M. Tyunina

Strain-controlled optical absorption in epitaxial ferroelectric BaTiO3 films

A lattice strain of 0.3%–1.3% is achieved in epitaxial tetragonal BaTiO3 films grown on (001)-oriented SrTiO3 single-crystal substrates. Our experimental studies of absorption spectra in the range of 0.74–9.0 eV demonstrate that epitaxy produces significant changes in the optical properties of the films compared with those of a reference polydomain BaTiO3 crystal: the absorption edge and the peak at 5 eV strongly blue-shift by 0.2–0.4 eV, the magnitude of the peak at 5 eV drops, and certain spectral features disappear, whereas the absorption peak at 8.5 eV remains unchanged. The observed behavior is attributed to ferroelectric polarization, which is enhanced by epitaxial strain in the films. Our results indicate that epitaxially induced variations of ferroelectric polarization may be used to tailor the optical properties of thin films for photonic and optoelectronic applications.

Size effects and dielectric behaviour in ferroelectric heterostructures

The low-frequency dielectric response of thin-film and bulk ferroelectric or relaxor heterostructures was analysed. For epitaxial crystallographic strain-free thin films of ferroelectric (Ba,Sr)TiO3 and relaxor PbMg1/3Nb2/3O3, more experimental data supporting the interface layer model were obtained. The combined effects of properties and thicknesses of both the films and electrode layers on the dielectric response were demonstrated using the comparison of the experimental results with the results of estimations. In thin-film heterostructures, the anomalous frequency dispersion of the dielectric permittivity and losses was explained as originating from the joint film–electrode scaling. The study of the interface parameters using the thickness dependence of the permittivity was shown to be incorrect. In bulk relaxors, the relaxor–electrode pair was found to give apparent additional relaxation laws not related to the true dielectric relaxation. Both in thin-film and bulk heterostructures, a lower-resistivity layer was suggested to exist at the surface of perovskite ferroelectrics and relaxors.

Ferroelectricity in antiferroelectric NaNbO3 crystal.

Sodium niobate (NaNbO3, or NNO) is known to be antiferroelectric at temperatures between 45 and 753 K. Here we show experimentally the presence of the ferroelectric phase at temperatures between 100 and 830 K in the NNO crystals obtained by top-seeded solution growth. The ferroelectric phase and new phase transitions are evidenced using a combination of thermo-optical studies by variable angle spectroscopic ellipsometry, Raman spectroscopy analysis, and photoelectron emission microscopy. The possibility for strain-induced ferroelectricity in NNO is suggested.

Tensile strain induced changes in the optical spectra of SrTiO3 epitaxial thin films

Effect of biaxial tensile strains on optical function and band edge transitions of ultra thin epitaxial films was studied using as an example a 13 nm thick SrTiO3 films deposited on KTaO3 (100) single-crystal substrates. Optical functions in the 200–1200 nm spectral range were determined by spectroscopic ellipsometry technique. It was found that tensile strains result in a shift of the low energy band gap optical transitions to higher energies and decrease the refractive index in the visible region. Comparison of the optical spectra for strained SrTiO3 films and for homoepitaxial strain-free SrTiO3: Cr (0.01 at %) films deposited on SrTiO3 (100) single crystalline substrates showed that this “blue” shift of the band gap could not be related to technological imperfections or to reduced thickness. The observed effect is connected with changes in the lowest conduction and in the top valence bands that are due to increase of the in-plane lattice constant and/or onset of the polar phase in the tensile strain-induced ultra-thin epitaxial SrTiO3 films.

Quantitative analysis of structural inhomogeneity in nanomaterials using transmission electron microscopy

A method for quantifying inhomogeneity of crystal structure at the nanoscale is suggested and experimentally verified. The method is based on digital processing of images obtained by high-resolution transmission electron microscopy. A series of images is acquired and each image is divided into several overlapping sliding windows. Interplanar distances are determined using a fast Fourier transform and the CrysTBox software. A spatial distribution of the estimated distances is obtained considering the size and position of the sliding window within the analysed sample. This approach provides for a picometric precision and accuracy if applied on ideal data. Although this accuracy was verified on experimental data, it can be worsened by errors specific to a particular application and data acquisition technique. The achieved spatial resolution ranges from a few to tens of nanometres. These levels of accuracy, precision and spatial resolution are reached without the need for aberration correction or for a reference lattice parameter, and using samples prepared by focused ion beam milling.

PLD prepared bioactive BaTiO3 films on TiNb implants

BaTiO3 (BTO) layers were deposited by pulsed laser deposition (PLD) on TiNb, Pt/TiNb, Si (100), and fused silica substrates using various deposition conditions. Polycrystalline BTO with sizes of crystallites in the range from 90nm to 160nm was obtained at elevated substrate temperatures of (600°C-700°C). With increasing deposition temperature above 700°C the formation of unwanted rutile phase prevented the growth of perovskite ferroelectric BTO. Concurrently, with decreasing substrate temperature below 500°C, amorphous films were formed. Post-deposition annealing of the amorphous deposits allowed obtaining perovskite BTO. Using a very thin Pt interlayer between the BTO films and TiNb substrate enabled high-temperature growth of preferentially oriented BTO. Raman spectroscopy and electrical characterization indicated polar ferroelectric behaviour of the BTO films.

Concurrent bandgap narrowing and polarization enhancement in epitaxial ferroelectric nanofilms.

Abstract Perovskite-type ferroelectric (FE) crystals are wide bandgap materials with technologically valuable optical and photoelectric properties. Here, versatile engineering of electronic transitions is demonstrated in FE nanofilms of KTaO3, KNbO3 (KNO), and NaNbO3 (NNO) with a thickness of 10–30 unit cells. Control of the bandgap is achieved using heteroepitaxial growth of new structural phases on SrTiO3 (001) substrates. Compared to bulk crystals, anomalous bandgap narrowing is obtained in the FE state of KNO and NNO films. This effect opposes polarization-induced bandgap widening, which is typically found for FE materials. Transmission electron microscopy and spectroscopic ellipsometry measurements indicate that the formation of higher-symmetry structural phases of KNO and NNO produces the desirable red shift of the absorption spectrum towards visible light, while simultaneously stabilizing robust FE order. Tuning of optical properties in FE films is of interest for nanoscale photonic and optoelectronic devices.

Optical properties of epitaxial relaxor ferroelectric PbSc0.5Nb0.5O3 films

The optical properties of epitaxial perovskite-structure relaxor ferroelectric PbSc0.5Nb0.5O3 thin films are studied in broad spectral and temperature ranges by variable-angle spectroscopic ellipsometry. The films possess a metrically tetragonal crystal structure with a biaxial in-plane compressive strain of 0.1%–0.8%. The optical constants of the films with thickness of 10–50 nm are determined accurately using the advanced ellipsometry technique. The dramatic changes in the spectra of the dielectric functions and the absorption coefficient are found under various strain conditions. The characteristic energies of the spectra, including the bandgaps, vary by 0.1–0.5 eV. A frustration of the ferroelectric phase transition is evidenced by thermo-optical studies. A complex relationship between strain, polarization, and optical properties is discussed in terms of possible ionic displacements in metrically tetragonal PbSc0.5Nb0.5O3 films.

Ambience-sensitive optical refraction in ferroelectric nanofilms of NaNbO3

Abstract Optical index of refraction n is studied by spectroscopic ellipsometry in epitaxial nanofilms of NaNbO3 with thickness ∼10 nm grown on different single-crystal substrates. The index n in the transparency spectral range (n ≈ 2.1 – 2.2) exhibits a strong sensitivity to atmospheric-pressure gas ambience. The index n in air exceeds that in an oxygen ambience by δn ≈ 0.05 – 0.2. The thermo-optical behaviour n(T) indicates ferroelectric state in the nanofilms. The ambience-sensitive optical refraction is discussed in terms of fundamental connection between refraction and ferroelectric polarization in perovskites, screening of depolarizing field on surfaces of the nanofilms, and thermodynamically stable surface reconstructions of NaNbO3.

Elasto-optic behaviour in epitaxial films of perovskite oxide ferroelectrics

ABSTRACT Large variations of refractive index in the visible spectral range are obtained in epitaxial perovskite oxide ferroelectric films experiencing lattice strain. The strain is imposed by substrates, on top of which the films are grown. The optical constants are determined using the spectroscopic ellipsometry. As a reference and for comparison, also prototype single crystals are inspected. The variations in refraction are related to the lattice strain in the films. Elasto-optic coefficient is formally estimated using the out-of-plane lattice elongation or shrinkage in the films compared to bulk. The obtained elasto-optic coefficients exceed significantly those previously reported for ferroelectric materials.