ArticlePDF Available

Abstract and Figures

The influence of lattice strain on the refractive index and optical band gap of NaNbO3 thin films, deposited by the liquid-delivery spin metalorganic chemical vapor deposition method, was investigated by spectroscopic ellipsometry. Epitaxial growth of coherently strained NaNbO3 films was confirmed by high-resolution x-ray diffraction and transmission electron microscopy. Incorporated lattice strain in the films was varied by the use of the oxide substrates NdGaO3, SrTiO3 and DyScO3, which exhibit lattice mismatches to NaNbO3 with different sign, magnitude and anisotropy. The Sellmeier dispersion was employed to analyze the ellipsometry data in energy region of 1.49–2.75 eV. The refractive index at 632.8 nm of the pseudomorphically grown NaNbO3 films critically depends on the incorporated elastic lattice strain and results in a continuous decrease from 2.46 to 2.18 by varying the in-plane strain from compressive to tensile. Band gap energies for films grown under compressive and tensile lattice strain were determined by collecting spectroscopic ellipsometry data in a larger energy range between 0.73–6.48 eV and evaluating them by the Tauc-Lorentz dispersion. We observed that for tensily strained NaNbO3 films deposited on DyScO3 and SrTiO3, the band gap energies increased to 3.60-/+0.01 and 3.64-/+0.02 eV, respectively. For the compressively strained NaNbO3 film deposited on NdGaO3 the band gap is shifted to still higher energies (3.80-/+ 0.01 eV).
This content is subject to copyright. Terms and conditions apply.
A preview of the PDF is not available
... Recently, we have reported epitaxial growth of high quality NaNbO 3 thin films by MOVPE 14,[17][18][19][20] and found a sequence of phase transitions when the films are grown on various substrates with varying lattice mismatch. 17,21 In particular, fully compressively strained NaNbO 3 thin films grown on the NdGaO 3 substrate exhibit an orthorhombic c phase with exclusive vertical electrical polarization, which transforms into the inclined monoclinic M A phase when the epitaxial strain is partially relaxed. ...
... The experimental spectra agree with those typically observed in the transparency range of perovskite oxide ferroelectrics and comparable to that of the NaNbO 3 film deposited on DyScO 3 . 19,29 In the nearinfrared range, the real part slightly increases with temperature, while at the UV-visible region, the imaginary part shows a redshift tendency. This behavior is attributed to electron-phonon interaction that is enhanced with the increasing temperature, as observed in other ferroelectric materials. ...
Article
Full-text available
We have investigated high temperature phase transitions in NaNbO 3 thin films epitaxially grown under tensile lattice strain on (110) DyScO 3 substrates using metal-organic vapor phase epitaxy. At room temperature, a very regular stripe domain pattern consisting of the monoclinic a 1 a 2 ferroelectric phase was observed. Temperature-dependent studies of the refractive index and the optical bandgap as well as in situ high-resolution x-ray diffraction measurements prove a ferroelectric–ferroelectric phase transition in the range between 250 and 300 °C. The experimental results strongly suggest that the high-temperature phase exhibits a distorted orthorhombic a 1 /a 2 crystal symmetry, with the electric polarization vector lying exclusively in the plane. A second phase transition was observed at about 500 °C, which presumably signifies the transition to the paraelectric phase. Both phase transitions show a pronounced temperature-dependent hysteresis, indicating first-order phase transitions.
... Recently, we have reported epitaxial growth of high quality NaNbO 3 thin films by MOVPE 14,[17][18][19][20] and found a sequence of phase transitions when the films are grown on various substrates with varying lattice mismatch. 17,21 In particular, fully compressively strained NaNbO 3 thin films grown on the NdGaO 3 substrate exhibit an orthorhombic c phase with exclusive vertical electrical polarization, which transforms into the inclined monoclinic M A phase when the epitaxial strain is partially relaxed. ...
... The experimental spectra agree with those typically observed in the transparency range of perovskite oxide ferroelectrics and comparable to that of the NaNbO 3 film deposited on DyScO 3 . 19,29 In the nearinfrared range, the real part slightly increases with temperature, while at the UV-visible region, the imaginary part shows a redshift tendency. This behavior is attributed to electron-phonon interaction that is enhanced with the increasing temperature, as observed in other ferroelectric materials. ...
Article
Full-text available
We provide a combined theoretical and experimental study of the electronic structure and the optical absorption edge of the orthorhombic perovskite LaInO3, employing density functional theory and many-body perturbation theory. We find the lowest-energy excitation at 0.2 eV below the fundamental gap (5 eV), reflecting a sizable electron-hole attraction. Since the transition from the valence band maximum (Γ point) is, however, dipole forbidden, the onset is characterized by weak excitations from transitions around it. The first intense excitation appears about 0.32 eV above. Interestingly, this value coincides with an experimental value obtained by ellipsometry (4.80 eV) which is higher than the onset from optical absorption spectroscopy (4.35 eV). The latter discrepancy is attributed to the fact that the weak transitions that define the optical gap are not well enough resolved by the ellipsometry measurement. Through temperature-dependent measurements of the optical gap, we assess renormalization effects by electron-phonon coupling, enhancing the quantitative comparison between theoretical and experimental results.
... While in the energy range up to ∼3.5 eV the extinction coefficient k is close to zero indicating a transparent region, the refractive index n slightly increases from 2.2 to about 2.5 for both phases. A strong increase in k displays the onset of absorption at higher energies, which also results in an increase of n until a maximum is obtained at ∼4.5 eV and subsequently a strong decrease, often observed for many perovskite oxide thin films [9,41]. From Fig. 4(b) we also conclude that n and k are quite similar for the film in the monoclinic M c -phase and the orthorhombic c-phase in the transparent region, but in the absorption region (>3.5 eV) significant differences can be detected. ...
Article
Full-text available
The dielectric function and interband critical points of compressively strained ferroelectric K0.85Na0.15NbO3 thin film grown by metal-organic vapor phase epitaxy (MOVPE) are studied in broad spectral and temperature ranges by spectroscopic ellipsometry (SE). The temperature dependence of the measured pseudodielectric functions is strongly affected by a structural phase transition from the monoclinic Mc-phase to the orthorhombic c-phase at about 428 K. Using a parametric optical constant model, the corresponding dielectric functions as well as the interband optical transitions of the film are determined in the spectral range of 0.73–6.00 eV. Standard critical point (SCP) analysis of the 2nd derivatives of the dielectric functions identified three and four critical points for monoclinic and orthorhombic symmetries, respectively. A systematic redshift of the threshold energies with increasing temperatures was observed.
... NaNbO 3 has an orthorhombic symmetry at room temperature with lattice constants a o = 5.569 Å, b o = 5.505 Å, c o = 15.523 Å, and we also can calculate the pseudocubic lattice parameters of NaNbO 3 to a c = 3.881 Å, b c = 3.915 Å, c c = 3.915, and ␣ c = 90.67 • [7,8]. As a photocatalyst, it has the extensive potential applications in solar fuel production and organic pollutant removal [9][10][11][12][13][14][15][16]. ...
Article
Full-text available
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.
Article
Full-text available
Epitaxial a-axis oriented NaNbO3 films are grown on (110) oriented NdGaO3 substrates. The lattice mismatch between substrate and film leads to compressive strain of ∼0.7% in the a-c plane. As a consequence, the in-plane permittivity and tunability are strongly enhanced compared to bulk NaNbO3, and a pronounced maximum in the temperature dependence of the permittivity occurs. Below the maximum at Tmax ≈ 250 K, ferroelectric behavior is observed that seems to vanish above Tmax. The pristine phase of the film at T < Tmax is antiferroelectric and is easily suppressed by small applied electric fields. The ferroelectric phase shows a relaxor type behavior.
Article
Full-text available
To improve the photocatalytic activity of NaNbO3 for water splitting, the bandgap and the band edges of NaNbO3 should be tailored to match the visible part of the solar spectrum and hydrogen and oxygen redox potentials. By analyzing the band structures of La/Bi-doped and (La/Bi + N)-codoped NaNbO3, we found that the pseudointermediate band (PIB) was formed in the bandgap in all the doped systems because of the orbital splitting of the Nb 4d induced by the dramatically enlarged O-Nb-O angles. The PIB could make the wide bandgap semiconductors absorb visible-light photons as long as it was degenerate or partially degenerate. Considering that the appropriate band edges and absorption properties, we believe that (La/Bi + N)-codoped NaNbO3 materials are promising photocatalysts for hydrogen production through water splitting under visible-light irradiation without other modifications.
Article
Full-text available
Environmental concerns are strongly driving the need to replace the lead-based piezoelectric materials currently employed as multilayer actuators. The current review describes both compositional and structural engineering approaches to achieve enhanced piezoelectric properties in lead-free materials. The review of the compositional engineering approach focuses on compositional tuning of the properties and phase behavior in three promising families of lead-free perovskite ferroelectrics: the titanate, alkaline niobate and bismuth perovskites and their solid solutions. The 'structural engineering' approaches focus instead on optimization of microstructural features including grain size, grain orientation or texture, ferroelectric domain size and electrical bias field as potential paths to induce large piezoelectric properties in lead-free piezoceramics. It is suggested that a combination of both compositional and novel structural engineering approaches will be required in order to realize viable lead-free alternatives to current lead-based materials for piezoelectric actuator applications.
Article
Full-text available
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.
Article
NaNbO3 thin films have been grown under anisotropic biaxial strain on several oxide substrates by liquid-delivery spin metalorganic chemical vapor deposition. Compressive lattice strain of different magnitude, induced by the deposition of NaNbO3 films with varying film thickness on NdGaO3 single crystalline substrates, leads to modifications of film orientation and phase symmetry, which are similar to the phase transitions in Pb-containing oxides near the morphotropic phase boundary. Piezoresponse force microscopy measurements exhibit large out-of-plane polarization components, but no distinctive domain structure, while C-V measurements indicate relaxor properties in these films. When tensile strain is provoked by the epitaxial growth on DyScO3, TbScO3, and GdScO3 single crystalline substrates, NaNbO3 films behave rather like a normal ferroelectric. The application of these rare-earth scandate substrates yields well-ordered ferroelectric stripe domains of the type a1 /a2 with coherent domain walls aligned along the [001] substrate direction as long as the films are fully strained. With increasing plastic lattice relaxation, initially, a 2D domain pattern with still exclusively in-plane electric polarization, and finally, domains with in-plane and out-of-plane polar components evolve.
Article
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.
Article
Optical properties of A-site disordered Na0.5Bi0.5TiO3-x%BaTiO3 (NBT-xBT) single crystals with three typical compositions were studied systematically. Refractive index as a function of wavelength was measured by Spectroscopic ellipsometry, and modified Sellmeier dispersion equations were obtained by the least square fitting. High optical transmittance (65%) over a wide transparent region (from 400 to 6000 nm) has been found in NBT-7.5BT, much higher than that of NBT and NBT-5BT. Optical band gap energies were calculated using the absorption coefficient through Tauc equation. With increasing BT content, refractive index and absorption coefficient decrease, while transmission and band gap energy increase.
Article
Sodium niobate (NaNbO3) microcrystals were crystallized by a technically flexible ion exchange method in solution phase. A potassium niobate hollow sphere (KNHS) precursor was first grown via a hydrothermal route, the metastable compound is chemically active in NaOH solution, leading to the crystallization of NaNbO3 microcrystals by a spontaneous ion exchange and recrystallization process. The crucial influences of ion exchange duration, NaOH concentration, surfactant, and reaction medium (water, ethylene glycol/water, ethylenediamine/water) on both the morphology and crystal phase of the NaNbO3 microcrystals have also been established. This current chemical route provides an extremely simple, mild, and effective recipe to crystallize NaNbO3, which could possibly be expanded to more niobate crystals with well controlled chemical compositions, structures, and particle morphologies.