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XPS depth profile of the full device Cu/TiNO/ITO (Glass) as a function of sputtering time: a surface scan after cleaning the surface contamination for 30 s, b sub-surface after sputtering for 211 s, c sub-surface after sputtering for 301 s, and d sub-surface after sputtering for 361 s
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A TiNxOy (TiNO) material system has been synthesized in thin film form for the first time using a pulsed laser deposition process. X-ray diffraction and X-ray photoelectron spectroscopy measurements have been carried out to show partial oxidation of TiN to TiNO. The current (I)-voltage (V) characteristics recorded from TiNO films sandwiched between...
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... The downgrade in the plasmonic properties with an increase in the O/N ratio is explained on the basis of a decrease in free electron density, which is, in turn, caused by an increase in the bandgap of TiNO with increasing oxygen content. 31,108 Nevertheless, the TiNO films continue to possess dielectric constants in the film composition range studied in the present research. Aside from low losses, a large negative dielectric constant ε 1 is required for plasmonic devices, which has indeed been accomplished, as seen in Figure 7a for all films. ...
The present paper reports on the fabrication, detailed structural characterizations, and theoretical modeling of titanium nitride (TiN) and its isostructural oxide derivative, titanium oxynitride (TiNO) thin films that have excellent plasmonic properties and that also have the potential to overcome the limitation of noble metal and refractory metals. The TiNO films deposited at 700 °C in high vacuum conditions have the highest reflectance (R = ∼ 95%), largest negative dielectric constant (ε1 = −161), and maximal plasmonic figure of merit (FoM = −ε1/ε2) of 1.2, followed by the 600 °C samples deposited in a vacuum (R = ∼ 85%, ε1 = −145, FoM = 0.8) and 700 °C–5 mTorr sample (R = ∼ 82%, ε1 = −8, FoM = 0.3). To corroborate our experimental observations, we calculated the phonon dispersions and Raman active modes of TiNO by using the virtual crystal approximation. From the experimental and theoretical studies, a multilayer optical model has been proposed for the TiN/TiNO epitaxial thin films for obtaining individual complex dielectric functions from which many other optical parameters can be calculated. The advantages of oxide derivatives of TiN are the continuation of similar free electron density as in TiN and the acquisition of additional features such as oxygen-dependent semiconductivity with a tunable bandgap.
... Sci: Mater Eng. (2025) 20:2 (Zheng et al. 2022;Mishra et al. 2021;Mucha et al. 2020aMucha et al. , 2020bRoy et al. 2021Roy et al. , 2019Roy et al. , 2023Seki 2017). It has been shown that TiN possesses the optical and electronic properties required to be a plasmonic material. ...
... Therefore, if one oxidizes a TiN epitaxial film to obtain TiN x O y , the resulting film possesses the same crystalline structure and active surface sites. Titanium oxynitrides have recently attracted an increasing amount of attention, especially in titanium oxides and nitrides ultra-broadband solar energy absorbers, refractory plasmonics, and solar energy harvesting, to mention a few (Zheng et al. 2022;Mishra et al. 2021;Mucha et al. 2020a;Roy et al. 2021Roy et al. , 2019Roy et al. , 2023. The material properties of TiN x O y films are determined by the nitrogen-oxygen (N/O) ratio in the films. ...
... Furthermore, a reduction in the density of free electrons is brought about by the higher electronegativity of oxygen that hinders the mobility of otherwise free 3d electrons of Ti available for plasmonic oscillations (Cheng et al. 2017). By changing the stoichiometry, TiN can be changed from the metallic to the semiconducting TiN x O y state (Mucha et al. 2020a), thereby creating the potential to develop films with tunable electronic properties-a step that is critical in application to real-world optoelectronic devices (Photovoltaic and photoactive materials -properties, technology and applications. Springer,Netherlands. 2002;Iakobson et al. 2021). ...
This study reports a pulsed laser deposition-assisted synthesis of highly metallic titanium nitride (TiN) and a series of semiconducting titanium oxynitride (TiN x O 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 x O y by 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 x O y with 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 x O y thin 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 x O y samples 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 x O y have the potential to replace gold and silver in the visible and near-infrared spectral regions.
... Figure 9C shows the N 1s region for the TiN/C sample, which was deconvolved into two peaks located at 398.3 and 399.9 eV. The peaks corresponded to N-Ti and N-O/N-O-Ti binding environments, respectively [17,73,78,79]. Figure 8D presents Table 3. Atomic composition based on the XPS analysis of the synthesized TiOTPP, VOTPP, TiN/C, and VN/C and TiN and VN synthesized using a sol-gel method [16,17]. Figure 8A shows the Ti 2p XPS spectrum for the TiOTPP precursor with two peaks at 457.1 and 463.0 eV, which corresponds to the Ti 2p 1/2 and 2p 3/2 regions, respectively, indicating the presence of the Ti 4+ environment [68]. ...
... Figure 9C shows the N 1s region for the TiN/C sample, which was deconvolved into two peaks located at 398.3 and 399.9 eV. The peaks corresponded to N-Ti and N-O/N-O-Ti binding environments, respectively [17,73,78,79]. Figure 8D presents the O 1s XPS spectrum for the TiOTPP, which was deconvolved into three peaks: 529.2, 531.4, and 532.7 eV assigned to oxygen adsorbed on the surface, Ti-O, and water adsorbed, respectively [70,71,[80][81][82]. Figure 9D shows the O 1s spectrum for the TiOTPP. ...
... and 532.7 eV assigned to oxygen adsorbed on the surface, Ti-O, and water adsorbed, respectively [70,71,[80][81][82]. Figure 9D shows the O 1s spectrum for the TiOTPP. The region was deconvolved into three peaks, 530.1, 531.8, and 533.3 eV, which were determined to be adsorbed oxygen on the surface, Ti-N-O/Ti-O and adsorbed water, respectively [69,70,79,80,82]. Figure 10A displays the vanadium spectra for the VOTPP precursor, which presents two peaks representing V 2p 3/2 and V 2p 1/2 . The V 2p 3/2 V 2p 1/2 peaks were located at 515.3 and 522.7 eV, respectively [16,83]. Figure 11A shows the V 2p XPS spectrum for the VN/C composite. ...
Titanium nitride and vanadium nitride–carbon-based composite systems, TiN/C and VN/C, were prepared using a new synthesis method based on the thermal decomposition of titanyl tetraphenyl porphyrin (TiOTPP) and vanadyl tetraphenyl porphyrin (VOTPP), respectively. The structure of the TiN/C and VN/C composite materials, as well as their precursors, were characterized using Fourier Transformed Infrared Spectroscopy, X-Ray diffraction (XRD), X-Ray energy dispersive (EDS) and X-Ray photoelectron spectroscopy (XPS). Morphologies of the TiN/C and VN/C composites were examined by means of scanning electron (SEM) and transmission electron (TEM) microscopy. The synthesis of the non-metalated tetraphenyl porphyrin, the titanium, and vanadium tetraphenyl porphyrin complexes were confirmed using FTIR. The thermal decomposition of the titanium and vanadium tetraphenyl porphyrin complexes produced the respective metal nitride encapsulated in a carbon matrix; this was confirmed by XRD, SEM, TEM, and XPS. From the XRD patterns, it was determined that the TiN and VN were presented in cubic form with expected space group FM-3M and 1:1 (metal:N) stoichiometry. The XPS results confirmed the presence of both TiN and VN in the carbon matrix without metal carbides. The SEM and TEM results showed that both TiN and VN nanoparticles formed small clusters throughout the carbon matrix; the EDS results revealed a uniform composition. The synthesis method presented in this work is novel and serves as an effective means to produce TiN and VN NPs with good structure and morphology embedded in a carbon matrix.
... However, they lack plasmonic properties in the visible range and exhibit poor resonances in the near-infrared region [25]. Besides materials, structure, periodicity, and oxidation states, the shape and architecture of materials also have a profound effect on the properties of these materials [28][29][30][31][32][33][34][35][36][37][38][39][40]. For example, in nanowire form, the permittivity (ε) is different along the axes parallel or perpendicular to the propagation of light, where ∥ < 0, ⊥ > 0. This relationship is reversed for thin-film materials, where ∥ > 0, ⊥ < 0. When signs of the two components of permittivity are opposite, the isofrequency contours are unbounded and result in regular hyperbola for 2D thin film configuration as opposed to inverted hyperbolas in the case of 1D nanowires [10]. ...
This work reports a pulsed laser-assisted synthesis, detailed structural characterization, and study of plasmonic properties of three sets of TiN/TiNO thin films with high electron density. The first two sets of TiN films were grown at 600C and 700C under a high vacuum condition. The third set of TiN film was grown in the presence of 5 mTorr of molecular oxygen at 700C. The results have shown that TiN films deposited in a high vacuum are metallic, have large optical reflectance, and have high optical and electrical conductivity. The TiN films, grown in 5 mTorr O2, were partially oxidized and semiconducting with room temperature resistivity nearly three times larger than those of the TiN films grown under high vacuum conditions. The optical conductivity of these films was analyzed using a Kramers-Kronig transformation of reflectance and a Lorentz-Drude model; the optical conductivity determined by these two different methods agreed very well. To corroborate our experimental spectral observations, we have calculated the phonon dispersions and Raman active modes of TiNO using the virtual crystal approximation. A comparative analysis of the phonon dispersions between rutile TiO2 and rocksalt TiNO has shown that the incorporation of nitrogen atoms does not significantly alter the phonon dispersions of rutile TiO2. However, it results in the emergence of new phonon modes at approximately 7.128 THz at the Gamma point, which corresponds to the experimentally observed Multi-Photon Phase-MPP. From the collateral study of experimental results and theoretical corroboration, a suitable multi-layer optical model was proposed for the TiN/TINO epitaxial thin films to extract the individual complex dielectric function from which many other optical parameters can be calculated.
... 29 Bulk plasmon peaks around a binding energy of approximately 410 eV are apparent on TiFelt readings, which is commonly reported. 44,45 Moreover, the oxynitride character from residual oxide on the surface can also be noted at binding energies slightly above Fe−N, around 399.5 eV corresponding to N−O bonds. 44 The identification of the oxynitride character suggests the presence of mixed bonding environments, which might play a role in the catalytic process. ...
Chlorine evolution reaction (CER) is a critical reaction in many processes, such as chlor-alkali electrolysis and electrochemical wastewater treatment. The scarce and high-cost iridium and ruthenium content of benchmark dimensionally stable anodes (DSA) coupled with subpar activities at commercially relevant current densities (≥150 mA cm–2) opens the door for additional material groups to be investigated. Herein, a highly porous, conductive, and chemically resilient trigonal ε-Fe3N-based electroactive catalytic substrate is used toward CER in industrial acidic brine (4.0 M NaCl, pH = 2) environments. Consecutive hydrothermal-nitridation steps were fine-tuned for homogeneous dispersion of Cu3N moieties atop FeN, which exhibited a similar overpotential to DSA at a commercially relevant current density. An approximately 562 mV overpotential was needed to sustain a current density of 200 mA cm–2 for 75 h of chronoamperometric conditions. Moreover, online GC measurements with a chlorine trap were employed to indirectly obtain CER’s Faradaic efficiency (FE) by measuring the FE of the competing oxygen evolution reaction. Textural, chemical, and electrochemical characterization techniques were employed to confirm the identity of the developed anodes and depict the electrocatalytic performance. The findings reported herein could offer potential avenues for similar catalytic systems in both conventional CER and emerging electrosynthesis approaches utilizing saline waters.
... C is the capacitance of the interfacial layer. The circuit shows that R 1 and R 3 are connected in series with R 2 and C. It should be noted that the starting material, TiN, is well known to electrically be very conducting with room temperature resistivity of the order of ∼50 µΩ cm [69]. The resistivity of TiN thin films increases with the incorporation of oxygen in the TiN lattice. ...
Electrocatalytically active titanium oxynitride (TiNO) thin films were fabricated on commercially available titanium metal plates using a pulsed laser deposition (PLD) method for energy storage applications. The elemental composition and nature of bonding were analyzed using x-ray photoelectron spectroscopy (XPS) to reveal the reacting species and active sites responsible for the enhanced electrochemical performance of the TiNO electrodes. Symmetric supercapacitor devices were fabricated using two TiNO working electrodes separated by an ion-transporting layer to analyze their real-time performance. The galvanostatic charge-discharge studies on the symmetric cell have indicated that TiNO films deposited on the polycrystalline titanium plates at lower temperatures are superior to TiNO films deposited at higher temperatures in terms of storage characteristics. For example, TiNO films deposited at 300°C exhibited the highest specific capacity of 69 mF/cm2 at 0.125 mA/cm2 with an energy density of 7.5 Wh/cm2. The performance of this supercapacitor (300°C TiNO) device is also found to be ∼ 22 % better compared to that of a 500°C TiNO supercapacitor with a capacitance retention ability of 90% after 1000 cycles. The difference in the electrochemical storage and capacitance properties is attributed to the reduced leaching away of oxygen from the TiNO films by the Ti plate at lower deposition temperatures, leading to higher oxygen content in the TiNO films and, consequently, a high redox activity at the electrode/electrolyte interface.
... However, oxidation was not too extensive, as it was not apparent in the XRD. The Ti 2p 1/2 portion of the spectrum had low intensity and was deconvolved into two peaks at 461.3 eV and 463.9 eV, corresponding to the Ti-N and Ti-O binding environments, respectively [46]. In addition, the peak representing the Ti-N-O binding environment was not observed. ...
... The XPS spectrum of the TiN(TD) sample was deconvolved into two peaks located at 398.2 eV and 400.5 eV. The two peaks observed in the N1s spectrum corresponded to the N-Ti and N-C binding environments [44,46]. Figure 5D shows the O 1s XPS spectrum for TiN(SG), which was deconvolved into two individual peaks at 529.9 and 531.7 eV, determined to be the O 2 adsorbed and the O-N-Ti oxygen environments, respectively [46,58]. ...
... The two peaks observed in the N1s spectrum corresponded to the N-Ti and N-C binding environments [44,46]. Figure 5D shows the O 1s XPS spectrum for TiN(SG), which was deconvolved into two individual peaks at 529.9 and 531.7 eV, determined to be the O 2 adsorbed and the O-N-Ti oxygen environments, respectively [46,58]. These results are consistent with the binding environments observed in the Ti 2p for TiN(SG). ...
This work focuses on the synthesis of titanium nitride–carbon (TiN–carbon) composites by the thermal decomposition of a titanyl phthalocyanine (TiN(TD)) precursor into TiN. The synthesis of TiN was also performed using the sol-gel method (TiN(SG)) of an alkoxide/urea. The structure and morphology of the TiN–carbon and its precursors were characterized by XRD, FTIR, SEM, TEM, EDS, and XPS. The FTIR results confirmed the presence of the titanium phthalocyanine (TiOPC) complex, while the XRD data corroborated the decomposition of TiOPC into TiN. The resultant TiN exhibited a cubic structure with the FM3-M lattice, aligning with the crystal system of the synthesized TiN via the alkoxide route. The XPS results indicated that the particles synthesized from the thermal decomposition of TiOPC resulted in the formation of TiN–carbon composites. The TiN particles were present as clusters of small spherical particles within the carbon matrix, displaying a porous sponge-like morphology. The proposed thermal decomposition method resulted in the formation of metal nitride composites with high carbon content, which were used as anodes for Li-ion half cells. The TiN–carbon composite anode showed a good specific capacity after 100 cycles at a current density of 100 mAg⁻¹.
... 19,20 However, the applications of TiO x N y in RRAM technology are seldom observed. 21 Hence, further investigation on the TiO x N y -based RRAMs is required. Ga 2 O 3 contains a large number of oxygen vacancies, which can be used as the oxygen vacancies reservoir. ...
In this study, the resistive memory devices with Ag/TiOxNy/Pt structure and Ag/TiOxNy/Ga2O3/Pt structure are fabricated. The results showed that they exhibit typical resistive behaviors as well as excellent cycling and retention characteristics (>10⁴ s). Especially, the double-layer device with Ga2O3 layer exhibits superior resistive behavior, which has a larger storage window (ON/OFF ratio >10⁵), a smaller set voltage (0.17 V) and a reset voltage (−0.057 V), and lower power consumption (21.7, 0.17 μW) compared with the single-layer device. Furthermore, the Ag/TiOxNy/Ga2O3/Pt device demonstrates ultraviolet light (UV-365 nm)-dependent resistance state (RS), which is advantageous for multilevel memory cells. As the intensity of UV light increases, eight high resistance state (HRS) levels are produced. Finally, the conductive mechanism for both device structures is discussed, and it is found that the conductive filaments mechanism dominates in the low resistance state. However, for the HRS, the single-layer TiOxNy device is dominated by the space charge-limited conduction mechanism, and the double-layer TiOxNy/Ga2O3 device is dominated by the Schottky emission mechanism.
... Ti-based alloys are significant in various applications, including biomedical ones, due to their excellent strength-toweight ratio, superior corrosion resistance, notable thermal and electrical conductivity, and biocompatibility, among other properties [1][2][3] . Furthermore, these properties are highly dependent on the composition of the alloys, particularly nitrogen and/or oxygen gases, the main constituents of the atmosphere-air [4][5][6][7] . ...
The incorporation of oxygen and/or nitrogen into the titanium lattice has garnered significant attention due to the broad spectrum of intermediate properties that can be achieved between TiN and TiO2. This article delves into the investigation of surface modification of titanium through plasma-assisted thermochemical treatments employing H2-N2-O2 mixtures. The flow rate of the reducing gas (H2) remained constant at 24 sccm, while the flow rates of N2 and O2 were adjusted to yield a total flow rate of 60 sccm. Analysis using GIXRD, Raman spectroscopy, and XPS demonstrated that TiN exhibits stability exclusively in an oxygen-free atmosphere, while TiO2, in contrast, necessitates an oxygen flux equal to or exceeding 18 sccm for stability. Furthermore, it was found that the presence of nitrogen in the plasma atmosphere resulted in a greater expansion of the α-titanium lattice, although the solubility of interstitials decreased. These findings highlight the potential for a controlled approach to producing solid solutions or titanium oxynitrides.
... Transition-metal oxynitrides, such as Ti(O,N), are known for their optical and electronic properties, mechanical behavior, and chemical stability [1][2][3][4][5]. A large number of studies have been reported on the formation and properties of titanium oxynitride, Ti(O,N), where the properties of these materials strongly depend on their compositions, notably the O/N ratio. ...
... Ti(O,N) thin films have been fabricated by various techniques including DC magnetron sputtering, RF magnetron sputtering, pulsed laser deposition, electron beam evaporation, ion-assisted deposition, and chemical vapor deposition [3,[10][11][12][13][14]. Magnetron sputtering is a common technique, thanks to its versatility and reliability to control the microstructure and composition of the Ti(O,N) films which allows to tune mechanical, electrical and optical properties of the films [8,11,15]. ...
... N) closer to r-Ti 2 O 3 at high nitrogen content while closer to a-TiO 2 for high oxygen content film ( Table 2). Similar investigation on TiO x N y thin films have shown that the films deposited at 500°C or above were composed of a mixture of NaCl type TiN 1-x O x and anatase TiO 2 while being amorphous when grown at lower temperature [3,31]. As shown in Fig. 2, at high oxygen content, e.g., TiO 1.53 N 0.22 and TiO 1.83 N 0.08 films were comprised of a mixture of r-Ti 2 O 3 , in which the nitrogen could be inserted in anion lattice sites (r-Ti 2 (O 1y N y ) 3 ), and an a-TiO 2 phases. ...
Phase formation, morphology, and optical properties of Ti(O,N) thin films with varied oxygen-to- nitrogen ration content were investigated. The films were deposited by magnetron sputtering at 500 °C on Si(100) and c-plane sapphire substrate. A competition between a NaCl B1 structure TiN1−xOx, a rhombohedral structure Ti2(O1−yNy)3, and an anatase structure Ti(O1−zNz)2 phase was observed. While the N-rich films were composed of a NaCl B1 TiN1−xOx phase, an increase of oxygen in the films yields the growth of rhombohedral Ti2(O1-yNy)3 phase and the oxygen-rich films are comprised of a mixture of the rhombohedral Ti2(O1−yNy)3 phase and anatase Ti(O1−zNz)2 phase. The optical properties of the films were correlated to the phase composition and the observation of abrupt changes in terms of refractive index and absorption coefficient. The oxide film became relatively transparent in the visible range while the addition of nitrogen into films increases the absorption. The oxygen rich-samples have bandgap values below 3.75 eV, which is higher than the value for pure TiO2, and lower than the optical bandgap of pure TiN. The optical properties characterizations revealed the possibility of adjusting the band gap and the absorption coefficient depending on the N-content, because of the phases constituting the films combined with anionic substitution.
