Abstract:The morphology of poly(sulfur nitride) (SNx) in bulk crystals and in thin films is investigated by grazing incidence wide‐angle X‐ray scattering (GI WAXS) and atomic force microscopy (AFM). SNx crystals are grown in S2N2 crystals by topochemical solid‐state polymerization and thin SNx films are prepared by sublimation/repolymerization of SNx or by mechanical deformation of crystals onto silicon substrates. Details of the crystallographic orientation of two different thin films are observed by GI WAXS. PeakForc… Show more
“…The PF-TUNA image in Fig. 8b maps the electrical conductivity in the picoampere range [26]. Obviously, the SN x fibers have a higher electrical conductivity at room temperature compared to YBCO.…”
Abstract15N‐labeled tetrasulfur tetranitride (S415N4) was synthesized by reacting S2Cl2 with 15NH3. The reaction was finalized with 14NH3. The successful labeling was confirmed by solution 15N nuclear magnetic resonance (NMR) spectroscopy. S415N4 was used for the synthesis of poly(sulfur nitride) S15Nx via the intermediate species of S2N2. It was a topochemical polymerization in the solid state. The isotope ratio in the labeled polymer was obtained by laser deposition ionization time‐of‐flight mass spectroscopy. Solid‐state 15N NMR spectroscopy of S15Nx indicates that at least three different chemical environments for 15N atoms are present in the crystals. Finally, SNx was polymerized in the presence of two other superconductors, MgB2 and yttrium barium copper oxide (YBCO), which demonstrates the capability of SNx for grain boundary engineering.
“…The PF-TUNA image in Fig. 8b maps the electrical conductivity in the picoampere range [26]. Obviously, the SN x fibers have a higher electrical conductivity at room temperature compared to YBCO.…”
Abstract15N‐labeled tetrasulfur tetranitride (S415N4) was synthesized by reacting S2Cl2 with 15NH3. The reaction was finalized with 14NH3. The successful labeling was confirmed by solution 15N nuclear magnetic resonance (NMR) spectroscopy. S415N4 was used for the synthesis of poly(sulfur nitride) S15Nx via the intermediate species of S2N2. It was a topochemical polymerization in the solid state. The isotope ratio in the labeled polymer was obtained by laser deposition ionization time‐of‐flight mass spectroscopy. Solid‐state 15N NMR spectroscopy of S15Nx indicates that at least three different chemical environments for 15N atoms are present in the crystals. Finally, SNx was polymerized in the presence of two other superconductors, MgB2 and yttrium barium copper oxide (YBCO), which demonstrates the capability of SNx for grain boundary engineering.
“…Eventually, a chemistry-physics collaboration between MacDiarmid, A. J. Heeger and A. F. Garito showed that pure polymeric (SN) x could be prepared by slowly growing explosive crystals of S 2 N 2 from the vapour phase at 0°C over a period of 48 hours, followed by room temperature solid-state polymerization over about three days (4). The resulting golden diamagnetic crystals, as illustrated by subsequent work carried out by J. Kressler (see figure 6; Amado et al 2021), were an ordered array of (SN) x fibres that can also explode when mechanically shocked (6). These fibres exhibited room temperature conductivity of 2500 S cm −1 in a direction parallel to the fibres, which was comparable to that of metallic mercury.…”
“…The young M ac Diarmid graduated from washing glassware and general cleaning duties to providing classroom demonstrations for Mr A. D. Monro, who was one of only two academic staff at Victoria University. He then commenced a four-year part-time BSc degree, which was followed by an MSc, during which he developed an interest in the chemistry of tetrasulfur tetranitride, S 4 N 4 , which produces beautiful orange crystals (1, 24); this experience would be the basis of his early collaboration with Alan J. Heeger in subsequent collaborative work at the University of Pennsylvania.…”
Alan G. MacDiarmid was an inorganic chemist by training who pioneered the field of synthetic metals. He grew up in a family that lived frugally, and he had to work in the Chemistry Department of the Victoria University of Wellington as a laboratory assistant before he could undertake part-time degree studies. He was awarded a Fulbright Scholarship to the University of Wisconsin, where he completed his first PhD with Norris Hall. The desire to receive a higher degree in the UK led to a Shell Scholarship to complete a second doctorate with Harry Emeléus FRS. After a sojourn at the University of St Andrews, Alan MacDiarmid was appointed to an academic position at the University of Pennsylvania, where he remained essentially for his whole career. His early research was based on the properties of silicon hydrides, but he also became interested in poly(sulfur nitride). This led to a search in collaboration with Alan J. Heeger for intrinsically conducting non-metallic materials. A chance meeting with Hideki Shirakawa at the University of Tokyo led to MacDiarmid being shown thin metallic-like films of poly(acetylene) made in Shirakawa's laboratory. Shirakawa travelled to Philadelphia to collaborate with MacDiarmid and Heeger on the halogen ‘doping’ of poly(acetylene), which led to the discovery that the doped material was an excellent conductor. Thus, the field of synthetic metals was born. This paradigm-shifting work in which a polymer was shown to be a conductor led to the award of the 2000 Nobel Prize in Chemistry to these three individuals. MacDiarmid went on to study in great detail the properties of polyaniline; the fact that it could be processed from solution and further modified by oxidative and protonic doping led to all sorts of potentially interesting opportunities in optoelectronics. From all this research, the modern field of organic electronic materials emerged as an important disruptive technology whose advancement depended on an entirely new branch of interdisciplinary science.
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