Due to their exceptional plasmonic properties, noble metals such as gold and silver have been the materials of choice for the demonstration of various plasmonic and nanophotonic phenomena. However, noble metals' softness, lack of tailorability and low melting point along with challenges in thin film fabrication and device integration have prevented the realization of real-life plasmonic devices.In the recent years, titanium nitride (TiN) has emerged as a promising plasmonic material with good metallic and refractory (high temperature stable) properties. The refractory nature of TiN could enable practical plasmonic devices operating at elevated temperatures for energy conversion and harsh-environment industries such as gas and oil. Here we report on the temperature dependent dielectric functions of TiN thin films of varying thicknesses in the technologically relevant visible and near-infrared wavelength range from 330 nm to 2000 nm for temperatures up to 900 0C using in-situ high temperature ellipsometry. Our findings show that the complex dielectric function of TiN at elevated temperatures deviates from the optical parameters at room temperature, indicating degradation in plasmonic properties both in the real and imaginary parts of the dielectric constant. However, quite strikingly, the relative changes of the optical properties of TiN are significantly smaller compared to its noble metal counterparts. Using simulations, we demonstrate that incorporating the temperature-induced deviations into the numerical models leads to significant differences in the optical responses of high temperature nanophotonic systems. These studies hold the key for accurate modeling of high temperature TiN based optical elements and nanophotonic systems for energy conversion, harsh-environment sensors and heat-assisted applications.
The search for alternative plasmonic materials with improved optical properties over the traditional materials like silver and gold could ultimately lead to the long-awaited, real-life applications of plasmonic devices and metamaterials. In this work, we show that titanium nitride could perform as an alternative plasmonic material in the visible wavelength range. We evaluate the performances of various plasmonic and metamaterial structures with titanium nitride as a plasmonic component and show that transformation-optics devices and an important class of metamaterials with hyperbolic dispersio…
Optical properties of colloidal plasmonic titanium nitride nanoparticles are examined with an eye on their photothermal via transmission electron microscopy and optical transmittance measurements. Single crystal titanium nitride cubic nanoparticles with an average size of 50 nm exhibit plasmon resonance in the biological transparency window. With dimensions optimized for efficient cellular uptake, the nanoparticles demonstrate a high photothermal conversion efficiency. A self-passivating native oxide at the surface of the nanoparticles provides an additional degree of freedom for surface funct…
To integrate plasmonic devices into industry, it is essential to develop scalable and CMOS compatible plasmonic materials. In this work, we report high plasmonic quality titanium nitride (TiN) on c-plane sapphire by plasma enhanced atomic layer deposition (PE-ALD). TiN with low losses and high metallicity was achieved at temperatures below 500°C, by exploring the effects of chemisorption time, substrate temperature and plasma exposure time on material properties. Reduction in chemisorption time mitigates premature precursor decomposition at T_S > 375°C , and a trade-off between reduced impurit…
The development of plasmonic and metamaterial devices requires the research of high-performance materials, alternative to standard noble metals. Renewed as refractory stable compound for durable coatings, titanium nitride has been recently proposed as an efficient plasmonic material. Here, by using a first principles approach, we investigate the plasmon dispersion relations of TiN bulk and we predict the effect of pressure on its optoelectronic properties. Our results explain the main features of TiN in the visible range and prove a universal scaling law which relates its mechanical and plasmo…
We have performed first-principles evolutionary searches for all stable titanium nitrides and have found, in addition to the well-known rocksalt-type TiN, new ground states Ti$_3$N$_2$, Ti$_4$N$_3$, Ti$_6$N$_5$ at atmospheric pressure, and Ti$_2$N and TiN$_2$ at higher pressures. The latest nitrogen-rich structure presents encapsulated N$_2$ dumbbells with a N-N distance of 1.348 Å at 60 GPa and TiN$_2$ is predicted to be mechanically stable (quenchable). Our calculations of the mechanical properties (bulk modulus, shear modulus, Young's modulus, Poisson's ratio, and hardness) are in excellent…
The temperature dependence of optical constants of titanium nitride thin film is investigated using spectroscopic ellipsometry between 1.4 to 5 eV in the temperature range 300 K to 650 K in steps of 50 K. The real and imaginary parts of the dielectric functions "1(E) and "2(E) increase marginally with increase in temperature. A Drude Lorentz dielectric analysis based on free electron and oscillator model are carried out to describe the temperature behavior. The parameters of the Lorentz oscillator model also showed that the relaxation time decreased with temperature while the oscillator energi…
In this work we introduce the use of TiN/Ti2 N layers as a back contact for lifted-off membranes of anodic Ta3N5 nanotube layers. In photoelectrochemical H2 generation experiments under simulated AM 1.5G light, shift of the onset potential for anodic photocurrents to lower potentials is observed, as well as a higher magnitude of the photocurrents compared to conventional Ta3N5 nanotubes (~ 0.5 V RHE ). We ascribe this beneficial effect to the improved conductive properties of the TiNx -based back contact layer that enables a facilitated electron-transport for tantalum-nitride based materials t…
As alternatives to conventional metals, new plasmonic materials offer many advantages in the rapidly growing fields of plasmonics and metamaterials. These advantages include low intrinsic loss, semiconductor-based design, compatibility with standard nanofabrication processes, tunability, and others. Transparent conducting oxides such as Al:ZnO, Ga:ZnO and indium-tin-oxide (ITO) enable many high-performance metamaterial devices operating in the near-IR. Transition-metal nitrides such as TiN or ZrN can be substitutes for conventional metals in the visible frequencies. In this paper we provide th…
The use of hot electrons generated from the decay of surface plasmons is a new paradigm to increase the conversion yield in solar energy technologies. Titanium nitride (TiN) is an emerging plasmonic ceramic that offers compatibility with CMOS technology, corrosion resistance, as well as mechanical strength and durability thus outperforming noble metals (i.e., Au, Ag) in terms of cost, mechanical, chemical and thermal stability. Here, we show that plasmonic TiN nanoparticles produce 25% higher photocurrent enhancement than Au nanoparticles decorated on TiO2 nanowires for photoelectrochemical wa…
Experimental data are given on the structure and properties of nanocrystalline hardening coatings of titanium nitride doped with copper, produced by plasma-assisted vacuum arc deposition by evaporating powder cathodes. A model of nanostructurization of this type of coatings is proposed. According to the model, the nanocrystallization in these materials is due to the dopant atoms, which form an amorphous sheath around a crystallite, thus defining its size.
The structural, elastic and electronic properties of two-dimensional (2D) titanium carbide/nitride based pristine (Tin+1Cn/Tin+1Nn) and functionalized MXenes (Tin+1CnT2/Tin+1NnT2, T stands for the terminal groups: -F, -O and -OH, n = 1, 2, 3) are investigated by density functional theory calculations. Carbide-based MXenes possess larger lattice constants and monolayer thicknesses than nitride-based MXenes. The in-plane Young's moduli of Tin+1Nn are larger than those of Tin+1Cn, whereas in both systems they decrease with the increase of the monolayer thickness. Cohesive energy calculations indi…
Extensive density-functional calculations are performed to understand atomic chemisorption on the TiC(111) and TiN(111) surfaces, in particular the calculated pyramid-shaped trends in the adsorption energies for second- and third-period adatoms. Our previously proposed concerted-coupling model for chemisorption on TiC(111) is tested against new results for adsorption on TiN(111) and found to apply on this surface as well, thus reflecting both similarities and differences in electronic structure between the two compounds.
We have studied the thermalization of hot carriers in both pristine and defective titanium nitride (TiN) using a two-temperature model. All parameters of this model, including the electron-phonon coupling parameter, were obtained from first-principles density-functional theory calculations. The virtual crystal approximation was used to describe defective systems. We find that thermalization of hot carriers occurs on much faster time scales than in gold as a consequence of the significantly stronger electron-phonon coupling in TiN. Specifically, the largest thermalization times, on the order of…
Developing colloidal plasmonic nanomaterials with high carrier density that show optical resonances and photochemical activity extending from the visible to the mid-infrared (MIR) ranges remains a challenging pursuit. Here, we report the fabrication of titanium nitride (TiN) nanobars obtained using a two step procedure based on a wet chemical route synthesis of TiO2 nanowires and their subsequent high temperature annealing in ammonia flow. Electromagnetic simulations of the resulting TiN nanobars reveal a rich set of optical resonances featuring transverse, longitudinal and mixed transverse lo…
In this work, ZnO nanowire arrays decorated with titanium nitride (TiN) nanoparticles as surface enhanced Raman scattering (SERS) substrates is demonstrated. ZnO nanowires were grown by hydrothermal synthesis while ~100 nm TiN nanoparticles were obtained by grinding commercial powders for several hours. They were then decorated on the ZnO nanowire arrays using acetone as the medium. Scanning electron microscopy confirmed the presence of TiN nanoparticles on the ZnO nanowires. TiN nanoparticles exhibited localized surface plasmon resonances at 430, 520 and 600 nm. SERS experiments using Nile Bl…
In this work, sintered polycrystalline cubic boron nitride (cBN) compacts, with titanium carbonitride (TiC0.7N0.3) and titanium nitride (TiN), respectively, as binders, were prepared at temperature of 1450°C and pressure of 5.5 GPa during 3 minutes, and the influence of binders on the plastic deformation of cBN powder due to the sintering process was experimentally investigated by X-ray diffraction (XRD) analysis. It was shown that the sintered compact with titanium carbonitride as a binder displays more intense plastic deformation of cBN grains than that with titanium nitride binder. This res…
The growth rate during reactive high power pulsed magnetron sputtering (HIPIMS) of titanium nitride is measured with a temporal resolution of up to 25 us using a rotating shutter concept. According to that concept a 200 um slit is rotated in front of the substrate synchronous with the HIPIMS pulses. Thereby, the growth flux is laterally distributed over the substrate. By measuring the resulting deposition profile with profilometry and with x-ray photoelectron spectroscopy, the temporal variation of the titanium and nitrogen growth flux per pulse is deduced. The analysis reveals that film growt…
Extraction of non-equilibrium hot carriers generated by plasmon decay in metallic nanostructures is an increasingly exciting prospect for utilizing plasmonic losses, but the search for optimum plasmonic materials with long-lived carriers is ongoing. Transition metal nitrides are an exciting class of new plasmonic materials with superior thermal and mechanical properties compared to conventional noble metals, but their suitability for plasmonic hot carrier applications remains unknown. Here, we present fully first-principles calculations of the plasmonic response, hot carrier generation and sub…
Extensive density-functional calculations on atomic chemisorption of H, B, C, N, O, F, Al, Si, P, S, and Cl on the polar TiC(111) and TiN(111) yield similar adsorption trends for the two surfaces: (i) pyramid-like adsorption-energy trends along the adatom periods; (ii) strongest adsorption for O, C, N, S, and F; (iii) large adsorption variety; (iv) record-high adsorption energy for O (8.4-8.8 eV). However, a stronger adsorption on TiN is found for elements on the left of the periodic table and on TiC for elements on the right. The results support that a concerted-coupling model, proposed for c…
Titanium nitride (TiN) shows low resistivity at room temperature, high thermal stability and thus has the potential to serve as seed layer in magnetic tunnel junctions. High quality TiN thin films with regard to the crystallographic and electrical properties were grown and characterized by X-ray diffraction and 4-terminal transport measurements. Element specific X-ray absorption spectroscopy revealed pure TiN in the bulk. To investigate the influence of a TiN seed layer on a ferro(i)magnetic bottom electrode, an out-of-plane magnetized Mn2.45Ga as well as in- and out-of-plane magnetized Co2FeA…
We report on the direct measurement of the electron-phonon relaxation time, τeph, in disordered TiN films. Measured values of τeph are from 5.5 ns to 88 ns in the 4.2 to 1.7 K temperature range and consistent with a T-3 temperature dependence. The electronic density of states at the Fermi level N0 is estimated from measured material parameters. The presented results confirm that thin TiN films are promising candidate-materials for ultrasensitive superconducting detectors.
In the present work, a simple strategy is used to thermally oxidize TiN nanopowder (ca. 20 nm) to an anatase phase of a TiO2:Ti3+:N compound. In contrast to the rutile phase of such a compound this photocatalyst provides photocatalytic activity for hydrogen evolution under AM1.5 conditions - this without the use of any noble metal co-catalyst. Moreover the photocatalyst is active and stable over extended periods of time (tested for 4 months). Importantly, to achieve successful conversion to the active anatase polymorph, sufficiently small starting particles of TiN are needed. The key factor fo…
Transition metal nitrides have received significant interest for use within plasmonic and optoelectronic devices. However, deposition temperature remains a significant barrier to the integration of transition metal nitrides as plasmonic materials within CMOS fabrication processes. Binary, ternary and layered transition metal nitride thin films based on titanium and niobium nitride are deposited using High Power Impulse Magnetron Sputtering (HIPIMS). The increased plasma densities achieved in the HIPIMS process allow high quality plasmonic thin films to be deposited at CMOS compatible temperatu…
Although titanium nitride (TiN) is among the most extensively studied and thoroughly characterized thin-film ceramic materials, detailed knowledge of relevant dislocation core structures is lacking. By high-resolution scanning transmission electron microscopy (STEM) of epitaxial single crystal (001)-oriented TiN films, we identify different dislocation types and their core structures. These include, besides the expected primary full a/2{110}<1$\bar{1}$0> dislocation, Shockley partial dislocations a/6{111}<11$\bar{2}$> and sessile Lomer edge dislocations a/2{100}<011>. Density-functional theory…
Chemical composition is the primary factor that determines the electronic band structure and thus also influences the optical properties of plasmonic ceramics including nitrides and oxides. In this work, the optical and plasmonic properties of TiN, ZrN and their hypothetical intermediate alloys Ti1-xZrxN (x= 0, 0.25, 0.50, 0.75, and 1), are studied by using first-principles density functional theory. We demonstrate the effects of electronic band structure tuning (band engineering) on the dielectric properties by varying the concentration of metallic constituents. Our calculations reveal that b…
We present topographic and spectroscopic scanning tunneling microscopy measurements taken on a 21 nm thick TiN film at a temperature of 4.2 K -- above the superconducting transition temperature (T_c = 3.8 K) of the sample. The film was polycrystalline with crystallite diameters of d~19 nm, consistent with other films prepared under similar conditions. The spectroscopic maps show on average a shallow V-shape around V_b = 0 V consistent with a sample near the Mott insulation transition. In selected regions on several samples we additionally observed signs of Coulomb blockade. The corresponding p…
We present a calculational method to predict terminations of growing or as-deposited surfaces as a function of the deposition conditions. Such characterizations are valuable for understanding catalysis and growth phenomena. The method combines ab-initio density functional theory (DFT) calculations and experimental thermodynamical data with a rate-equations description of partial pressures in the reaction chamber. The use of rate equations enables a complete description of a complex gas environment in terms of a few, (experimentally accessible) parameters. The predictions are based on compariso…
Niobium Titanium Nitride as a High Tensile Stress Material for Nanomechanics
Walther-Meißner-Institut, Bayerische Akademie der Wissenschaften（瓦尔特·迈斯纳研究所，巴伐利亚科学院）；Physics Department, TUM School of Natural Sciences, Technical University of Munich（慕尼黑工业大学自然科学学院物理系）；Munich Center for Quantum Science and Technology (MCQST)（慕尼黑量子科学与技术中心）；Department of Microtechnology and Nanoscience (MC2), Chalmers University of Technology（查尔姆斯理工大学微技术与纳米科学系）；School of Computation, Information and Technology, Technical University of Munich（慕尼黑工业大学计算、信息与技术学院）；TUM Center for Quantum Engineering (ZQE)（慕尼黑工业大学量子工程中心）
Today's supercapacitor energy storages are typically discrete devices aimed for printed boards and power applications. The development of autonomous sensor networks and wearable electronics and the miniaturisation of mobile devices would benefit substantially from solutions in which the energy storage is integrated with the active device. Nanostructures based on porous silicon (PS) provide a route towards integration due to the very high inherent surface area to volume ratio and compatibility with microelectronics fabrication processes. Unfortunately, pristine PS has limited wettability and po…
MXenes are a family two-dimensional transition metal carbide and nitride materials, which often exhibit very good metallic conductivity and are thus of great interest for applications in, e.g., flexible electronics, electrocatalysis, and electromagnetic interference shielding. However, surprisingly little is known about the fermiology of MXenes, i.e, the shape and size of their Fermi-surfaces, and its effect on the material properties. One reason for this may be that MXene surfaces are almost always covered by a mixture of functional groups, and studying Fermi-surfaces of disordered systems is…
The structural and electrical properties of Ti-N films deposited by reactive sputtering depend on their growth parameters, in particular the Ar:N2 gas ratio. We show that the nitrogen percentage changes the crystallographic phase of the film progressively from pure α-Ti, through an α-Ti phase with interstitial nitrogen, to stoichiometric Ti2N, and through a substoichiometric TiNX to stoichiometric TiN. These changes also affect the superconducting transition temperature, Tc, allowing, the superconducting properties to be tailored for specific applications. After decreasing from a Tc of 0.4 K f…
Thin films of TiN were sputter-deposited onto Si and sapphire wafers with and without SiN buffer layers. The films were fabricated into RF coplanar waveguide resonators, and internal quality factor measurements were taken at millikelvin temperatures in both the many photon and single photon limits, i.e. high and low power regimes, respectively. At high power, internal quality factors ($Q_i$'s) higher than $10^7$ were measured for TiN with predominantly a (200)-TiN orientation. Films that showed significant (111)-TiN texture invariably had much lower $Q_i$'s, on the order of $10^5$. Our studies…
Gallium is a plasmonic material offering ultraviolet to near-infrared tunability, facile and scalable preparation, and good stability of nanoparticles. In our contribution, we experimentally demonstrate the link between the shape and size of individual gallium nanoparticles and their optical properties. To this end, we utilize scanning transmission electron microscopy combined with electron energy loss spectroscopy. Lens-shaped gallium nanoparticles with a diameter between 10 nm and 200 nm were grown directly on a silicon nitride membrane using an in-house developed effusion cell operated at u…
The field of plasmonics seeks to find materials with an intensive plasmon (large plasmon pole weight) with low Landau, phonon and other losses (small decay width). In this paper we propose a new class of materials that show exceptionally good plasmonic properties. These materials consist of van der Waals stacked 'plasmon active' layers (atomically thin metallic layers) and 'supporting' layers (atomically thin wide band gap insulating layers). One such material that can be experimentally realized - lithium intercalated hexagonal boron-nitride is studied in detail. We show that its 2D plasmon in…
Two-dimensional (2D) materials, such as graphene and hexagonal boron nitride, are new kind of materials that can serve as substrates for surface enhanced Raman spectroscopy (SERS). When combined with traditional metallic plasmonic structures, the hybrid 2D materials/metal SERS platform brings extra benefits, including higher SERS enhancement factors, oxidation protection of metal surface, and protection of molecules from photo-induced damage. This perspective gives an overview of recent progress in 2D materials coated plasmonic structure in SERS application. This paper focuses on the fabricati…
We have studied electrical transport as a function of carrier density, temperature and bias in multi-terminal devices consisting of hexagonal boron nitride (h-BN) encapsulated titanium trisulfide (TiS$_3$) sheets. Through the encapsulation with h-BN, we observe metallic behavior and high electron mobilities. Below $\sim$60 K an increase in the resistance, and non-linear transport with plateau-like features in the differential resistance are present, in line with the expected charge density wave (CDW) formation. Importantly, the critical temperature and the threshold field of the CDW phase can …
Titanium nitride (TiN) is a paradigm of refractory transition metal nitrides with great potential in vast applications. Generally, the plasmonic performance of TiN can be tuned by oxidation, which was thought to be only temperature-, oxygen partial pressure-, and time-dependent. Regarding the role of crystallographic orientation in the oxidation and resultant optical properties of TiN films, little is known thus far. Here we reveal that both the oxidation resistance behavior and the plasmonic performance of epitaxial TiN films follow the order of (001) < (110) < (111). The effects of crystallo…
Using the first-principles calculations, we report the existence of the single-layer (SL) di-titanium oxide Ti$_2$O (labeled as MOene) that constructs a novel family of MXene based on transition metal oxides. This MOene material strongly contrasts the conventional ones consisting of transition metal carbides and/or nitrides. SL Ti$_2$O has high thermal and dynamical stabilities due to the strong Ti$-$O ionic bonding interactions. Moreover, this material is an intrinsic electride and exhibits extremely low diffusion barriers of $\sim$12.0 and 6.3 meV for Li- and Na diffusion, respectively. When…
Results on the chemical composition, structure and growth kinetics of titanium nitride (TiN) films deposited on mild steel substrates by pyrolytic laser-induced chemical vapour deposition (LCVD) are presented. Golden coloured lines of TiN were deposited from a reactive gas mixture of TiCl4, N2 and H2 using a continuous wave TEM00 CO2 laser beam as heat source. The chemical composition and structure of the films were determined by electron probe microanalysis (EPMA) and glancing incidence X-ray diffraction (GIXRD). A non-contact laser profilometer was used to measure the thickness profiles of t…
Synaptic devices with linear high-speed switching can accelerate learning in artificial neural networks (ANNs) embodied in hardware. Conventional resistive memories however suffer from high write noise and asymmetric conductance tuning, preventing parallel programming of ANN arrays as needed to surpass conventional computing efficiency. Electrochemical random-access memories (ECRAMs), where resistive switching occurs by ion insertion into a redox-active channel address these challenges due to their linear switching and low noise. ECRAMs using two-dimensional (2D) materials and metal oxides suf…
We propose a composite layered structure for tunable, low-loss plasmon resonances, which con- sists of a noble-metal thin film coated in graphene and supported on a hexagonal boron nitride (hBN) substrate. We calculate electron energy loss spectra (EELS) for these structures, and nu- merically demonstrate that bulk plasmon losses in noble-metal films can be significantly reduced, and surface coupling enhanced, through the addition of a graphene coating and the wide-bandgap hBN substrate. Silver films with a trilayer graphene coating and hBN substrate demonstrated sur- face plasmon-dominant spe…
Layered and two-dimensional (2D) materials such as graphene, boron nitride, transition metal dichalcogenides(TMDCs), and black phosphorus (BP) have intriguing fundamental physical properties and bear promise of numerous important applications in electronics and optics. Of them, BP is a novel 2D material that has been theoretically predicted to acquire plasmonic behavior for frequencies below ~0.4 eV when highly doped. The electronic properties of BP are unique due to an anisotropic structure, which could strongly influence collective electronic excitations. Advantages of BP as a material for n…
Hydrogen as a fuel can be stored safely with high volumetric density in metals. It can, however, also be detrimental to metals causing embrittlement. Understanding fundamental behavior of hydrogen at atomic scale is key to improve the properties of metal-metal hydride systems. However, currently, there is no robust technique capable of visualizing hydrogen atoms. Here, we demonstrate that hydrogen atoms can be imaged unprecedentedly with integrated differential phase contrast, a recently developed technique performed in a scanning transmission electron microscope. Images of the titanium-titani…
