Misfit Strain Relaxation Research Articles

Dissociation of [formula omitted] misfit dislocation at the interface of α-Ga2O3 thin film deposited on m-plane sapphire

In this study, α-Ga2O3 films of thickness about 1 μm were epitaxially deposited on m-plane sapphire substrate by halide vapor phase epitaxy. The lattice mismatch between α-Ga2O3 and sapphire substrate is about 3.5 % along c-axis and 4.8 % along a-axis, resulting in the formation of misfit dislocations. High-angle annular dark-field scanning transmission electron microscopy was employed to study the misfit dislocations at the α-Ga2O3/sapphire interface. The study was carried out along the [112‾0] zone axis and focused on the dislocations responsible for a misfit strain relaxation along c-axis. The resulting magnitude of the projected Burgers vector onto (112‾0) plane has been compared with the estimated values for 13<1‾101> and 13<2‾021> dislocations. It has been revealed, that misfit dislocations tend to dissociate into partial dislocations at the interface.

Effect of Film Thickness on Microstructural and Magnetic Properties of Lithium Ferrite Films Prepared on Strontium Titanate (001) Substrates

Epitaxial lithium ferrite (LiFe5O8) films with different thicknesses were successfully fabricated on strontium titanate (SrTiO3) (001) substrates using the magnetron sputtering deposition technique. The microstructural and magnetic properties of the films were characterized by an advanced transmission electron microscope and a magnetic measurement device. It was found that the formation of structural defects can be influenced by the thickness of the film. In addition to misfit dislocations, orientation domains form in thinner films and twin boundaries appear in thicker films, respectively, contributing to the misfit strain relaxation in the heterosystem. The magnetic measurement showed that the thinner films have enhanced magnetization and a relatively lower coercive field compared with the thicker films containing antiferromagnetic twin boundaries. Our results provide a way of tuning the microstructure and magnetic properties of lithium ferrite films by changing the film thickness.

Dislocation interactions during plastic relaxation of epitaxial colloidal crystals

The severe difficulty to resolve simultaneously both the macroscopic deformation process and the dislocation dynamics on the atomic scale limits our understanding of crystal plasticity. Here we use colloidal crystals, imaged on the single particle level by high-speed three-dimensional (3D) confocal microscopy, and resolve in real-time both the relaxation of the epitaxial misfit strain and the accompanying evolution of dislocations. We show how dislocation interactions give rise to the formation of complex dislocation networks in 3D and to unexpectedly sharp plastic relaxation. The sharp relaxation is facilitated by attractive interactions that promote the formation of new dislocations that are more efficient in mediating strain. Dislocation networks form fragmented structures, as dislocation growth is blocked by either attractive interactions, which result in the formation of sessile dislocation junctions, or by repulsion from perpendicular segments. The strength of these blocking mechanisms decreases with the thickness of the crystal film. These results reveal the critical role of dislocation interactions in plastic deformation of thin films and can be readily generalized from the colloidal to the atomic scale.

Effects of flexoelectric polarization on surface potential of dielectric thin-film heterostructures: A comparative study

Recently, flexoelectric effect has attracted considerable attention owing to ubiquitous existence in all dielectrics, regardless of the symmetry. It promises intriguingly physical phenomena, such as strain gradient-induced electric polarizations, photocurrents, and interfacial transports, as well as their electromechanical coupling with external force loading, in diverse materials for multifunctional applications in electronics. In this work, we report the flexoelectric-modulation on surface potential of LaFeO3 (LFO) thin-film heterostructures. The LFO thin film with or without the flexoelectric effect has been achieved by controlling epitaxial misfit against a substrate. Lattice structures and strain behaviors are observed by atomic-resolution high-angle annular dark-field imaging. Grown on a LaAlO3 substrate, a giant strain gradient of ∼3 × 106 m−1 is generated in the LFO thin film due to the gradual relaxation of large misfit strain with increasing thickness, yielding a robust flexoelectric polarization pointing to the heterostructure surface. In contrast, the LFO is almost fully strained on a SrTiO3 substrate due to the small lattice mismatch. The flexoelectric polarization results in an increase in surface potential in the LFO heterostructure due to the incomplete screening of positive polarization bound charges, as observed by scanning kelvin probe microscopy. Furthermore, x-ray photoelectron spectroscopy reveals that the flexoelectric polarization can downward bend the band alignment of the LFO layer and modulate the interfacial potential barriers. These results provide the way for experimental observations of the flexoelectric effect and deliver physical insight into deep understanding of interfacial electronic structures of flexoelectric-based devices.

Sierpiński Structure and Electronic Topology in Bi Thin Films on InSb(111)B Surfaces

Deposition of Bi on InSb(111)B reveals a striking Sierpiński-triangle (ST)-like structure in Bi thin films. Such a fractal geometric topology is further shown to turn off the intrinsic electronic topology in a thin film. Relaxation of a huge misfit strain of about 30% to 40% between Bi adlayer and substrate is revealed to drive the ST-like island formation. A Frenkel-Kontrova model is developed to illustrate the enhanced strain relief in the ST islands offsetting the additional step energy cost. Besides a sufficiently large tensile strain, forming ST-like structures also requires larger adlayer-substrate and intra-adlayer elastic stiffnesses, and weaker intra-adlayer interatomic interactions.

Defects in epitaxial Ru(0001) on Al2O3(0001): Dislocations, stacking faults, and deformation twins

Defects in epitaxial Ru(0001) films on c-plane sapphire, with nominal thicknesses of 10–80 nm, deposited at 350 °C and step-annealed to 950 °C, were characterized using transmission electron microscopy. The variation of Ru and sapphire lattice parameters with temperature is such that the misfit strain for the observed 30° rotated-honeycomb epitaxial relationship is essentially constant with temperature at 1.5%, resulting in a biaxial stress of 10.0 GPa and an energy density of 150 MJ m−3 in unrelaxed films. Stress relaxation occurs by the formation of defects. For the 20–80 nm thick films, the defects are a- and c-type dislocations and stacking faults, argued to be of I2 type. In addition, the films show the surprising presence of {112¯1}1/3⟨112¯6¯⟩ deformation twins. The 10 nm-thick films were found to be defect free. The critical thickness for misfit strain relaxation via the formation of threading and misfit dislocations is computed as 7±2nm, depending on the choice of the dislocation core radius. Energetic analysis of twin formation, using both the infinite-matrix and the finite-matrix (Mori–Tanaka) approaches, provides values of the twin aspect ratios, assumed to be ellipsoidal, and shows that the latter but not the former approach can qualitatively explain the formation of the observed twins. In addition to providing the maximum strain relief compared to other potential twin types, {112¯1}1/3⟨112¯6¯⟩ twins do not require lattice shuffles and have a boundary that is a special boundary, namely, a 35° tilt boundary with a-type dislocations every other {0002} plane, that may also favor their formation.

Vertically Aligned Single-Crystalline CoFe2O4 Nanobrush Architectures with High Magnetization and Tailored Magnetic Anisotropy.

Micrometer-tall vertically aligned single-crystalline CoFe2O4 nanobrush architectures with extraordinarily large aspect ratio have been achieved by the precise control of a kinetic and thermodynamic non-equilibrium pulsed laser epitaxy process. Direct observations by scanning transmission electron microscopy reveal that the nanobrush crystal is mostly defect-free by nature, and epitaxially connected to the substrate through a continuous 2D interface layer. In contrast, periodic dislocations and lattice defects such as anti-phase boundaries and twin boundaries are frequently observed in the 2D interface layer, suggesting that interface misfit strain relaxation under a non-equilibrium growth condition plays a critical role in the self-assembly of such artificial architectures. Magnetic property measurements have found that the nanobrushes exhibit a saturation magnetization value of 6.16 μB/f.u., which is much higher than the bulk value. The discovery not only enables insights into an effective route for fabricating unconventional high-quality nanostructures, but also demonstrates a novel magnetic architecture with potential applications in nanomagnetic devices.

Graphene-assisted spontaneous relaxation towards dislocation-free heteroepitaxy.

Although conventional homoepitaxy forms high-quality epitaxial layers1-5, the limited set of material systems for commercially available wafers restricts the range of materials that can be grown homoepitaxially. At the same time, conventional heteroepitaxy of lattice-mismatched systems produces dislocations above a critical strain energy to release the accumulated strain energy as the film thickness increases. The formation of dislocations, which severely degrade electronic/photonic device performances6-8, is fundamentally unavoidable in highly lattice-mismatched epitaxy9-11. Here, we introduce a unique mechanism of relaxing misfit strain in heteroepitaxial films that can enable effective lattice engineering. We have observed that heteroepitaxy on graphene-coated substrates allows for spontaneous relaxation of misfit strain owing to the slippery graphene surface while achieving single-crystalline films by reading the atomic potential from the substrate. This spontaneous relaxation technique could transform the monolithic integration of largely lattice-mismatched systems by covering a wide range of the misfit spectrum to enhance and broaden the functionality of semiconductor devices for advanced electronics and photonics.

Generation of misfit dislocations in a core-shell nanowire near the edge of prismatic core

The misfit strain relaxation via generation of partial and perfect misfit dislocations and their dipoles at the interface in core-shell nanowires with faceted cores is considered. The core has the shape of a long parallelepiped of a square cross-section and is placed symmetrically with respect to the cylindrical shell surface. The energy change caused by dislocation generation in such nanowires is calculated. Critical conditions for the onset of such dislocations are calculated and analyzed. The energy barriers for the dislocation generation are defined with respect to different values of the nanowire parameters. The preference of dislocation configuration and generation sites in the nanowire are determined.

Generation of Misfit Dislocations in a Core-Shell Nanowire Near the Edge of Prismatic Core

The misfit strain relaxation via generation of partial and perfect misfit dislocations and their di-poles at the interface in core-shell nanowires with faceted cores is considered. The core has the shape of a long parallelepiped of a square cross-section and placed symmetrically with respect to the cylindrical shell surface. The energy change caused by dislocation generation in such nanowires is calculated. Critical conditions for the onset of such dislocations are calculated and analyzed. The energy barriers for the dislocation generation are defined with respect to different values of the nanowire parameters. The preference of dislocation configuration and generation sites in the nanowire are determined.

Lattice strain-enhanced exsolution of nanoparticles in thin films

Nanoparticles formed on oxide surfaces are of key importance in many fields such as catalysis and renewable energy. Here, we control B-site exsolution via lattice strain to achieve a high degree of exsolution of nanoparticles in perovskite thin films: more than 1100 particles μm−2 with a particle size as small as ~5 nm can be achieved via strain control. Compressive-strained films show a larger number of exsolved particles as compared with tensile-strained films. Moreover, the strain-enhanced in situ growth of nanoparticles offers high thermal stability and coking resistance, a low reduction temperature (550 °C), rapid release of particles, and wide tunability. The mechanism of lattice strain-enhanced exsolution is illuminated by thermodynamic and kinetic aspects, emphasizing the unique role of the misfit-strain relaxation energy. This study provides critical insights not only into the design of new forms of nanostructures but also to applications ranging from catalysis, energy conversion/storage, nano-composites, nano-magnetism, to nano-optics.

Effects of ultrathin AlN prelayers on the spontaneous growth of GaN nanowires by plasma assisted molecular beam epitaxy

The effects of ultrathin AlN prelayers, with nominal thicknesses between 0 and 1.5 nm, on the spontaneous growth of GaN nanowires (NWs) on Si (1 1 1) substrates were investigated. The morphological and structural characteristics of GaN NWs were analyzed by electron microscopy and X-ray diffraction techniques. The results quantify how the AlN prelayer thickness affects GaN NWs. The increase of AlN thickness gradually limits nitridation of the substrate surface and accelerates 3D GaN nucleation. The formation of amorphous SixNy by Si nitridation is completely avoided for 1.5 nm of AlN that fully covers the Si surface. The dependence of the height, diameter and density of GaN NWs on the AlN thickness was also determined. The 1.5 nm AlN provided the optimum condition for GaN NW nucleation and growth; the NWs exhibited a large homogeneous height with almost no parasitic GaN formation between them. High resolution transmission electron microscopy showed the full relaxation of misfit strain of AlN on Si (1 1 1) and of GaN NWs on AlN. In-situ reflection high energy electron diffraction during AlN nucleation revealed the immediate relaxation of the AlN prelayer before GaN NW nucleation. Formation of β-Si3N4 before AlN nucleation was also observed.

Misfit strain relaxations of (101)-oriented ferroelectric PbTiO3/(La, Sr)(Al, Ta)O3thin film systems

Abstract

Transformation of the defect structure of InGaAs and InAlAs metamorphic buffer layers depending on indium concentration

A study of samples grown by molecular beam epitaxy using the technology of InxAl1-xAs or InxGa1-xAs metamorphic buffer layer formation on GaAs (001) substrate was performed by transmission electron microscopy. The 1 μm thick buffer layers with square-root dependence of In content on buffer layer thickness were studied in plan-view and cross-section geometries. The results demonstrate cascade step-wise relaxation of misfit strain along buffer layer thickness with the reduction of dislocation density to less than 10−6 cm−2 at the subsurface region. An inhomogeneous distribution of dislocations observed on plan-view TEM images is explained by overlap of split-level dislocation networks with different periods.

Dislocation baskets in thick InxGa1−xN epilayers

Dislocation clusters have been observed in thick InxGa1−xN films with 0.07 ≤ x ≤ 0.12. The clusters resemble baskets with a higher indium content at their interior. Threading dislocations at the basket boundaries are of the misfit edge type, and their separation is consistent with misfit strain relaxation due to the difference in indium content between the baskets and the surrounding matrix. The interior of the base of the baskets exhibits no observable dislocations connecting the threading dislocations, and often no net displacements like those due to stacking faults. We argue that the origin of these threading dislocation arrays is associated with misfit dislocations at the basal plane that dissociate, forming stacking faults. And when the stacking faults form simultaneously satisfying the crystal symmetry, the sum of their translation vectors add up to a lattice vector, or equivalently to no change in the stacking sequence, which is consistent with our observations.

Ferroelastically protected polarization switching pathways to control electrical conductivity in strain-graded ferroelectric nanoplates

Charged domain walls have rarely been observed in ferroelectric materials because of instability by large electrostatic energy. In this work, the authors have stabilized charged domain structures by ferroelastic clamping and manipulated resultant electric conductance in ferroelectric nanomaterials. Ferroelectric nanoplates subjected to compressive misfit strain at the bottom but less external stress on the sidewalls exhibit a radial-quadrant in-plane ferroelectric domain structure that is electrostatically unstable but emerges due to the flexoelectric effect associated with the misfit strain relaxation. They report that significant electronic conduction occurs near the edge of a ferroelectric nanoplate and the enhanced electronic conduction can be suppressed by 180${}^{\ensuremath{\circ}}$ polarization switching in a reversible way.

Ascertaining the Nature and Distribution of Extended Crystalline Defects in Emerging Semiconductor Materials Using Electron Channeling Contrast Imaging

Semiconductor heterostructures represent the key building blocks for most nanoelectronics and photonics devices. However, the performance and reliability of these devices is often limited by the presence of extended defects arising from plastic relaxation of misfit strain. Hence, metrology for assessing the nature, density and distribution of such defects is of crucial importance in order to support the development and fabrication of novel semiconductor devices. Electron Channeling Contrast Imaging (ECCI) has emerged as the method of choice for analyzing the crystalline quality of semiconductor heterostructures with excellent precision even at low defect densities. The present paper discusses the most relevant theoretical and experimental aspects one needs to consider to obtain high-quality ECCI micrographs. Moreover, the capabilities of the methodology are illustrated on the example of various different defect types in the most relevant semiconductor material systems and structures.

Control of misfit strain in ferroelectric BaTiO3 thin-film capacitors with SrRuO3-based electrodes on (Ba, Sr)TiO3-buffered SrTiO3 substrates

We investigate ferroelectric BaTiO3 capacitors with SrRuO3-based electrodes employing a (BaxSr1−x)TiO3 (BST) buffer layer on (100) SrTiO3 substrates prepared by pulsed laser deposition. Structural analysis by high-resolution X-ray diffraction reciprocal space mapping shows that the BST (x = 0.5 and 0.7) layers are relaxed and have their bulk in-plane lattices in the upper part owing to strain relief. The bottom electrodes on the buffer layers grow heteroepitaxially but cannot withstand a tensile stress and then show a diminution of the in-plane lattice. On the BST (x = 0.7) layer, compared with the capacitor with an SrRuO3 electrode, that with a Ba0.1Sr0.9RuO3 one has a reduced in-plane lattice relaxation of the BaTiO3 film and then exhibits a larger remanent polarization (Pr) of 34 μC/cm2 associated with a smaller shift of the hysteresis loop. The polarization hysteresis shift is attributed to a flexoelectric effect stemming from the coupling between out-of-plane polarization and a strain gradient in the BaTiO3 film. We conclude that a reduced misfit strain relaxation in the ferroelectric film achieved with the Ba0.1Sr0.9RuO3 electrode on the thicker BST (x = 0.7) buffer layer is the origin of an enhanced Pr with a smaller hysteresis shift.

Perfect Strain Relaxation in Metamorphic Epitaxial Aluminum on Silicon through Primary and Secondary Interface Misfit Dislocation Arrays.

Understanding the atomically precise arrangement of atoms at epitaxial interfaces is important for emerging technologies such as quantum materials that have function and performance dictated by bonds and defects that are energetically active on the micro-electronvolt scale. A combination of atomistic modeling and dislocation theory analysis describes both primary and secondary dislocation networks at the metamorphic Al/Si (111) interface, which is experimentally validated by atomic resolution scanning transmission electron microscopy. The electron microscopy images show primary misfit dislocations for the majority of the strain relief and evidence of a secondary structure allowing for complete relaxation of the Al-Si misfit strain. This study demonstrates the equilibrium interface that represents the lowest energy structure of a highly mismatched and semicoherent single-crystal interface with complete strain relief in an atomically abrupt structure.

Impact of thickness variation on structural, dielectric and piezoelectric properties of (Ba,Ca)(Ti,Zr)O3 epitaxial thin films

It is shown that the dielectric and piezoelectric properties of Ba(Ti0.8Zr0.2)O3-x(Ba0.7Ca0.3)TiO3 (x = 0.45) (BCTZ 45) epitaxial thin films have a nontrivial dependence on film thickness. BCTZ 45 epitaxial films with different thicknesses (up to 400 nm) have been deposited on SrTiO3 by pulsed laser deposition and investigated by different combined techniques: conventional and off-axis X-ray diffraction, high resolution transmission electron microscopy and dielectric and piezoforce microscopy. The changes occurring in epitaxial films when their thickness increases have been attributed to a partial relaxation of misfit strain, driving the induced tetragonal symmetry in very thin films to the original rhombohedral symmetry of the bulk material in the thickest film, which influences directly and indirectly the dielectric and piezoelectric properties.