itself is not well understood in this nanoscale form, where interface and surface effects become particularly relevant and where loss of net polarization is often observed. In this work, we show that the precise control of the structure of the top surface and bottom interface of the thin film is crucial toward this aim. We explore the properties of thin films of the prototypical ferroelectric lead titanate (PbTiO3) on a metallic strontium ruthenate (SrRuO3) buffer using a combination of computational (density functional theory) and experimental (optical second harmonic generation) methods. We find that the polarization direction and strength are influenced by chemical and electronic processes occurring at the epitaxial interface and at the surface. The polarization is particularly sensitive to adsorbates and to surface and interface defects. These results point to the possibility of controlling the polarization direction and magnitude by engineering specific interface and surface chemistries.

Inversion-Symmetry Engineering in Layered Oxide Thin Films.

Inversion-symmetry breaking is a ubiquitous concept in condensed-matter science: It is a prerequisite for technologically relevant effects such as piezoelectricity, nonlinear optical properties, and spin-transport phenomena. It also determines abstract properties, like the electronic topology in quantum materials. Therefore, the creation of materials where inversion symmetry can be turned on or off by design may be a versatile approach for controlling parity-related functionalities. Here, we engineer inversion symmetry on a sub-unit-cell level in ultrathin hexagonal manganite films. Although an odd number of half-unit-cell layers breaks inversion symmetry, an even number of such layers remains centrosymmetric. Optical second harmonic generation as an inversion-symmetry-sensitive functionality is thus activated and deactivated on demand and at the same time used for in situ tracking of the symmetry state of our films. Symmetry engineering on the sub-unit-cell level thus suggests a new platform for controlled activation and deactivation of symmetry-governed functionalities in oxide-electronic epitaxial thin films.

Observation of Uncompensated Bound Charges at Improper Ferroelectric Domain Walls.

Low-temperature electrostatic force microscopy (EFM) is used to probe unconventional domain walls in the improper ferroelectric semiconductor Er0.99Ca0.01MnO3 down to cryogenic temperatures. The low-temperature EFM maps reveal pronounced electric far fields generated by partially uncompensated domain-wall bound charges. Positively and negatively charged walls display qualitatively different fields as a function of temperature, which we explain based on different screening mechanisms and the corresponding relaxation time of the mobile carriers. Our results demonstrate domain walls in improper ferroelectrics as a unique example of natural interfaces that are stable against the emergence of electrically uncompensated bound charges. The outstanding robustness of improper ferroelectric domain walls in conjunction with their electronic versatility brings us an important step closer to the development of durable and ultrasmall electronic components for next-generation nanotechnology.

Publisher Correction: Symmetry and magnetism allied.

In the version of this News & Views originally published, the placement of the white circle in Fig. 1 was in the wrong position; it should have been over the six-domain vortex. This has now been corrected; see the correction notice for details.

Microstructure and ferroelectricity of BaTiO3 thin films on Si for integrated photonics.

Significant progress has been made in integrating novel materials into silicon photonic structures in order to extend the functionality of photonic circuits. One of these promising optical materials is BaTiO3 or barium titanate (BTO) that exhibits a very large Pockels coefficient as required for high-speed light modulators. However, all previous demonstrations show a noticable reduction of the Pockels effect in BTO thin films deposited on silicon substrates compared to BTO bulk crystals. Here, we report on the strong dependence of the Pockels effect in BTO thin films on their microstructure, and provide guidelines on how to engineer thin films with strong electro-optic response. We employ several deposition methods such as molecular beam epitaxy and chemical vapor deposition to realize BTO thin films with different morphology and crystalline structure. While a linear electro-optic response is present even in porous, polycrystalline BTO thin films with an effective Pockels coefficient r eff = 6 pm V-1, it is maximized for dense, tetragonal, epitaxial BTO films (r eff = 140 pm V-1). By identifying the key structural predictors of electro-optic response in BTO/Si, we provide a roadmap to fully exploit the linear electro-optic effect in novel hybrid oxide/semiconductor nanophotonic devices.

Antireflective nanocoatings for UV-sensation: the case of predatory owlfly insects.

Moth-eye nanostructures, discovered to coat corneae of certain nocturnal insects, have inspired numerous technological applications to reduce light reflectance from solar cells, light-emitting diodes, and optical detectors. Technological developments require such nanocoatings to possess broadband antireflective properties, transcending the visual light spectrum, in which animals typically operate. Here we describe the corneal nanostructures of the visual organ exclusive in UV sensation of the hunting insect Libelloides macaronius and report their supreme anti-light-reflectance capacity.

Alternative moth-eye nanostructures: antireflective properties and composition of dimpled corneal nanocoatings in silk-moth ancestors.

Moth-eye nanostructures are a well-known example of biological antireflective surfaces formed by pseudoregular arrays of nipples and are often used as a template for biomimetic materials. Here, we provide morphological characterization of corneal nanostructures of moths from the Bombycidae family, including strains of domesticated Bombyx mori silk-moth, its wild ancestor Bombyx mandarina, and a more distantly related Apatelodes torrefacta. We find high diversification of the nanostructures and strong antireflective properties they provide. Curiously, the nano-dimple pattern of B. mandarina is found to reduce reflectance as efficiently as the nanopillars of A. torrefacta. Access to genome sequence of Bombyx further permitted us to pinpoint corneal proteins, likely contributing to formation of the antireflective nanocoatings. These findings open the door to bioengineering of nanostructures with novel properties, as well as invite industry to expand traditional moth-eye nanocoatings with the alternative ones described here.

Magnetically driven second-harmonic generation with phase matching in MnWO4.

Phase matching is known to enhance the nonlinear optical response in materials with a non-centrosymmetric crystallographic or electronic structure. In contrast, phase-matched frequency doubling driven by non-centrosymmetric magnetism that induces acentricity in otherwise centrosymmetric structures has not been reported yet. In our study we demonstrate the emergence of magnetically driven second-harmonic generation (SHG) with phase matching in MnWO4. The phase-matched wavelength for SHG can be tuned continuously between 450 nm to 630 nm with the conversion efficiency being determined by the refractive indices and their dispersion. Our findings reveal a new strategy towards magnetism-based conversion-materials and a route for controlling the nonlinear signal yield by acting primarily on the material's spin degree of freedom rather than employing its electronic or structural properties.

Reversible Optical Control of Polarization in Epitaxial Ferroelectric Thin Films.

Light is an effective tool to probe the polarization and domain distribution in ferroelectric materials passively, that is, non-invasively, for example, via optical second harmonic generation (SHG). With the emergence of oxide electronics, there is now a strong demand to expand the role of light toward active control of the polarization. In this work, optical control of the ferroelectric polarization is demonstrated in prototypical epitaxial PbZrxTi1-xO3 (PZT)-based heterostructures. This is accomplished in three steps, using above-bandgap UV light, while tracking the response of the polarization with optical SHG. First, it is found that UV-light exposure induces a transient enhancement or suppression of the ferroelectric polarization in films with an upward- or downward-oriented polarization, respectively. This behavior is attributed to a modified charge screening driven by the separation of photoexcited charge carriers at the Schottky interface of the ferroelectric thin film. Second, by taking advantage of this optical handle on electrostatics, remanent optical poling from a pristine multi-domain into a single-domain configuration is accomplished. Third, via thermal annealing or engineered electrostatic boundary conditions, a complete reversibility of the optical poling is further achieved. Hence, this work paves the way for the all-optical control of the spontaneous polarization in ferroelectric thin films.

Observation of ferrotoroidic domains.

Domains are of unparalleled technological importance as they are used for information storage and for electronic, magnetic and optical switches. They are an essential property of any ferroic material. Three forms of ferroic order are widely known: ferromagnetism, a spontaneous magnetization; ferroelectricity, a spontaneous polarization; and ferroelasticity, a spontaneous strain. It is currently debated whether to include an ordered arrangement of magnetic vortices as a fourth form of ferroic order, termed ferrotoroidicity. Although there are reasons to expect this form of order from the point of view of thermodynamics, a crucial hallmark of the ferroic state--that is, ferrotoroidic domains--has not hitherto been observed. Here ferrotoroidic domains are spatially resolved by optical second harmonic generation in LiCoPO4, where they coexist with independent antiferromagnetic domains. Their space- and time-asymmetric nature relates ferrotoroidics to multiferroics with magnetoelectric phase control and to other systems in which space and time asymmetry leads to possibilities for future applications.

Critical slowing down near a magnetic quantum phase transition with fermionic breakdown.

When a system close to a continuous phase transition is subjected to perturbations, it takes an exceptionally long time to return to equilibrium. This critical slowing down is observed universally in the dynamics of bosonic excitations, such as order-parameter collective modes, but it is not generally expected to occur for fermionic excitations. Here using terahertz time-domain spectroscopy, we find evidence for fermionic critical slowing down in YbRh2Si2 close to a quantum phase transition between an antiferromagnetic phase and a heavy Fermi liquid. In the latter phase, the relevant quasiparticles are a quantum superposition of itinerant and localized electronic states with a strongly enhanced effective mass. As the temperature is lowered on the heavy-Fermi-liquid side of the transition, the heavy-fermion spectral weight builds up until the Kondo temperature TK ≈ 25 K, then decays towards the quantum phase transition and is, thereafter, followed by a logarithmic rise of the quasiparticle excitation rate below 10 K. A two-band heavy-Fermi-liquid theory shows that this is indicative of the fermionic critical slowing down associated with heavy-fermion breakdown near the quantum phase transition. The critical exponent of this breakdown could be used to classify this system among a wider family of fermionic quantum phase transitions that is yet to be fully explored.

Multilevel polarization switching in ferroelectric thin films.

Ferroic order is characterized by hystereses with two remanent states and therefore inherently binary. The increasing interest in materials showing non-discrete responses, however, calls for a paradigm shift towards continuously tunable remanent ferroic states. Device integration for oxide nanoelectronics furthermore requires this tunability at the nanoscale. Here we demonstrate that we can arbitrarily set the remanent ferroelectric polarization at nanometric dimensions. We accomplish this in ultrathin epitaxial PbZr0.52Ti0.48O3 films featuring a dense pattern of decoupled nanometric 180° domains with a broad coercive-field distribution. This multilevel switching is achieved by driving the system towards the instability at the morphotropic phase boundary. The phase competition near this boundary in combination with epitaxial strain increases the responsiveness to external stimuli and unlocks new degrees of freedom to nano-control the polarization. We highlight the technological benefits of non-binary switching by demonstrating a quasi-continuous tunability of the non-linear optical response and of tunnel electroresistance.

Magnetoelectric transfer of a domain pattern.

The utility of ferroic materials is determined by the formation of domains and their poling behavior under externally applied fields. For multiferroics, which exhibit several types of ferroic order at once, it is also relevant how the domains of the coexisting ferroic states couple and what kind of functionality this might involve. In this work, we demonstrate the reversible transfer of a domain pattern between magnetization and electric-polarization space in the multiferroic Dy0.7Tb0.3FeO3. A magnetic field transfers a ferromagnetic domain pattern into an identical ferroelectric domain pattern while erasing it at its magnetic origin. Reverse transfer completes the cycle. To assess the generality of our experiment, we elaborate on its conceptual origin and aspects of application.

Emerging spin-phonon coupling through cross-talk of two magnetic sublattices.

Many material properties such as superconductivity, magnetoresistance or magnetoelectricity emerge from the non-linear interactions of spins and lattice/phonons. Hence, an in-depth understanding of spin-phonon coupling is at the heart of these properties. While most examples deal with one magnetic lattice only, the simultaneous presence of multiple magnetic orderings yield potentially unknown properties. We demonstrate a strong spin-phonon coupling in SmFeO3 that emerges from the interaction of both, iron and samarium spins. We probe this coupling as a remarkably large shift of phonon frequencies and the appearance of new phonons. The spin-phonon coupling is absent for the magnetic ordering of iron alone but emerges with the additional ordering of the samarium spins. Intriguingly, this ordering is not spontaneous but induced by the iron magnetism. Our findings show an emergent phenomenon from the non-linear interaction by multiple orders, which do not need to occur spontaneously. This allows for a conceptually different approach in the search for yet unknown properties.