While controlled crystallization of organic thin films holds great potential for enhancing the performance of electronic devices, quantitative understanding of the processes involved is limited. Here, we characterize the thin film crystal growth of the organic semiconductor rubrene during annealing using polarized optical microscopy with a heated stage for in situ measurements, followed by atomic force microscopy and X-ray diffraction. During annealing, the film undergoes transitions from predominant growth of a polycrystalline triclinic crystal structure to single crystal orthorhombic, followed by polycrystalline growth of the orthorhombic polymorph. Observation of crystal morphology with time allows determination of the crystal orientation, which is used in conjunction with crystal size measurements to determine the crystallization activation energies for the observed growth phases and crystal planes.
We characterized the prominent electron transport layer 2,2′,2″-(1,3,5-benzinetriyl)-tris(1-phenyl-1-H-benzimidazole) (TPBi) via single-crystal X-ray diffraction, grazing incidence X-ray diffraction (GIXRD), infrared reflection absorption spectroscopy (IRRAS), and quantum mechanical calculations. The crystals generated via vapor diffusion are of the orthorhombic space group Pbca , with a unit cell [a = 19.3935(2) b = 12.81750(10) c = 28.5610(3) Å] containing eight TPBi molecules, and screw axes and glide planes along all three crystallographic axes. Thin-film analysis becomes viable with unit cell and symmetry data, and GIXRD measurements, which demonstrate that when the amorphous TPBi thin films are annealed, the molecules preferentially orient with the a–b crystallographic face exposed at the surface and with the central benzene rings oriented 29° from the surface normal. Changes in vibrational modes at the surface, studied via infrared reflection absorption spectroscopy (IRRAS), concur with the X-ray based assignments. A minor conformer of TPBi with C 3 symmetry was also identified via computational methods, appearing 0.95 kcal/mol higher in energy at the MP2/6-31G*//B3LYP/6-31G* level of theory. The combined structural insight allows fine-tuning of a device structure for organic light-emitting diodes (OLEDs) and organic photovoltaic applications.
We report on the synthesis and characterization of catalytic palladium nanoparticles (Pd NPs) and their immobilization in microfluidic reactors fabricated from polydimethylsiloxane (PDMS). The Pd NPs were stabilized with D-biotin or 3-aminopropyltrimethoxysilane (APTMS) to promote immobilization inside the microfluidic reactors. The NPs were homogeneous with narrow size distributions between 2 and 4 nm, and were characterized by transmission electron microscopy (TEM), selected-area electron diffraction (SAED), and x-ray diffraction (XRD). Biotinylated Pd NPs were immobilized on APTMS-modified PDMS and glass surfaces through the formation of covalent amide bonds between activated biotin and surface amino groups. By contrast, APTMS-stabilized Pd NPs were immobilized directly onto PDMS and glass surfaces rich in hydroxyl groups. Fourier transform infrared spectroscopy (FT-IR) and x-ray photoelectron spectroscopy (XPS) results showed successful attachment of both types of Pd NPs on glass and PDMS surfaces. Both types of Pd NPs were then immobilized in situ in sealed PDMS microfluidic reactors after similar surface modification. The effectiveness of immobilization in the microfluidic reactors was evaluated by hydrogenation of 6-bromo-1-hexene at room temperature and one atmosphere of hydrogen pressure. An average first-run conversion of 85% and selectivity of 100% were achieved in approximately 18 min of reaction time. Control experiments showed that no hydrogenation occurred in the absence of the nanocatalysts. This system has the potential to provide a reliable tool for efficient and high throughput evaluation of catalytic NPs, along with assessment of intrinsic kinetics.
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