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Developing new methods that reveal the structure of electrode materials under polarization is key to constructing robust structure-property relationships. However, many existing methods lack the spatial resolution in structural changes and fidelity to electrochemical operating conditions that are needed to probe catalytically relevant structures. Here, we combine a nanopipette electrochemical cell with three-dimensional X-ray Bragg coherent diffractive imaging to study how strain in a single Pt grain evolves in response to applied potential. During polarization, marked changes in surface strain arise from the Coulombic attraction between the surface charge on the electrode and the electrolyte ions in the electrochemical double layers, while the strain in the bulk of the crystal remains unchanged. The concurrent surface redox reactions have a strong influence on the magnitude and nature of the strain changes under polarization. Our studies provide a powerful blueprint to understand how structural evolution influences electrochemical performance at the nanoscale.

All-solid-state lithium batteries promise significant improvements in energy density and safety over traditional liquid electrolyte batteries. The Al-doped Li7La3Zr2O12 (LLZO) solid-state electrolyte shows excellent potential given its high ionic conductivity and good thermal, chemical, and electrochemical stability. Nevertheless, further improvements on electrochemical and mechanical properties of LLZO call for an in-depth understanding of its local microstructure. Here, we employ Bragg coherent diffractive imaging to investigate the atomic displacements inside single grains of LLZO with various Al-doping concentrations, resulting in cubic, tetragonal, and cubic-tetragonal mixed structures. We observe coexisting domains of different crystallographic orientations in the tetragonal structure. We further show that Al doping leads to crystal defects such as dislocations and phase boundaries in the mixed- and cubic-phase grain. This study addresses the effect of Al doping on the nanoscale structure within individual grains of LLZO, which is informative for the future development of solid-state batteries.

Lithium uptake and release in lithium titanate (LTO) anode materials during a discharge and charge cycle is one of the fundamental processes of a lithium-ion battery (LIB), still not fully understood at the microscopic level. During the discharge cycle, LTO undergoes a phase transformation between Li4Ti5O12 and Li7Ti5O12 states within a cubic crystal lattice. To reveal the details of the microscopic mechanism, it is necessary to track the sequence of phase transformations at different discharge/charge states under operating conditions. Here, we use in situ Bragg coherent diffraction imaging (BCDI) and in situ X-ray diffraction (XRD) experiments to examine the lithium insertion-induced materials phase transformation within a single LTO particle and a bulk battery analogue, respectively. BCDI analysis from (111) Bragg peak shows the two-phase transformation manifesting as a distinct image phase modulation within a single LTO nanoparticle occurring in the middle of the discharge region then subsiding toward the end of the discharge cycle. We observe the biggest phase variation at the two-phase stage, indicating the formation of phase domains of 200 nm in size during the discharge process. We also observe a lattice contraction of >0.2% in a single LTO nanoparticle at the (400) Bragg peak measurement, larger than that in the corresponding bulk material. Our observation of this phase transformation at a single-particle level has implications for the understanding of the microscopic/mesoscale picture of the phase transformation in anode and cathode LIBs materials.

Fundamental understanding of structural changes during catalytic reactions is crucial to understanding the underlying mechanisms and optimizing efficiencies. Surface energy and related catalytic mechanisms are widely studied. However, the catalyst lattice deformation induced by catalytic processes is not well understood. Here, we study the strain in an individual platinum (Pt) nanoparticle (NP) using Bragg coherent diffraction imaging under in situ oxidation and reduction reactions. When Pt NPs are exposed to H

Emerging two-dimensional (2-D) materials such as transition-metal dichalcogenides show great promise as viable alternatives for semiconductor and optoelectronic devices that progress beyond silicon. Performance variability, reliability, and stochasticity in the measured transport properties represent some of the major challenges in such devices. Native strain arising from interfacial effects due to the presence of a substrate is believed to be a major contributing factor. A full three-dimensional (3-D) mapping of such native nanoscopic strain over micron length scales is highly desirable for gaining a fundamental understanding of interfacial effects but has largely remained elusive. Here, we employ coherent X-ray diffraction imaging to directly image and visualize in 3-D the native strain along the (002) direction in a typical multilayered (∼100–350 layers) 2-D dichalcogenide material (WSe2) on silicon substrate. We observe significant localized strains of ∼0.2% along the out-of-plane direction. Experimen...

Dissolution is critical to nanomaterial stability, especially for partially dealloyed nanoparticle catalysts. Unfortunately, highly active catalysts are often not stable in their reactive environments, preventing widespread application. Thus, focusing on the structure–stability relationship at the nanoscale is crucial and will likely play an important role in meeting grand challenges. Recent advances in imaging capability have come from electron, X-ray, and other techniques but tend to be limited to specific sample environments and/or two-dimensional images. Here, we report investigations into the defect-stability relationship of silver nanoparticles to voltage-induced electrochemical dissolution imaged in situ in three-dimensional detail by Bragg coherent diffractive imaging. We first determine the average dissolution kinetics by stationary probe rotating disk electrode in combination with inductively coupled plasma mass spectrometry, which allows in situ measurement of Ag+ ion formation. We then observe...

Imaging the dynamical response of materials following ultrafast excitation can reveal energy transduction mechanisms and their dissipation pathways, as well as material stability under conditions far from equilibrium. Such dynamical behavior is challenging to characterize, especially operando at nanoscopic spatiotemporal scales. In this letter, we use X-ray coherent diffractive imaging to show that ultrafast laser excitation of a ZnO nanocrystal induces a rich set of deformation dynamics including characteristic "hard" or inhomogeneous and "soft" or homogeneous modes at different time scales, corresponding respectively to the propagation of acoustic phonons and resonant oscillation of the crystal. By integrating the 3D nanocrystal structure obtained from the ultrafast X-ray measurements with a continuum thermo-electro-mechanical finite element model, we elucidate the deformation mechanisms following laser excitation, in particular, a torsional mode that generates a 50% greater electric potential gradient than that resulting from the flexural mode. Understanding of the time-dependence of these mechanisms on ultrafast scales has significant implications for development of new materials for nanoscale power generation.

Bottom-contact bottom-gate organic field-effect transistors (OFETs) are fabricated using a low band gap pDTTDPP-DT polymer as a channel material and single-layer graphene (SLG) or Au source/drain electrodes. The SLG-based ambipolar OFETs significantly outperform the Au-based ambipolar OFETs, and thermal annealing effectively improves the carrier mobilities of the pDTTDPP-DT films. The difference is attributed to the following facts: (i) the thermally annealed pDTTDPP-DT chains on the SLG assume more crystalline features with an edge-on orientation as compared to the polymer chains on the Au, (ii) the morphological features of the thermally annealed pDTTDPP-DT films on the SLG electrodes are closer to the features of those on the gate dielectric layer, and (iii) the SLG electrode provides a flatter, more hydrophobic surface that is favorable for the polymer crystallization than the Au. In addition, the preferred carrier transport in each electrode-based OFET is associated with the HOMO/LUMO alignment relative to the Fermi level of the employed electrode. All of these experimental results consistently explain why the carrier mobilities of the SLG-based OFET are more than 10 times higher than those of the Au-based OTFT. This work demonstrates the strong dependence of ambipolar carrier transport on the source/drain electrode and annealing temperature.

We characterized the electrical properties of a field-effect transistor (FET) and a nonvolatile memory device based on a solution-processable low bandgap small molecule, Si1TDPP-EE-C6. The small molecule consisted of electron-rich thiophene-dithienosilole-thiophene (Si1T) units and electron-deficient diketopyrrolopyrrole (DPP) units. The as-spun Si1TDPP-EE-C6 FET device exhibited ambipolar transport properties with a hole mobility of 7.3×10(-5) cm2/(Vs) and an electron mobility of 1.6×10(-5) cm2/(Vs). Thermal annealing at 110 °C led to a significant increase in carrier mobility, with hole and electron mobilities of 3.7×10(-3) and 5.1×10(-4) cm2/(Vs), respectively. This improvement is strongly correlated with the increased film crystallinity and reduced π-π intermolecular stacking distance upon thermal annealing, revealed by grazing incidence X-ray diffraction (GIXD) and atomic force microscopy (AFM) measurements. In addition, nonvolatile memory devices based on Si1TDPP-EE-C6 were successfully fabricated by incorporating Au nanoparticles (AuNPs) as charge trapping sites at the interface between the silicon oxide (SiO2) and cross-linked poly(4-vinylphenol) (cPVP) dielectrics. The device exhibited reliable nonvolatile memory characteristics, including a wide memory window of 98 V, a high on/off-current ratio of 1×10(3), and good electrical reliability. Overall, we demonstrate that donor-acceptor-type small molecules are a potentially important class of materials for ambipolar FETs and nonvolatile memory applications.