Yulan Li

Room-temperature ferroelectricity in strained SrTiO3

Systems with a ferroelectric to paraelectric transition in the vicinity of room temperature are useful for devices. Adjusting the ferroelectric transition temperature (Tc) is traditionally accomplished by chemical substitution—as in BaxSr1-xTiO3, the material widely investigated for microwave devices in which the dielectric constant (εr) at GHz frequencies is tuned by applying a quasi-static electric field. Heterogeneity associated with chemical substitution in such films, however, can broaden this phase transition by hundreds of degrees, which is detrimental to tunability and microwave device performance. An alternative way to adjust Tc in ferroelectric films is strain. Here we show that epitaxial strain from a newly developed substrate can be harnessed to increase Tc by hundreds of degrees and produce room-temperature ferroelectricity in strontium titanate, a material that is not normally ferroelectric at any temperature. This strain-induced enhancement in Tc is the largest ever reported. Spatially resolved images of the local polarization state reveal a uniformity that far exceeds films tailored by chemical substitution. The high εr at room temperature in these films (nearly 7,000 at 10 GHz) and its sharp dependence on electric field are promising for device applications.

Effect of substrate constraint on the stability and evolution of ferroelectric domain structures in thin films

The stability and evolution of ferroelectric domain structures in thin films are studied. Elastic solutions are derived for both elastically anisotropic and isotropic thin films with arbitrary domain structures, subject to the mixed stress-free and constraint boundary conditions. These solutions are employed in a three-dimensional phase-field model to investigate simultaneously the effect of substrate constraint and temperature on the volume fractions of domain variants, domain-wall orientations, surface topology, domain shapes, and their temporal evolution for a cubic-to-tetragonal ferroelectric phase transition. A specific example of a [001] orientated film heteroepitaxially grown on a [001] cubic substrate is considered. It is shown that the shapes of a-domains with tetragonal axes parallel to the film surface are significantly different from those of c-domains with tetragonal axes perpendicular to the film surface. For the substrate constraints and temperatures under which both a- and c-domains coexist, both types of a-domains are present with their tetragonal axes perpendicular to each other, and the domain wall orientations deviate from the 45 orientation generally assumed in thermodynamic analyses. It is demonstrated that a substrate constraint results in sequential nucleation and growth of different tetragonal domains during a ferroelectric phase transition.

A Ferroelectric Oxide Made Directly on Silicon

Metal oxide semiconductor field-effect transistors, formed using silicon dioxide and silicon, have undergone four decades of staggering technological advancement. With fundamental limits to this technology close at hand, alternatives to silicon dioxide are being pursued to enable new functionality and device architectures. We achieved ferroelectric functionality in intimate contact with silicon by growing coherently strained strontium titanate (SrTiO3) films via oxide molecular beam epitaxy in direct contact with silicon, with no interfacial silicon dioxide. We observed ferroelectricity in these ultrathin SrTiO3 layers by means of piezoresponse force microscopy. Stable ferroelectric nanodomains created in SrTiO3 were observed at temperatures as high as 400 kelvin.

A phenomenological thermodynamic potential for BaTiO3 single crystals

A phenomenological thermodynamic potential was constructed based on the properties of bulk BaTiO3 single crystals. An eighth-order polynomial of Landau-Devonshire expansion was employed. It reproduces bulk properties including the three possible ferroelectric transition temperatures and their dependence on electric fields, as well as the dielectric and piezoelectric constants. Different from the existing thermodynamic potential, it is applicable to predicting the ferroelectric phase transitions and properties of BaTiO3 thin films under large compressive biaxial strains.

Ferroelastic switching for nanoscale non-volatile magnetoelectric devices

Multiferroics, where (anti-) ferromagnetic, ferroelectric and ferroelastic order parameters coexist, enable manipulation of magnetic ordering by an electric field through switching of the electric polarization. It has been shown that realization of magnetoelectric coupling in a single-phase multiferroic such as BiFeO(3) requires ferroelastic (71 degrees, 109 degrees) rather than ferroelectric (180 degrees) domain switching. However, the control of such ferroelastic switching in a single-phase system has been a significant challenge as elastic interactions tend to destabilize small switched volumes, resulting in subsequent ferroelastic back-switching at zero electric field, and thus the disappearance of non-volatile information storage. Guided by our phase-field simulations, here we report an approach to stabilize ferroelastic switching by eliminating the stress-induced instability responsible for back-switching using isolated monodomain BiFeO(3) islands. This work demonstrates a critical step to control and use non-volatile magnetoelectric coupling at the nanoscale. Beyond magnetoelectric coupling, it provides a framework for exploring a route to control multiple order parameters coupled to ferroelastic order in other low-symmetry materials.

Phase-field model of domain structures in ferroelectric thin films

A phase-field model for predicting the coherent microstructure evolution in constrained thin films is developed. It employs an analytical elastic solution derived for a constrained film with arbitrary eigenstrain distributions. The domain structure evolution during a cubic→tetragonal proper ferroelectric phase transition is studied. It is shown that the model is able to simultaneously predict the effects of substrate constraint and temperature on the volume fractions of domain variants, domain-wall orientations, domain shapes, and their temporal evolution.

Probing Nanoscale Ferroelectricity by Ultraviolet Raman Spectroscopy

We demonstrated that ultraviolet Raman spectroscopy is an effective technique to measure the transition temperature (Tc) in ferroelectric ultrathin films and superlattices. We showed that one-unit-cell-thick BaTiO3 layers in BaTiO3/SrTiO3 superlattices are not only ferroelectric (with Tc as high as 250 kelvin) but also polarize the quantum paraelectric SrTiO3 layers adjacent to them. Tc was tuned by ∼500 kelvin by varying the thicknesses of the BaTiO3 and SrTiO3 layers, revealing the essential roles of electrical and mechanical boundary conditions for nanoscale ferroelectricity.

Effect of electrical boundary conditions on ferroelectric domain structures in thin films

The domain structures in a ferroelectric thin film are studied using a phase-field model. A cubic-to-tetragonal ferroelectric phase transition in lead titanate thin film is considered. Both elastic interactions and electrostatic interactions are taken into account. The focus is on the effect of electrical boundary conditions on the domain morphologies and volume fractions. It is shown that different electric boundary conditions may have a significant effect on the domain structures.

Temperature-strain phase diagram for BaTiO3 thin films

The shifts of ferroelectric phase transition temperatures and domain stabilities of BaTiO3 thin films as a function of strain and temperature were studied using phase-field simulations. A new Landau-Devonshire thermodynamic potential based on an eighth-order polynomial was employed for describing the bulk free energy of BaTiO3 single crystals, which allows the exploration of domain stability in the full range of experimentally accessible compressive and tensile strains. Based on the simulation results, a phase diagram was constructed, which displays the stability of various ferroelectric phases and domain structures as a function of temperature and strain.

Effect of substrate-induced strains on the spontaneous polarization of epitaxial BiFeO3 thin films

A single-domain thermodynamic theory is employed to predict the spontaneous polarizations of (001)c, (101)c, and (111)c oriented epitaxial BiFeO3 thin films grown on dissimilar substrates. The effects of various substrate-induced strains on the spontaneous polarization were studied. The dependences of the spontaneous polarization on film orientations and the types of substrate-induced strains were analyzed.