Tetragonal Domains Research Articles

Test of the Dynamic-Domain and Critical Scattering Hypotheses in Cubic Methylammonium Lead Triiodide

We investigate the hypothesis of dynamic tetragonal domains occuring in cubic CH$_3$NH$_3$PbI$_3$ using high-resolution neutron spectroscopy to study a fully deuterated single crystal. The $\textit{R}$-point scattering above the 327.5 K tetragonal-cubic phase transition is always resolution-limited in energy and therefore inconsistent with dynamic domain predictions. This behavior is instead consistent with the central peak phenomenon observed in other perovskites. The scattering may originate from small, static, tetragonal-phase domains nucleating about crystal defects, and the temperature dependence demonstrates the transition is first-order.

Investigating the Tetragonal‐to‐Orthorhombic Phase Transition of Methylammonium Lead Iodide Single Crystals by Detailed Photoluminescence Analysis

AbstractHere, the phase‐transition from tetragonal to orthorhombic crystal structure of the halide perovskite methylammonium lead iodide single crystal is investigated. Temperature dependent photoluminescence (PL) measurements in the temperature range between 165 and 100 K show complex PL spectra where in total five different PL peaks can be identified. All observed PL features can be assigned to different optical effects from the two crystal phases using detailed PL analyses. This allows to quantify the fraction of tetragonal phase that still occurs below the phase transition temperature. It is found that at 150 K, 0.015% tetragonal phase remain, and PL signatures are observed from quantum confined tetragonal domains, suggesting their size to be about 7–15 nm down to 120 K. The tetragonal inclusions also exhibit an increased Urbach Energy, implying a high degree of structural disorder. The results first illustrate how a careful analysis of the PL can serve to deduce structural information, and second, how structural deviations in halide perovskites have a significant impact on the optoelectronic properties of this promising class of semiconductors.

Coupling Lattice Instabilities Across the Interface in Ultrathin Oxide Heterostructures.

Oxide heterointerfaces constitute a rich platform for realizing novel functionalities in condensed matter. A key aspect is the strong link between structural and electronic properties, which can be modified by interfacing materials with distinct lattice symmetries. Here, we determine the effect of the cubic-tetragonal distortion of SrTiO3 on the electronic properties of thin films of SrIrO3, a topological crystalline metal hosting a delicate interplay between spin-orbit coupling and electronic correlations. We demonstrate that below the transition temperature at 105 K, SrIrO3 orthorhombic domains couple directly to tetragonal domains in SrTiO3. This forces the in-phase rotational axis to lie in-plane and creates a binary domain structure in the SrIrO3 film. The close proximity to the metal–insulator transition in ultrathin SrIrO3 causes the individual domains to have strongly anisotropic transport properties, driven by a reduction of bandwidth along the in-phase axis. The strong structure–property relationships in perovskites make these compounds particularly suitable for static and dynamic coupling at interfaces, providing a promising route towards realizing novel functionalities in oxide heterostructures.

Mesoscopic origin of ferroelectric-ferroelectric transition in BaTiO3: Orthorhombic-to-tetragonal domain evolution

Ferroelectric materials are the core of common technologies, such as medical ultrasound, mobile-phone antennae and low-power memory devices. The technological interest in ferroelectrics stems from the existence of switchable mesoscale polarization domains. Hence, understanding the origin of ferroelectric functionality requires realization of the domain dynamics during a ferroelectric transformation. However, domain dynamics characterization at the mesoscale is typically too slow with respect to the abrupt ferroic transition. Using scanning probe microscopy with 15-mK thermal-, and deep-submicron spatial- resolution, we realized the domain dynamics during an orthorhombic-to-tetragonal transition in the seminal ferroelectric BaTiO3. We show that the transition comprises four distinguishable mechanisms. The dominant mechanism is a step-by-step progression of a tetragonal-domain wavefront into the orthorhombic phase. This progression is accompanied by ripple-like surface irregularities. Small island domains that remained orthorhombic diffuse then slowly after the wavefront progression. Finally, the resultant tetragonal domains equilibrate by coalescing in a constant-speed. These observations, which are accompanied by quantitative data, bridge between existing macroscopic and microscopic models regarding the nature of ferroelectric transitions, showing the mesoscale origin of ferroelectricity.

Evidence of precursor orthorhombic domains well above the electronic nematic transition temperature in Sr(Fe1−xCox)2As2

Raman scattering, synchrotron x-ray diffraction, specific heat, resistivity and magnetic susceptibility measurements were performed in Sr(Fe1−xCox)2As2 [] single crystals with superconducting critical temperature K and two additional transitions at 132 and 152 K observed in both specific heat and resistivity data. A quasielastic Raman signal with B2g symmetry (tetragonal cell) associated with electronic nematic fluctuations is observed. Crucially, this signal shows maximum intensity at K, marking the nematic transition temperature. X-ray diffraction shows evidence of coexisting orthorhombic and tetragonal domains between and ∼ 152 K, implying that precursor orthorhombic domains emerge over an extended temperature range above . While the height of the quasielastic Raman peak is insensitive to , the temperature-dependence of the average nematic fluctuation rate indicates a slowing down of the nematic fluctuations inside the precursor orthorhombic domains. These results are analogous to those previously reported for the LaFeAsO parent oxypnictide (Kaneko et al 2017 Phys. Rev. B 96 014506). We propose a scenario where the precursor orthorhombic phase may be generated within the electronically disordered regime () as long as the nematic fluctuation rate is sufficiently small in comparison to the optical phonon frequency range. In this regime, the local atomic structure responds adiabatically to the electronic nematic fluctuations, creating a net of orthorhombic clusters that, albeit dynamical for , may be sufficiently dense to sustain long-range phase coherence in a diffraction process up to .

Active subspace analysis and uncertainty quantification for a polydomain ferroelectric phase-field model

We perform parameter subset selection and uncertainty analysis for phase-field models that are applied to the ferroelectric material lead titanate. A motivating objective is to determine which parameters are influential in the sense that their uncertainties directly affect the uncertainty in the model response, and fix noninfluential parameters at nominal values for subsequent uncertainty propagation. We employ Bayesian inference to quantify the uncertainties of gradient exchange parameters governing 180° and 90° tetragonal phase domain wall energies. The uncertainties of influential parameters determined by parameter subset selection are then propagated through the models to obtain credible intervals when estimating energy densities quantifying polarization and strain across domain walls. The results illustrate various properties of Landau and electromechanical coupling parameters and their influence on domain wall interactions. We employ energy statistics, which quantify distances between statistical observations, to compare credible intervals constructed using a complete set of parameters against an influential subset of parameters. These intervals are obtained from the uncertainty propagation of the model input parameters on the domain wall energy densities. The investigation provides critical insight into the development of parameter subset selection, uncertainty quantification, and propagation methodologies for material modeling domain wall structure evolution, informed by density functional theory simulations.

A micro–macro scale approach for thermal effects in ferroelectrics

The influence of thermal fields on the electromechanical behavior of ferroelectric ceramics under cyclic electric loading is presented. To predict the temperature effect, a 3D micromechanical model for tetragonal domain switching is extended by including thermal effects. Numerical simulations were done through the finite element program Abaqus with the help of a user-defined element. Besides external heat sources, a change in temperature is considered by internal heat generated due to domain switching. Material properties are assumed to be linearly dependent on the temperature. The temperature influence on the behavior of ferroelectrics is shown by means of the strain and polarization hysteresis loops. The model shows a good qualitative agreement with the experimental results available in the literature.

Anisotropic strain: A critical role in domain evolution in (111)- Oriented ferroelectric films

Domain behavior of (111)- oriented perovskite ferroelectric films is significantly different from (001)-/(101)- oriented ones, resulting in enhancing property responses such as a superior susceptibility and a reduced coercive field. However, the domain structures and evolutions with the thickness of (111)-oriented ferroelectric films, which are crucial to further understand the distinctive properties, are still obscure. In this study, the ferroelectric domains of (111)- oriented PbTiO3 films are investigated by transmission electronic microscopy (TEM) and piezoresponse force microscopy (PFM). We identify the domain evolution with the film thicknesses under anisotropic strains imposed by the orthorhombic GdScO3 (101)O substrates. Contrast analysis and electron diffraction patterns reveal that only four ferroelectric variants evolve in PTO films: d2+, d2-, d3+ and d3-, with the polarization directions along [010], [01¯0], [001] and [001¯], respectively. Two kinds of domain walls are formed: “inclined” (011) domain walls for d2-/d3+ (d2+/d3-) domains, “normal” (011¯) domain walls for d2-/d3+ (d2+/d3-) domains. The width of periodically distributed d2+/d3+ (d2-/d3-) domains increases with film thickness following the square root rule. Aberration-corrected scanning transmission electronic microscopy demonstrates the lattice characteristics of domains in (111)- oriented PbTiO3 films are consistent with tetragonal ferroelectric domains. PFM studies reveal that both the out-of-plane and in-plane polarization components of d2-/d3+ (d2+/d3-) domains are non-identical, whereas the d2+/d3+ (d2-/d3-) domains possess uniform out-of-plane polarization component and non-uniform in-plane polarization component. This study discloses the domain structure in (111)- oriented tetragonal ferroelectric films under anisotropic strains and the association with the ferroelectric properties.

Realization of rhombohedral, mixed, and tetragonal like phases of BiFeO3 and ferroelectric domain engineering using a strain tuning layer on LaAlO3(001) substrate

BiFeO3 (BFO), a room temperature multiferroic, undergoes a series of structural transformations under varying strain conditions by utilizing appropriate substrates for a specific strain condition. In this study, epitaxial thin films of BFO were grown on La0.7Sr0.3MnO3±δ (LSMO), a strain tuning layer on LaAlO3[LAO (001)] substrates, using pulsed laser ablation. LSMO layers of varying thicknesses from 2 nm to 20 nm were grown followed by a BFO layer of a fixed thickness (20 nm). A strained layer of ∼2 nm thick LSMO stabilizes the tetragonal like phase of BFO. Increasing the thickness of the LSMO layer to 10 nm results in a mixed phase with rhombohedral (R) and tetragonal (T) domains, and a further increment of the LSMO layer thickness to 20 nm stabilizes the rhombohedral phase of BFO. The tetragonal phase with weak monoclinic distortion possessed 180° domains with dominant out-of-plane polarization components. However, the mixed phase (R + T) possessed various plausible polarization components in both out-of-plane and in-plane directions. Further, a thermodynamically consistent model based on the phase field approach was implemented to investigate the role of strain on the formation of domain patterns with various polarization components and piezoelectric coefficients. The simulated domain structure exhibited a similar transformation on the dominant polarization components as observed in experiments across different phases of BFO. Our simulations show that the elastic constraint along the z-direction enhances the tetragonality of BFO. The piezoelectric (d33) coefficient was found to be ∼46 pm/V for the 20 nm mixed phase BFO, which was nearly a 200% increment compared to the single phase BFO thin films on LAO.

Zr0.70[Y1-xNdx]0.30O1.85 as a potential candidate for inert matrix fuel: Structural and thermo-physical property investigations

In order to mimic the loading of americium (Am) and curium (Cm) oxide in yttria stabilized zirconia, Zr0.70 [Y1-xNdx]0.30O1.85 (0.0 ≤ x ≤ 1.0) system was synthesized by solid state route and characterized by X-ray diffraction (XRD) and Raman spectroscopy. The entire system appeared single-phasic fluorite-type by XRD. However, Raman spectroscopy revealed the existence of tetragonal domains for the Nd-rich composition, Zr0.70Nd0.30O1.85 (x = 1.0). Bulk thermal expansion coefficient was found to increase with increasing NdO1.5 content in this series in the temperature range 298–1473 K. The heat capacity of sintered samples was measured by heat flux-type differential scanning calorimeter over the temperature range 313–713 K and it was observed to decrease with increasing Nd3+-content. Thermal conductivity values were determined from measured thermal diffusivity, temperature dependent density and specific heat capacity values. The thermal conductivity of Nd3+ stabilized zirconia was lower than yttria stabilized zirconia.

Development of 0.8Pb(Zr0.48Ti0.52)O3–0.2Pb [(Zn1/3Nb2/3)0.625(Mn1/3Nb2/3)0.375]O3 Ceramics for High-Intensity Ultrasound Applications

The B-site oxide mixing technique has been used to fabricate 0.8Pb(Zr0.48 Ti0.52)O3–0.2Pb[(Zn1/3Nb2/3)0.625(Mn1/3Nb2/3)0.375]O3 (PZT–PZMnN) + x wt.% ZnO nanoparticle ceramics, where x = 0.0, 0.20, 0.25, 0.30, 0.35, 0.40, and 0.45. The perovskite PZT–PZMnN + x wt.% ZnO solid solution was sintered at 950°C. Presence of tetragonal and rhombohedral phases in the sintered PZT–PZMnN + 0.35 wt.% ZnO compound at room temperature was confirmed by simultaneously investigating the structure, microstructure, and dielectric properties. The largest grain size was exhibited by the PZT–PZMnN + 0.35 wt.% ZnO nanoparticle ceramic near the morphotropic phase boundary. For this composition, small rhombohedral domains with 71° or 108° domain walls were observed around relatively large tetragonal domains with 180° and 90° domain walls. The width of these domains was found to be about 100 nm. The PZT–PZMnN ceramics exhibited the following optimal properties at this ZnO nanoparticle content of 0.35 wt.%: electromechanical coupling factors of kp of 0.60 and kt of 0.46, piezoelectric constant d31 of 130 pC N−1, mechanical quality factor Qm of 1280, high remanent polarization Pr of 30.4 μC cm−2, and low coercive field Ec of 6.2 kV cm−1, making it a promising material for use in high-intensity ultrasound applications.

High electromechanical response in the non morphotropic phase boundary piezoelectric system PbTiO3−Bi(Zr1/2Ni1/2)O3

There is a general perception that large piezoelectric response in ferroelectric alloys requires tuning the system towards a morphotropic phase boundary (MPB), i.e., a composition driven inter-ferroelectric instability. Here we show that high piezoelectric response can be realized even in non-MPB alloy systems. This is demonstrated on (1-x)PbTiO3-(x)Bi(Zr0.5Ni0.5)O3 (PT-BNZ) by a comprehensive study involving electric-field and temperature dependent XRD, Raman spectroscopy, dielectric, piezoelectric and high field electrostrain measurements. We found that poling-field irreversibly suppresses the cubic-like phase at room temperature. Based on our results, we argue that that which appears as MPB, comprising of tetragonal and cubic-like phases on the global scale, is not so actually. The large piezoresponse is due to coexistence of tetragonal regions of long and short-range coherence. The PT-BNZ system is therefore qualitatively different from the conventional MPB systems such as PZT, PMN-PT, and PbTiO3-BiScO3, etc., which exhibits coexisting tetragonal and rhombohedral/monoclinic phases in thermodynamic equilibrium. In the absence of inter-ferroelectric instability as a phenomenon, field induced polarization-rotation and inter-ferroelectric transformation are no longer plausible mechanisms to explain the large piezoelectric response in PT-BNZ. The large piezoelectricity is primarily due to enhanced mobility of the tetragonal domain walls enabled by domain miniaturization. Our study proves that attainment of large piezoelectricity does not require inter-ferroelectric instability as a necessary criterion.

Modulation of Superconducting Transition Temperature in LaAlO3/SrTiO3 by SrTiO3 Structural Domains

The tetragonal domain structure in SrTiO3 (STO) is known to modulate the normal-state carrier density in LaAlO3/SrTiO3 (LAO/STO) heterostructures, among other electronic properties, but the effect of STO domains on the superconductivity in LAO/STO has not been fully explored. Using a scanning SQUID susceptometer microscope to map the superconducting response as a function of temperature in LAO/STO, we find that the superconducting transition temperature is spatially inhomogeneous and modulated in a pattern that is characteristic of structural domains in the STO.

Temperature-Dependent Evolution of Crystallographic and Domain Structures in (K,Na,Li)(Ta,Nb)O3 Piezoelectric Single Crystals.

(K,Na)NbO3-based ferroelectric single crystals have recently undergone a substantial development, resulting in improved crystal quality and large piezoelectric coefficients, exceeding 700 pC/N, over a broad temperature range. However, further development necessitates a detailed understanding of the mechanisms defining the domain structure and its temperature evolution. This paper presents the investigation into the crystallographic structure and domain configurations of a (K,Na,Li)(Ta,Nb)O3 single crystal over a broad temperature range. The crystal was grown by the submerged-seed solution growth technique and investigated using in situ transmission electron microscopy, X-ray diffraction, dielectric measurements, and polarized light microscopy. The lattice distortion, structural phase transitions, and domain configurations are reported. A transition from the lamellar orthorhombic to the rectangular tetragonal domain structure is observed upon heating. Moreover, the milky optical appearance of the crystal was investigated and found to result from the presence of regions with different domain configurations and domain sizes. The formation of these regions is related to the growth defects, which govern the domain formation when cooling below the Curie temperature.

Characterization and some fundamental features of Optically Stimulated Luminescence measurements of silver activated lithium tetraborate

A new lithium tetraborate (Li2B4O7 or abbreviated as LTB) material was produced by adding various concentrations of Ag impurities to allow better luminescent properties using the solution combustion synthesis (SCS) method. The formation of single phase LTB was confirmed using X-ray Diffraction (XRD) data and Scanning Electron Microscopy (SEM) analysis indicated the existence of a tetragonal crystalline domain. Two broad band emissions located at ∼ 272 nm (near UV region) and 526 nm (green region) were observed from room temperature photoluminescence (PL) under 205 nm excitation The synthesized material consisted of polycrystalline LTB with 1 wt% Ag (abbreviated herein as LTB:Ag) exhibits considerable thermoluminescence (TL) and Optically Stimulated Luminescence (OSL) which is several times more sensitive to beta radiation than the other concentrations attempted. It was determined that the OSL signal has been a collection of three component signals. A step-preheating procedure to investigate the depth of the trapping centers associated with the OSL signal was carried out. We suggest that the TL peak at 200 °C mainly contributes to the OSL signal. It was observed that the total OSL area shows a linear dose response for beta doses ranging from 1 to 100 Gy. The minimum detectable dose (MDD) value was found to be around 3 mGy using the total OSL area. Under optimum conditions (irradiation with beta-rays), the reproducibility of total OSL area was determined with a −3% deviation at the end of the 9th irradiation-blue light stimulation-readout cycle. The dark storage stability of the total OSL signals was investigated and fading of the total OSL area was found to be approximately 25% after one week. The trap depth corresponding to the OSL signal was found to be 0.99 eV and 0.94 eV using various heating rate and isothermal annealing methods, respectively. Finally, silver doped lithium tetraborate is shown to have promise as an optically stimulated luminescent dosimeter, particularly in medical and personal applications.

In-situ X-ray diffraction on functional thin films using a laboratory source during electrical biasing

A methodology that allows the quantification of structural changes in functional thin films during the application of external electrical field is reported. The originality of this method is the development of a set-up using a laboratory X-ray source since most of previous Operando studies have used synchrotron radiations. Several technical challenges have been addressed: the (i) optimization of the electrical contact and the sample geometry within the lab-source goniometers, (ii) evaluation of any X-ray dose effect on the Metal/Insulator/Metal structure to prevent eventual charge accumulation at the electrode interfaces and (iii) the quantification of the effect of the time-delay, needed for X-ray measurement, on domain switching. The validity of our method has been demonstrated on a prototypic sol-gel lead zirconate titanate (PZT) thin film where the polarization and structural changes have been simultaneously measured. The evolution of ferroelastic domains as a function of external electric field has been quantified and two different effects have been successfully separated: (a) the cell extension and (b) domain wall motion described as the switching between a and c tetragonal domains.

The Effect of Synthesis Conditions on the Phase Composition and Structure of EuBa2Cu3O6 + δ Samples

The composition and the structure of ceramic EuBa2Cu3O6 + δ (Eu-123) oxide samples annealed in steps with varying processing conditions (in air or oxygen and argon atmosphere at a temperature of 940–960°С for 1–70 h with or without homogenization) were studied by the X-ray phase and chemical analysis, electron diffraction pattern analysis, elemental analysis, and high-resolution transmission electron microscopy. Regardless of the processing conditions, Eu-123 nanostructured oxide with a tetragonal or orthorhombic structure and domains 1–20 nm in size was obtained as a result of annealing. Nanostructuring of the samples, which was revealed by high-resolution electron microscopy, is attributed to their chemical nature: the presence of identical structural elements in members of the homologous Eu n Ba m Cum + nO y series of oxides allows them to intergrow coherently and create an illusion of a single crystal. Just like any other member of the Eu n Ba m Cum + nO y series, oxide Eu-123 is disproportionate depending on the annealing conditions to form other members of this series located on either side of the dominant oxide. Temperature Tc of the superconducting transition of each member of the series depends on the average oxidation state of copper $$\overline {Cu} $$ . At $$\overline {Cu} $$ < 2, all members of the series have a tetragonal structure and do not exhibit superconducting properties. At $$\overline {Cu} $$ = 2.28, five members of the Eu n Ba m Cum + nO y series with matrices (Ba : Cu) 5 : 8, 3 : 5, 2 : 3, 5 : 7, and 3 : 4 exhibit superconducting properties with Tc = 82–90 K.

Direct visualization of phase separation between superconducting and nematic domains in Co-doped CaFe2As2 close to a first-order phase transition

We show that biaxial strain induces alternating tetragonal superconducting and orthorhombic nematic domains in Co substituted CaFe2As2. We use Atomic Force, Magnetic Force and Scanning Tunneling Microscopy (AFM, MFM and STM) to identify the domains and characterize their properties, finding in particular that tetragonal superconducting domains are very elongated, more than several tens of micron long and about 30 nm wide, have the same Tc than unstrained samples and hold vortices in a magnetic field. Thus, biaxial strain produces a phase separated state, where each phase is equivalent to what is found at either side of the first order phase transition between antiferromagnetic orthorhombic and superconducting tetragonal phases found in unstrained samples when changing Co concentration. Having such alternating superconducting domains separated by normal conducting domains with sizes of order of the coherence length opens opportunities to build Josephson junction networks or vortex pinning arrays and suggests that first order quantum phase transitions lead to nanometric size phase separation under the influence of strain.

Accelerated Discovery of Large Electrostrains in BaTiO3 -Based Piezoelectrics Using Active Learning.

A key challenge in guiding experiments toward materials with desired properties is to effectively navigate the vast search space comprising the chemistry and structure of allowed compounds. Here, it is shown how the use of machine learning coupled to optimization methods can accelerate the discovery of new Pb-free BaTiO3 (BTO-) based piezoelectrics with large electrostrains. By experimentally comparing several design strategies, it is shown that the approach balancing the trade-off between exploration (using uncertainties) and exploitation (using only model predictions) gives the optimal criterion leading to the synthesis of the piezoelectric (Ba0.84 Ca0.16 )(Ti0.90 Zr0.07 Sn0.03 )O3 with the largest electrostrain of 0.23% in the BTO family. Using Landau theory and insights from density functional theory, it is uncovered that the observed large electrostrain is due to the presence of Sn, which allows for the ease of switching of tetragonal domains under an electric field.

Spatially modulated magnetic structure of EuS due to the tetragonal domain structure of SrTiO3

The combination of ferromagnets with topological superconductors or insulators allows for new phases of matter that support excitations such as chiral edge modes and Majorana fermions. EuS, a wide-band-gap ferromagnetic insulator with a Curie temperature around 16 K, and SrTiO$_3$ (STO), an important substrate for engineering heterostructures, may support these phases. We present scanning superconducting quantum interference device (SQUID) measurements of EuS grown epitaxially on STO that reveal micron-scale variations in ferromagnetism and paramagnetism. These variations are oriented along the STO crystal axes and only change their configuration upon thermal cycling above the STO cubic-to-tetragonal structural transition temperature at 105 K, indicating that the observed magnetic features are due to coupling between EuS and the STO tetragonal structure. We speculate that the STO tetragonal distortions may strain the EuS, altering the magnetic anisotropy on a micron-scale. This result demonstrates that local variation in the induced magnetic order from EuS grown on STO needs to be considered when engineering new phases of matter that require spatially homogeneous exchange.