High Crystalline Dithienosilole-Cored Small Molecule Semiconductor for Ambipolar Transistor and Nonvolatile Memory

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/(V s) and an electron mobility of 1.6 × 10^–5 cm²/(V s). 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) (<i>c</i>PVP) dielectrics. The device exhibited reliable nonvolatile memory characteristics, including a wide memory window of 98 V, a high on/off-current ratio of 1 × 10³, 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

Ultrafast Three-Dimensional X‑ray Imaging of Deformation Modes in ZnO Nanocrystals

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 <i>operando</i> 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

Three-Dimensional Integrated X‑ray Diffraction Imaging of a Native Strain in Multi-Layered WSe₂

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. Experimentally informed continuum models built from X-ray reconstructions trace the origin of these strains to localized nonuniform contact with the substrate (accentuated by nanometer scale asperities, i.e., surface roughness or contaminants); the mechanically exfoliated stresses and strains are localized to the contact region with the maximum strain near surface asperities being more or less independent of the number of layers. Machine-learned multimillion atomistic models show that the strain effects gain in prominence as we approach a few- to single-monolayer limit. First-principles calculations show a significant band gap shift of up to 125 meV per percent of strain. Finally, we measure the performance of multiple WSe₂ transistors fabricated on the same flake; a significant variability in threshold voltage and the “off” current setting is observed among the various devices, which is attributed in part to substrate-induced localized strain. Our integrated approach has broad implications for the direct imaging and quantification of interfacial effects in devices based on layered materials or heterostructures

Ultrafast Three-Dimensional X‑ray Imaging of Deformation Modes in ZnO Nanocrystals

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 <i>operando</i> 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

Ultrafast Three-Dimensional Integrated Imaging of Strain in Core/Shell Semiconductor/Metal Nanostructures

Visualizing the dynamical response of material heterointerfaces is increasingly important for the design of hybrid materials and structures with tailored properties for use in functional devices. In situ characterization of nanoscale heterointerfaces such as metal–semiconductor interfaces, which exhibit a complex interplay between lattice strain, electric potential, and heat transport at subnanosecond time scales, is particularly challenging. In this work, we use a laser pump/X-ray probe form of Bragg coherent diffraction imaging (BCDI) to visualize in three-dimension the deformation of the core of a model core/shell semiconductor–metal (ZnO/Ni) nanorod following laser heating of the shell. We observe a rich interplay of radial, axial, and shear deformation modes acting at different time scales that are induced by the strain from the Ni shell. We construct experimentally informed models by directly importing the reconstructed crystal from the ultrafast experiment into a thermo-electromechanical continuum model. The model elucidates the origin of the deformation modes observed experimentally. Our integrated imaging approach represents an invaluable tool to probe strain dynamics across mixed interfaces under operando conditions

Ultrafast Three-Dimensional Integrated Imaging of Strain in Core/Shell Semiconductor/Metal Nanostructures

Visualizing the dynamical response of material heterointerfaces is increasingly important for the design of hybrid materials and structures with tailored properties for use in functional devices. In situ characterization of nanoscale heterointerfaces such as metal–semiconductor interfaces, which exhibit a complex interplay between lattice strain, electric potential, and heat transport at subnanosecond time scales, is particularly challenging. In this work, we use a laser pump/X-ray probe form of Bragg coherent diffraction imaging (BCDI) to visualize in three-dimension the deformation of the core of a model core/shell semiconductor–metal (ZnO/Ni) nanorod following laser heating of the shell. We observe a rich interplay of radial, axial, and shear deformation modes acting at different time scales that are induced by the strain from the Ni shell. We construct experimentally informed models by directly importing the reconstructed crystal from the ultrafast experiment into a thermo-electromechanical continuum model. The model elucidates the origin of the deformation modes observed experimentally. Our integrated imaging approach represents an invaluable tool to probe strain dynamics across mixed interfaces under operando conditions

Nanoscopic Management of Molecular Packing and Orientation of Small Molecules by a Combination of Linear and Branched Alkyl Side Chains

We synthesized a series of acceptor–donor–acceptor-type small molecules (SIDPP-EE, SIDPP-EO, SIDPP-OE, and SIDPP-OO) consisting of a dithienosilole (SI) electron-donating moiety and two diketopyrrolopyrrole (DPP) electron-withdrawing moieties each bearing linear <i>n</i>-octyl (O) and/or branched 2-ethylhexyl (E) alkyl side chains. X-ray diffraction patterns revealed that SIDPP-EE and SIDPP-EO films were highly crystalline with pronounced edge-on orientation, whereas SIDPP-OE and SIDPP-OO films were less crystalline with a radial distribution of molecular orientations. Near-edge X-ray absorption fine structure spectroscopy disclosed an edge-on orientation with a molecular backbone tilt angle of ∼22° for both SIDPP-EE and SIDPP-EO. Our analysis of the molecular packing and orientation indicated that the shorter 2-ethylhexyl groups on the SI core promote tight π–π stacking of the molecular backbone, whereas <i>n</i>-octyl groups on the SI core hinder close π–π stacking to some degree. Conversely, the longer linear <i>n</i>-octyl groups on the DPP arms facilitate close intermolecular packing <i>via</i> octyl–octyl interdigitation. Quantum mechanics/molecular mechanics molecular dynamics simulations determined the optimal three-dimensional positions of the flexible alkyl side chains of the SI and DPP units, which elucidates the structural cause of the molecular packing and orientation explicitly. The alkyl-chain-dependent molecular stacking significantly affected the electrical properties of the molecular films. The edge-on oriented molecules showed high hole mobilities in organic field-effect transistors, while the radially oriented molecules exhibited high photovoltaic properties in organic photovoltaic cells. These results demonstrate that appropriate positioning of alkyl side chains can modulate crystallinity and molecular orientation in SIDPP films, which ultimately have a profound impact on carrier transport and photovoltaic performance