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Free, publicly-accessible full text available May 6, 2027
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Free, publicly-accessible full text available March 11, 2027
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Photocatalytic Controlled Halodefluorination of Perfluoroalkyl Compounds Using N -ArylphenothiazinesFree, publicly-accessible full text available July 15, 2027
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Free, publicly-accessible full text available April 8, 2027
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Appel halogenation reactions are widely used to convert alcohols to alkyl halides but are not suitable to prepare alkyl fluorides because fluoride is sequestered as a difluorophosphorane. In this work, we introduce bench-stable neopentoxyphosphonium salts to solve this enduring challenge. With these reagents, various alcohols undergo fluorination with potassium fluoride under hydrogen bonding phase-transfer catalysis, a manifold offering a pathway to enantioselective fluorination of alcohols. Mechanistically, a neopentoxyfluorophosphorane is formed, which undergoes reversible exchange with the alcohol substrate in preference to difluorophosphorane formation. The catalyst assists with potassium fluoride solubilization and with phosphorus–fluorine bond dissociation, leading to the alkoxyphosphonium fluoride ion pair undergoing stereoinvertive fluorination. Turnover results from stronger binding of the catalyst to fluoride than phosphine oxide, the by-product of the reaction, which is recyclable as starting material for the synthesis of the phosphonium reagents.more » « lessFree, publicly-accessible full text available July 30, 2027
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Abstract Perfluoroalkyl and polyfluoroalkyl substances (PFASs) are persistent, bioaccumulative and anthropogenic pollutants that have attracted the attention of the public and private sectors because of their adverse impact on human health1. Although various technologies have been deployed to degrade PFASs with a focus on non-polymeric functionalized compounds (perfluorooctanoic acid and perfluorooctanesulfonic acid)2–4, a general PFAS destruction method coupled with fluorine recovery for upcycling is highly desirable. Here we disclose a protocol that converts multiple classes of PFAS, including the fluoroplastics polytetrafluoroethylene and polyvinylidene fluoride, into high-value fluorochemicals. To achieve this, PFASs were reacted with potassium phosphate salts under solvent-free mechanochemical conditions, a mineralization process enabling fluorine recovery as KF and K2PO3F for fluorination chemistry. The phosphate salts can be recovered for reuse, implying no detrimental impact on the phosphorus cycle. Therefore, PFASs are not only destructible but can now contribute to a sustainable circular fluorine economy.more » « less
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Abstract GeSn photodetectors monolithically grown on Ge virtual substrates demonstrate mid‐wave infrared (MWIR) detection at room temperature. The lattice mismatch between GeSn and Ge causes dislocations and compressive strain, creating leakage pathways and unwanted indirect band transitions. Designed thin Ge0.91Sn0.09triple‐step buffer layers of ≈175 nm total thickness reduce dislocations and enable full relaxation, showing 100% lattice relaxation and smooth surface roughness of 0.83 nm with shorter auto‐correlation length in surface morphology compared to single‐step buffers. Ge1‐xSnxphotodetectors (x= 0.09, 0.12, and 0.15) on triple‐step buffers withn‐i‐pconfigurations achieve lattice strain relaxations of 99%, 88%, and 80%, respectively. Ge0.91Sn0.09and Ge0.88Sn0.12show gradual variation in auto‐correlation amplitude, while Ge0.85Sn0.15shows an increase due to lattice mismatch. Shockley–Read–Hall recombination current dominates at low reverse bias due to mismatch‐induced dislocations, while band‐to‐band tunneling current dominates at higher reverse bias due to narrowing bandgap under strong electric fields. The photodetectors show extended spectral response with increasing Sn composition ofi‐GeSn active layer sandwiched by barriers. Ge0.88Sn0.12and Ge0.85Sn0.15exhibit extended wavelength cut‐offs of 3.12 and 3.27 µm at room temperature, demonstrating significant potential for silicon‐based MWIR applications.more » « less
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Abstract In this work, TiO2thin films deposited by the atomic layer deposition (ALD) method were treated with a special N2O plasma surface treatment and used as the gate dielectric for AlGaN/GaN metal insulator semiconductor high electron mobility transistors (MISHEMTs). The N2O plasma surface treatment effectively reduces defects in the oxide during low-temperature ALD growth. In addition, it allows oxygen atoms to diffuse into the device cap layer to increase the barrier height and thus reduce the gate leakage current. These TiO2films exhibit a dielectric constant of 54.8 and a two-terminal current of 1.96 × 10−10A mm−1in 2μm distance. When applied as the gate dielectric, the AlGaN/GaN MISHEMT with a 2μm-gate-length shows a high on/off ratio of 2.59 × 108and a low subthreshold slope (SS) of 84 mV dec−1among all GaN MISHEMTs using TiO2as the gate dielectric. This work provides a feasible way to significantly improve the TiO2film electrical property for gate dielectrics, and it suggests that the developed TiO2dielectric is a promising high-κgate oxide and a potential passivation layer for GaN-based MISHEMTs, which can be further extended to other transistors.more » « less
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