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1. Optical properties of unoxidized and oxidized titanium nitride thin films

   https://doi.org/10.1186/s40712-024-00203-6  

   Odusanya, Abiodun A; Schall, J David; Pfeifer, Mark A; Wright, John; Martin, Catalin; Craciun, Valentin; Kumar, Dhananjay (December 2025, Journal of materials science Materials in engineering)

   Abstract This study reports a pulsed laser deposition-assisted synthesis of highly metallic titanium nitride (TiN) and a series of semiconducting titanium oxynitride (TiN_xO_y) compounds in thin film form with tunable plasmonic properties by carefully altering the nitrogen (N)-oxygen (O) ratio. The N/O ratio was controlled from 0.3 (highest oxygen doping of TiN) to ~ 1.0 (no oxygen doping of TiN) by growing the TiN films under nitrogen pressures of 50, 35, and 10 mTorr and high vacuum conditions of 2 × 10⁻⁶ Torr with no external gas introduced. The presence of nitrogen in the deposition chamber during the film growth affects the gas phase oxidation of TiN to TiN_xO_yby increasing the mean free path-dependent N and O inter-collisions per second by two to three orders of magnitudes. The evidence of increased oxidation of TiN to TiN_xO_ywith an increase in nitrogen deposition pressure was obtained using X-ray photoelectron spectroscopy analysis. While the TiN samples deposited in high vacuum conditions had the highest reflectance, TiN_xO_ythin films were also found to possess high reflectance at low frequency with a well-defined edge around 20,000 cm⁻¹. Furthermore, the vacuum-deposited TiN samples showed a large negative dielectric constant of -330 and the largest frequency of zero-crossing at 25,000 cm⁻¹; the TiN_xO_ysamples deposited in the presence of nitrogen ambient also showed promising plasmonic applications at the near-mid infrared range. A comparison of the dielectric constant and loss function data of this research with the literature values for noble metals seems to indicate that TiN and TiN_xO_yhave the potential to replace gold and silver in the visible and near-infrared spectral regions. 

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2. TiN‐Au/HfO ₂ ‐Au Multilayer Thin Films with Tunable Hyperbolic Optical Response

   https://doi.org/10.1002/smtd.202400087  

   Zhang, Yizhi; Shen, Jianan; Tsai, Benson Kunhung; Sheng, Xuanyu; Hu, Zedong; Zhang, Xinghang; Wang, Haiyan (March 2024, Small Methods)

   Abstract Hyperbolic metamaterials (HMM) possess significant anisotropic physical properties and tunability and thus find many applications in integrated photonic devices. HMMs consisting of metal and dielectric phases in either multilayer or vertically aligned nanocomposites (VAN) form are demonstrated with different hyperbolic properties. Herein, self‐assembled HfO₂‐Au/TiN‐Au multilayer thin films, combining both the multilayer and VAN designs, are demonstrated. Specifically, Au nanopillars embedded in HfO₂and TiN layers forming the alternative layers of HfO₂‐Au VAN and TiN‐Au VAN. The HfO₂and TiN layer thickness is carefully controlled by varying laser pulses during pulsed laser deposition (PLD). Interestingly, tunable anisotropic physical properties can be achieved by adjusting the bi‐layer thickness and the number of the bi‐layers. Type II optical hyperbolic dispersion can be obtained from high layer thickness structure (e.g., 20 nm), while it can be transformed into Type I optical hyperbolic dispersion by reducing the thickness to a proper value (e.g., 4 nm). This new nanoscale hybrid metamaterial structure with the three‐phase VAN design shows great potential for tailorable optical components in future integrated devices. 

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3. Enhanced non-volatile resistive switching performance through ion-assisted magnetron sputtering of TiN bottom electrodes

   https://doi.org/10.1038/s43246-025-00798-z  

   Bakhit, Babak; Hellenbrand, Markus; Tsai, Benson Kunhung; Choudhury, Abhijeet; Polcik, Peter; Kolozsvari, Szilard; Wang, Haiyan; Flewitt, Andrew J; MacManus-Driscoll, Judith L (December 2025, Communications Materials)

   Abstract Emerging non-volatile memristor-based devices with resistive switching (RS) materials are being widely researched as promising contenders for the next generation of data storage and neuromorphic technologies. Titanium nitride (TiN_x) is a common industry-friendly electrode system for RS; however, the precise TiN_xproperties required for optimum RS performance is still lacking. Herein, using ion-assisted DC magnetron sputtering, we demonstrate the key importance not only of engineering the TiN_xbottom electrodes to be dense, smooth, and conductive, but also understoichiometric in N. With these properties, RS in HfO₂-based memristive devices is shown to be optimised for TiN_0.96. These devices have switching voltages ≤ ±1 V with promising device-to-device uniformity, endurance, memory window of ~40, and multiple non-volatile intermediate conductance levels. This study highlights the importance of precise tuning of TiN_xbottom electrodes to achieve robust performance of oxide resistive switching materials. 

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4. Crystal structure of (1,4,7,10,13,16-hexaoxacyclooctadecane-κ ⁶ O )potassium-μ-oxalato-triphenylstannate(IV), the first reported 18-crown-6-stabilized potassium salt of triphenyloxalatostannate

   https://doi.org/10.1107/S2056989024007758  

   Song, Xueqing; Li, William; Torres, Yolanda; Greaves, Tazena (September 2024, Acta Crystallographica Section E Crystallographic Communications)

   The title complex, (1,4,7,10,13,16-hexaoxacyclooctadecane-1κ⁶O)(μ-oxalato-1κ²O¹,O²:2κ²O^1′,O^2′)triphenyl-2κ³C-potassium(I)tin(IV), [KSn(C₆H₅)₃(C₂O₄)(C₁₂H₂₄O₆)] or K[18-Crown-6][(C₆H₅)₃SnO₄C₂], was synthesized. The complex consists of a potassium cation coordinated to the six oxygen atoms of a crown ether molecule and the two oxygen atoms of the oxalatotriphenylstannate anion. It crystallizes in the monoclinic crystal system within the space groupP2₁. The tin atom is coordinated by one chelating oxalate ligand and three phenyl groups, forming acis-trigonal–bipyramidal geometry around the tin atom. The cations and anions form ion pairs, linked through carbonyl coordination to the potassium atoms. The crystal structure features C—H...O hydrogen bonds between the oxygen atoms of the oxalate group and the hydrogen atoms of the phenyl groups, resulting in an infinite chain structure extending alonga-axis direction. The primary inter-chain interactions are van der Waals forces. 

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5. A PEGylated Tin Porphyrin Complex for Electrocatalytic Proton Reduction: Mechanistic Insights into Main‐Group‐Element Catalysis

   https://doi.org/10.1002/anie.202206325  

   Chaturvedi, Ashwin; McCarver, Gavin A.; Sinha, Soumalya; Hix, Elijah G.; Vogiatzis, Konstantinos D.; Jiang, Jianbing (July 2022, Angewandte Chemie International Edition)

   Abstract Electrocatalytic proton reduction to form dihydrogen (H₂) is an effective way to store energy in the form of chemical bonds. In this study, we validate the applicability of a main‐group‐element‐based tin porphyrin complex as an effective molecular electrocatalyst for proton reduction. A PEGylated Sn porphyrin complex (SnPEGP) displayed high activity (−4.6 mA cm⁻²at −1.7 V vs. Fc/Fc⁺) and high selectivity (H₂Faradaic efficiency of 94 % at −1.7 V vs. Fc/Fc⁺) in acetonitrile (MeCN) with trifluoroacetic acid (TFA) as the proton source. The maximum turnover frequency (TOF_max) for H₂production was obtained as 1099 s⁻¹. Spectroelectrochemical analysis, in conjunction with quantum chemical calculations, suggest that proton reduction occurs via an electron‐chemical‐electron‐chemical (ECEC) pathway. This study reveals that the tin porphyrin catalyst serves as a novel platform for investigating molecular electrocatalytic reactions and provides new mechanistic insights into proton reduction. 

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