Ultrafast Optically Induced Perturbation of Oxygen Octahedral Rotations in Multiferroic BiFeO3 Thin Films.

The functional properties of complex oxides, including magnetism and ferroelectricity, are closely linked to subtle structural distortions. Ultrafast optical excitations provide the means to manipulate structural features and ultimately to affect the functional properties of complex oxides with picosecond-scale precision. We report that the lattice expansion of multiferroic BiFeO3 following above-bandgap optical excitation leads to distortion of the oxygen octahedral rotation (OOR) pattern. The continuous coupling between OOR and strain was probed using time-resolved X-ray free-electron laser diffraction with femtosecond time resolution. Density functional theory calculations predict a relationship between the OOR and the elastic strain consistent with the experiment, demonstrating a route to employing this approach in a wider range of systems. Ultrafast control of the functional properties of BiFeO3 thin films is enabled by this approach because the OOR phenomena are related to ferroelectricity, and via the Fe-O-Fe bond angles, the superexchange interaction between Fe atoms.

Benchmarking of X-Ray Fluorescence Microscopy with Ion Beam Implanted Samples Showing Detection Sensitivity of Hundreds of Atoms.

Single impurities in insulators are now often used for quantum sensors and single photon sources, while nanoscale semiconductor doping features are being constructed for electrical contacts in quantum technology devices, implying that new methods for sensitive, non-destructive imaging of single- or few-atom structures are needed. X-ray fluorescence (XRF) can provide nanoscale imaging with chemical specificity, and features comprising as few as 100 000 atoms have been detected without any need for specialized or destructive sample preparation. Presently, the ultimate limits of sensitivity of XRF are unknown - here, gallium dopants in silicon are investigated using a high brilliance, synchrotron source collimated to a small spot. It is demonstrated that with a single-pixel integration time of 1 s, the sensitivity is sufficient to identify a single isolated feature of only 3000 Ga impurities (a mass of just 350 zg). With increased integration (25 s), 650 impurities can be detected. The results are quantified using a calibration sample consisting of precisely controlled numbers of implanted atoms in nanometer-sized structures. The results show that such features can now be mapped quantitatively when calibration samples are used, and suggest that, in the near future, planned upgrades to XRF facilities might achieve single-atom sensitivity.

Giant electric field-induced second harmonic generation in polar skyrmions.

Electric field-induced second harmonic generation allows electrically controlling nonlinear light-matter interactions crucial for emerging integrated photonics applications. Despite its wide presence in materials, the figures-of-merit of electric field-induced second harmonic generation are yet to be elevated to enable novel device functionalities. Here, we show that the polar skyrmions, a topological phase spontaneously formed in PbTiO3/SrTiO3 ferroelectric superlattices, exhibit a high comprehensive electric field-induced second harmonic generation performance. The second-order nonlinear susceptibility and modulation depth, measured under non-resonant 800 nm excitation, reach ~54.2 pm V-1 and ~664% V-1, respectively, and high response bandwidth (higher than 10 MHz), wide operating temperature range (up to ~400 K) and good fatigue resistance (>1010 cycles) are also demonstrated. Through combined in-situ experiments and phase-field simulations, we establish the microscopic links between the exotic polarization configuration and field-induced transition paths of the skyrmions and their electric field-induced second harmonic generation response. Our study not only presents a highly competitive thin-film material ready for constructing on-chip devices, but opens up new avenues of utilizing topological polar structures in the fields of photonics and optoelectronics.

Ultrafast Switching of Interfacial Thermal Conductance.

Dynamical control of thermal transport at the nanoscale provides a time-domain strategy for optimizing thermal management in nanoelectronics, magnetic devices, and thermoelectric devices. However, the rate of change available for thermal switches and regulators is limited to millisecond time scales, calling for a faster modulation speed. Here, time-resolved X-ray diffraction measurements and thermal transport modeling reveal an ultrafast modulation of the interfacial thermal conductance of an FeRh/MgO heterostructure as a result of a structural phase transition driven by optical excitation. Within 90 ps after optical excitation, the interfacial thermal conductance is reduced by a factor of 5 and lasts for a few nanoseconds, in comparison to the value at the equilibrium FeRh/MgO interface. The experimental results combined with thermal transport calculations suggest that the reduced interfacial thermal conductance results from enhanced phonon scattering at the interface where the lattice experiences transient in-plane biaxial stress due to the structural phase transition of FeRh. Our results suggest that optically driven phase transitions can be utilized for ultrafast nanoscale thermal switches for device application.

Thermal atomic layer deposition of Er2O3 films from a volatile, thermally stable enaminolate precursor.

Thin films of Er2O3 films were grown by atomic layer deposition using the Er precursor tris(1-(dimethylamino)-3,3-dimethylbut-1-en-2-olate)erbium(III) (Er(L1)3), with water as the co-reactant. Saturative, self-limited growth was observed at a substrate temperature of 200 °C for pulse lengths of ≥4.0 s for Er(L1)3 and ≥0.2 s for water. An ALD window was observed from 175 to 225 °C with a growth rate of about 0.25 Å per cycle. Er2O3 films grown at 200 °C on Si(100) and SiO2 substrates with a thickness of 33 nm had root mean square surface roughnesses of 1.75 and 0.75 nm, respectively. Grazing incidence X-ray diffraction patterns showed that the films were composed of polycrystalline Er2O3 at all deposition temperatures on Si(100) and SiO2 substrates. X-ray photoelectron spectroscopy revealed stoichiometric Er2O3, with carbon and nitrogen levels below the detection limits after argon ion sputtering to remove surface impurities. Transmission electron microscopy studies of Er2O3 film growth in nanoscale trenches (aspect ratio = 10) demonstrated conformal coverage.

Low-temperature nanoscale heat transport in a gadolinium iron garnet heterostructure probed by ultrafast x-ray diffraction.

Time-resolved x-ray diffraction has been used to measure the low-temperature thermal transport properties of a Pt/Gd3Fe5O12//Gd3Ga5O12 metal/oxide heterostructure relevant to applications in spin caloritronics. A pulsed femtosecond optical signal produces a rapid temperature rise in the Pt layer, followed by heat transport into the Gd3Fe5O12 (GdIG) thin film and the Gd3Ga5O12 (GGG) substrate. The time dependence of x-ray diffraction from the GdIG layer was tracked using an accelerator-based femtosecond x-ray source. The ultrafast diffraction measurements probed the intensity of the GdIG (1 -1 2) x-ray reflection in a grazing-incidence x-ray diffraction geometry. The comparison of the variation of the diffracted x-ray intensity with a model including heat transport and the temperature dependence of the GdIG lattice parameter allows the thermal conductance of the Pt/GdIG and GdIG//GGG interfaces to be determined. Complementary synchrotron x-ray diffraction studies of the low-temperature thermal expansion properties of the GdIG layer provide a precise calibration of the temperature dependence of the GdIG lattice parameter. The interfacial thermal conductance of the Pt/GdIG and GdIG//GGG interfaces determined from the time-resolved diffraction study is of the same order of magnitude as previous reports for metal/oxide and epitaxial dielectric interfaces. The thermal parameters of the Pt/GdIG//GGG heterostructure will aid in the design and implementation of thermal transport devices and nanostructures.

Subpicosecond Optical Stress Generation in Multiferroic BiFeO3.

Optical excitation leads to ultrafast stress generation in the prototypical multiferroic BiFeO3. The time scales of stress generation are set by the dynamics of the population of excited electronic states and the coupling of the electronic configuration to the structure. X-ray free-electron laser diffraction reveals high-wavevector subpicosecond-time scale stress generation following ultraviolet excitation of a BiFeO3 thin film. Stress generation includes a fast component with a 1/e rise time with an upper limit of 300 fs and longer-rise time components extending to 1.5 ps. The contributions of the fast and delayed components vary as a function of optical fluence, with a reduced a fast-component contribution at high fluence. The results provide insight into stress-generation mechanisms linked to the population of excited electrons and point to new directions in the application of nanoscale multiferroics and related ferroic complex oxides. The fast component of the stress indicates that structural parameters and properties of ferroelectric thin film materials can be optically modulated with 3 dB bandwidths of at least 0.5 THz.

X-ray nanodiffraction imaging reveals distinct nanoscopic dynamics of an ultrafast phase transition.

SignificancePhase transitions, the changes between states of matter with distinct electronic, magnetic, or structural properties, are at the center of condensed matter physics and underlie valuable technologies. First-order phase transitions are intrinsically heterogeneous. When driven by ultrashort excitation, nanoscale phase regions evolve rapidly, which has posed a significant experimental challenge to characterize. The newly developed laser-pumped X-ray nanodiffraction imaging technique reported here has simultaneous 100-ps temporal and 25-nm spatial resolutions. This approach reveals pathways of the nanoscale structural rearrangement upon ultrafast optical excitation, different from those transitions under slowly varying parameters. The spatiotemporally resolved structural characterization provides crucial nanoscopic insights into ultrafast phase transitions and opens opportunities for controlling nanoscale phases on ultrafast time scales.

Reconfiguration of Amorphous Complex Oxides: A Route to a Broad Range of Assembly Phenomena, Hybrid Materials, and Novel Functionalities.

Reconfiguration of amorphous complex oxides provides a readily controllable source of stress that can be leveraged in nanoscale assembly to access a broad range of 3D geometries and hybrid materials. An amorphous SrTiO3 layer on a Si:B/Si1- x Gex :B heterostructure is reconfigured at the atomic scale upon heating, exhibiting a change in volume of ≈2% and accompanying biaxial stress. The Si:B/Si1- x Gex :B bilayer is fabricated by molecular beam epitaxy, followed by sputter deposition of SrTiO3 at room temperature. The processes yield a hybrid oxide/semiconductor nanomembrane. Upon release from the substrate, the nanomembrane rolls up and has a curvature determined by the stress in the epitaxially grown Si:B/Si1- x Gex :B heterostructure. Heating to 600 °C leads to a decrease of the radius of curvature consistent with the development of a large compressive biaxial stress during the reconfiguration of SrTiO3 . The control of stresses via post-deposition processing provides a new route to the assembly of complex-oxide-based heterostructures in 3D geometry. The reconfiguration of metastable mechanical stressors enables i) synthesis of various types of strained superlattice structures that cannot be fabricated by direct growth and ii) technologies based on strain engineering of complex oxides via highly scalable lithographic processes and on large-area semiconductor substrates.

Optical transient grating pumped X-ray diffraction microscopy for studying mesoscale structural dynamics.

A fundamental understanding of materials' structural dynamics, with fine spatial and temporal control, underpins future developments in electronic and quantum materials. Here, we introduce an optical transient grating pump and focused X-ray diffraction probe technique (TGXD) to examine the structural evolution of materials excited by modulated light with a precisely controlled spatial profile. This method adds spatial resolution and direct structural sensitivity to the established utility of a sinusoidal transient-grating excitation. We demonstrate TGXD using two thin-film samples: epitaxial BiFeO3, which exhibits a photoinduced strain (structural grating) with an amplitude proportional to the optical fluence, and FeRh, which undergoes a magnetostructural phase transformation. In BiFeO3, structural relaxation is location independent, and the strain persists on the order of microseconds, consistent with the optical excitation of long-lived charge carriers. The strain profile of the structural grating in FeRh, in comparison, deviates from the sinusoidal excitation and exhibits both higher-order spatial frequencies and a location-dependent relaxation. The focused X-ray probe provides spatial resolution within the engineered optical excitation profile, resolving the spatiotemporal flow of heat through FeRh locally heated above the phase transition temperature. TGXD successfully characterizes mesoscopic energy transport in functional materials without relying on a specific transport model.

Dynamic Tilting of Ferroelectric Domain Walls Caused by Optically Induced Electronic Screening.

Optical excitation perturbs the balance of phenomena selecting the tilt orientation of domain walls within ferroelectric thin films. The high carrier density induced in a low-strain BaTiO_{3} thin film by an above-band-gap ultrafast optical pulse changes the tilt angle that 90° a/c domain walls form with respect to the substrate-film interface. The dynamics of the changes are apparent in time-resolved synchrotron x-ray scattering studies of the domain diffuse scattering. Tilting occurs at 298 K, a temperature at which the a/b and a/c domain phases coexist but is absent at 343 K in the better ordered single-phase a/c regime. Phase coexistence at 298 K leads to increased domain-wall charge density, and thus a larger screening effect than in the single-phase regime. The screening mechanism points to new directions for the manipulation of nanoscale ferroelectricity.

Subterahertz collective dynamics of polar vortices.

The collective dynamics of topological structures1-6 are of interest from both fundamental and applied perspectives. For example, studies of dynamical properties of magnetic vortices and skyrmions3,4 have not only deepened our understanding of many-body physics but also offered potential applications in data processing and storage7. Topological structures constructed from electrical polarization, rather than electron spin, have recently been realized in ferroelectric superlattices5,6, and these are promising for ultrafast electric-field control of topological orders. However, little is known about the dynamics underlying the functionality of such complex extended nanostructures. Here, using terahertz-field excitation and femtosecond X-ray diffraction measurements, we observe ultrafast collective polarization dynamics that are unique to polar vortices, with orders-of-magnitude higher frequencies and smaller lateral size than those of experimentally realized magnetic vortices3. A previously unseen tunable mode, hereafter referred to as a vortexon, emerges in the form of transient arrays of nanoscale circular patterns of atomic displacements, which reverse their vorticity on picosecond timescales. Its frequency is considerably reduced (softened) at a critical strain, indicating a condensation (freezing) of structural dynamics. We use first-principles-based atomistic calculations and phase-field modelling to reveal the microscopic atomic arrangements and corroborate the frequencies of the vortex modes. The discovery of subterahertz collective dynamics in polar vortices opens opportunities for electric-field-driven data processing in topological structures with ultrahigh speed and density.

Instrument for in situ hard x-ray nanobeam characterization during epitaxial crystallization and materials transformations.

Solid-phase epitaxy (SPE) and other three-dimensional epitaxial crystallization processes pose challenging structural and chemical characterization problems. The concentration of defects, the spatial distribution of elastic strain, and the chemical state of ions each vary with nanoscale characteristic length scales and depend sensitively on the gas environment and elastic boundary conditions during growth. The lateral or three-dimensional propagation of crystalline interfaces in SPE has nanoscale or submicrometer characteristic distances during typical crystallization times. An in situ synchrotron hard x-ray instrument allows these features to be studied during deposition and crystallization using diffraction, resonant scattering, nanobeam and coherent diffraction imaging, and reflectivity. The instrument incorporates a compact deposition system allowing the use of short-working-distance x-ray focusing optics. Layers are deposited using radio-frequency magnetron sputtering and evaporation sources. The deposition system provides control of the gas atmosphere and sample temperature. The sample is positioned using a stable mechanical design to minimize vibration and drift and employs precise translation stages to enable nanobeam experiments. Results of in situ x-ray characterization of the amorphous thin film deposition process for a SrTiO3/BaTiO3 multilayer illustrate implementation of this instrument.

Phase Selection and Structure of Low-Defect-Density γ-Al2O3 Created by Epitaxial Crystallization of Amorphous Al2O3.

A multistep phase sequence following the crystallization of amorphous Al2O3 via solid-phase epitaxy (SPE) points to methods to create low-defect-density thin films of the metastable cubic γ-Al2O3 polymorph. An amorphous Al2O3 thin film on a (0001) α-Al2O3 sapphire substrate initially transforms upon heating to form epitaxial γ-Al2O3, followed by a transformation to monoclinic θ-Al2O3, and eventually to α-Al2O3. Epitaxial γ-Al2O3 layers with low mosaic widths in X-ray rocking curves can be formed via SPE by crystallizing the γ-Al2O3 phase from amorphous Al2O3 and avoiding the microstructural inhomogeneity arising from the spatially inhomogeneous transformation to θ-Al2O3. A complementary molecular dynamics (MD) simulation indicates that the amorphous layer and γ-Al2O3 have similar Al coordination geometry, suggesting that γ-Al2O3 forms in part because it involves the minimum rearrangement of the initially amorphous configuration. The lattice parameters of γ-Al2O3 are consistent with a structure in which the majority of the Al vacancies in the spinel structure occupy sites with tetrahedral coordination, consistent with the MD results. The formation of Al vacancies at tetrahedral spinel sites in epitaxial γ-Al2O3 can minimize the epitaxial elastic deformation of γ-Al2O3 during crystallization.

Resonant nanodiffraction x-ray imaging reveals role of magnetic domains in complex oxide spin caloritronics.

Spin electronic devices based on crystalline oxide layers with nanoscale thicknesses involve complex structural and magnetic phenomena, including magnetic domains and the coupling of the magnetism to elastic and plastic crystallographic distortion. The magnetism of buried nanoscale layers has a substantial impact on spincaloritronic devices incorporating garnets and other oxides exhibiting the spin Seebeck effect (SSE). Synchrotron hard x-ray nanobeam diffraction techniques combine structural, elemental, and magnetic sensitivity and allow the magnetic domain configuration and structural distortion to be probed in buried layers simultaneously. Resonant scattering at the Gd L2 edge of Gd3Fe5O12 layers yields magnetic contrast with both linear and circular incident x-ray polarization. Domain patterns facet to form low-energy domain wall orientations but also are coupled to elastic features linked to epitaxial growth. Nanobeam magnetic diffraction images reveal diverse magnetic microstructure within emerging SSE materials and a strong coupling of the magnetism to crystallographic distortion.

Nanosecond Optically Induced Phase Transformation in Compressively Strained BiFeO_{3} on LaAlO_{3}.

Above-band-gap optical illumination of compressively strained BiFeO_{3} induces a transient reversible transformation from a state of coexisting tilted tetragonal-like and rhombohedral-like phases to an untilted tetragonal-like phase. Time-resolved synchrotron x-ray diffraction reveals that the transformation is induced by an ultrafast optically induced lattice expansion that shifts the relative free energies of the tetragonal-like and rhombohedral-like phases. The transformation proceeds at interfaces between regions of the tetragonal-like phase and regions of a mixture of tilted phases, consistent with the motion of a phase boundary. The optically induced transformation demonstrates that there are new optically driven routes towards nanosecond-scale control of phase transformations in ferroelectrics and multiferroics.

Simultaneous scanning near-field optical and X-ray diffraction microscopy for correlative nanoscale structure-property characterization.

A multimodal imaging instrument has been developed that integrates scanning near-field optical microscopy with nanofocused synchrotron X-ray diffraction imaging. The instrument allows for the simultaneous nanoscale characterization of electronic/near-field optical properties of materials together with their crystallographic structure, facilitating the investigation of local structure-property relationships. The design, implementation and operating procedures of this instrument are reported. The scientific capabilities are demonstrated in a proof-of-principle study of the insulator-metal phase transition in samarium sulfide (SmS) single crystals induced by applying mechanical pressure via a scanning tip. The multimodal imaging of an in situ tip-written region shows that the near-field optical reflectivity can be correlated with the heterogeneously transformed structure of the near-surface region of the crystal.

Phase Behavior of Mixed Polymer Brushes Grown from Ultrathin Coatings.

Experimental validation of the predicted melt phase behavior of A/B mixed brush on planar substrate is presented using poly(methyl methacrylate) (A)/ polystyrene (B) (PMMA/PS) with equal number of A/B chains as an example. Well-defined mixed A/B brushes are synthesized using a single component inimer coating to achieve high grafting density (0.9 chains/nm2), uniformity of grafting sites, and predictable chain length. The inimer coating is a copolymer of nitroxide-mediated polymerization (NMP) inimer, atom transfer radical polymerization (ATRP) inimer, styrene, and glycidyl methacrylate (GMA). Cross-linking of the film provides the required stability to probe the melt morphology. Our studies show that even with equal grafting density of the A and B the morphology can be modulated by varying the length of B chains while keeping that of A fixed. We show the transition of self-assembled structures from disorder to cylinder to ripple phase at sub-30 nm length scale on a planar surface by thermal annealing of mixed brushes. These results are supported by a phase diagram established through Monte Carlo simulation using a coarse-grained particle-based model.

Photoisomerization Dynamics in a Densely Packed Optically Transformable Azobenzene Monolayer.

Molecular monolayers that can be reconfigured through the use of external stimuli promise to enable the creation of interfaces with precisely selected dynamically adjustable physical and electronic properties with potential impact ranging from electronics to energy storage. Azobenzene-containing molecular monolayers have multiple stable molecular conformations but face a challenging nanoscale problem associated with understanding the basic mechanisms of reconfiguration. Time-resolved X-ray reflectivity studies show that the reconfiguration of a densely packed rhenium-azobenzene monolayer occurs in a period of many seconds. The degree of reconfiguration from trans to cis forms depends on the integrated UV fluence and has kinetics that are consistent with a mechanism in which the transformation occurs through the nucleation and growth of nanoscale two-dimensional regions of the cis isomer.

Mesoscopic Elastic Distortions in GaAs Quantum Dot Heterostructures.

Quantum devices formed in high-electron-mobility semiconductor heterostructures provide a route through which quantum mechanical effects can be exploited on length scales accessible to lithography and integrated electronics. The electrostatic definition of quantum dots in semiconductor heterostructure devices intrinsically involves the lithographic fabrication of intricate patterns of metallic electrodes. The formation of metal/semiconductor interfaces, growth processes associated with polycrystalline metallic layers, and differential thermal expansion produce elastic distortion in the active areas of quantum devices. Understanding and controlling these distortions present a significant challenge in quantum device development. We report synchrotron X-ray nanodiffraction measurements combined with dynamical X-ray diffraction modeling that reveal lattice tilts with a depth-averaged value up to 0.04° and strain on the order of 10-4 in the two-dimensional electron gas (2DEG) in a GaAs/AlGaAs heterostructure. Elastic distortions in GaAs/AlGaAs heterostructures modify the potential energy landscape in the 2DEG due to the generation of a deformation potential and an electric field through the piezoelectric effect. The stress induced by metal electrodes directly impacts the ability to control the positions of the potential minima where quantum dots form and the coupling between neighboring quantum dots.