The cooperativity of van der Waals interactions in biomolecules and supramolecular assemblies has drawn significant scientific attention due to its offering of seamless opportunities to generate new materials. However, the potential of such cooperativity in synthetic polymers has not yet been explored. In this study, we demonstrate a strategy to achieve cooperativity via enhancement of weak interactions in a designed siloxane copolymer. Segmentation of siloxane copolymer with specific alkyl chain length (C18) induces cooperativity in van der Waals interaction among the alkyl chains, resulting in interdigitated as well as end-to-end packing. The cooperativity of van der Waals interactions is also evident by an excess melting enthalpy of ΔH = 1.86 kJ/mol in the designed block siloxane copolymer as compared to its control counterpart, i.e., a compositionally similar random siloxane copolymer. The dynamic relationship of cooperativity and physical properties is established by various analytical tools and further substantiated by disturbing the regularity of the block segments using a trace amount (1 per 99 octadecyl units) of a dissimilar alkyl chain as “dopant”.

Sputtered lead-free piezoelectric materials like potassium sodium niobate (K1-xNaxNbO3 or KNN) have received significant technological interest in recent years in light of several reports of piezoelectric constants comparable to lead zirconium titanate (PZT). Potential applications include self-powered sensors, actuators, and low acoustic impedance transducers. For large area printed applications, it is vital to develop low-temperature solution processed deposition methods. In this work, sol-gel synthesis of K-rich (70:30) KNN was carried out under an argon atmosphere, using acetate precursors, followed by precipitation of white KNN powder upon careful drying. Powder X-ray diffraction (XRD) scans of the product with a Cu Kα source after calcination revealed a dominant (110) peak, accompanied by smaller (100) and (010) peaks, in agreement with published standard KNN data. The composition of K-rich phase was confirmed using energy dispersive X-ray spectroscopy (EDX). To produce thin films, the sol was spin coated on a surface-treated Au-coated Si substrate, followed by slow annealing to obtain low surface roughness films (RMS roughness ﹤∼10 nm) of thickness ∼200 nm after solvent removal. Atomic force microscopy (AFM) scans revealed an unremarkable amorphous film. However, deposition of the sol on the Au-coated backside of Si wafer under similar processing conditions revealed limited polycrystalline film formation observed using optical profilometry. Thin film XRD measurements of the deposited film reveal orthorhombic phase growth of KNN, though the unannealed film was more amorphous than the calcined KNN film. Preliminary piezoresponse force microscopy (PFM) scans were used to estimate a piezoelectric constant (d33) ∼ 2.7 pC/N, consistent with the general expectation of lower piezoelectric constants for thin sol-gel films. The highest processing temperature used at any step during the deposition process was 90°C, consistent with the applications involving flexible polyimide substrates. This low-temperature thin-film growth suggests a potential route towards integration of large area piezoelectric generators for environmentally-friendly autonomous flexible sensor applications, with better control of phase and composition during the solution-phase deposition of KNN.

ABSTRACT:Cubic gallium nitride (GaN) is a wide bandgap semiconductor that exhibits a high crystallographic symmetry resulting in a lower inbuilt polarization which is useful for more efficient phosphor-free green light-emitting diodes. It has been grown using molecular beam epitaxy (MBE) and metal-organic chemical vapor deposition (MOCVD), which produce highly ordered thin films on compatible substrates. In this work, we report the chemical synthesis of GaN using chemical metathesis reaction in diethyl ether with lithium nitride and anhydrous gallium chloride as precursors, inside a nitrogen glove box at the room temperature. The resulting product was subsequently washed to remove lithium chloride and dried before vacuum annealing in a furnace at 850°C. Powder X-ray diffraction (XRD) scans of the as-prepared and annealed product reveal a mixed phase of GaN along with Ga2O3. Energy dispersive X-ray spectroscopy (EDAX) measurements show a nitrogen-poor product, which correlates well with the nearly black color of the powder. Diffuse reflectance spectroscopy (DRS) measurements were carried out with the obtained product on a barium sulfate substrate in a Perkin-Elmer Lambda 1050-UV-Vis-NIR spectrophotometer showing a strong absorbance below 400 nm. The energy band gap is bounded by values extracted from the Tauc plot and DRS measurements in the range of 3.2-3.5 eV, which is in good agreement with the known excitonic bandgap of cubic GaN (∼ 3.3 eV). Initial photoluminescence (PL) measurements using a Perkin-Elmer LS-55 spectrophotometer with an excitation wavelength of 310 nm reveal a weak emission centered around 440 nm corresponding to the known defect centers (D0X) in GaN. Further development of this process to form inks is expected to provide an alternate pathway to producing flexible phosphor-free lighting devices.

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