Results for “TiN” — Page 2

NASA NTRS2010

Estimating the Probability of Electrical Short Circuits from Tin Whiskers

To comply with lead-free legislation, many manufacturers have converted from tin-lead to pure tin finishes of electronic components. However, pure tin finishes have a greater propensity to grow tin whiskers than tin-lead finishes. Since tin whiskers present an electrical short circuit hazard in electronic components, simulations have been developed to quantify the risk of said short circuits occurring. Existing risk simulations make the assumption that when a free tin whisker has bridged two adjacent exposed electrical conductors, the result is an electrical short circuit. This conservative assumption is made because shorting is a random event that had an unknown probability associated with it. Note however that due to contact resistance electrical shorts may not occur at lower voltage levels. In our first article we developed an empirical probability model for tin whisker shorting. In this paper, we develop a more comprehensive empirical model using a refined experiment with a larger sample size, in which we studied the effect of varying voltage on the breakdown of the contact resistance which leads to a short circuit. From the resulting data we estimated the probability distribution of an electrical short, as a function of voltage. In addition, the unexpected polycrystalline structure seen in the focused ion beam (FIB) cross section in the first experiment was confirmed in this experiment using transmission electron microscopy (TEM). The FIB was also used to cross section two card guides to facilitate the measurement of the grain size of each card guide's tin plating to determine its finish .

Courey, Karim J.↗

NASA NTRS2009

Developing an Empirical Model for Estimating the Probability of Electrical Short Circuits from Tin Whiskers

To comply with lead-free legislation, many manufacturers have converted from tin-lead to pure tin finishes of electronic components. However, pure tin finishes have a greater propensity to grow tin whiskers than tin-lead finishes. Since tin whiskers present an electrical short circuit hazard in electronic components, simulations have been developed to quantify the risk of said short circuits occurring. Existing risk simulations make the assumption that when a free tin whisker has bridged two adjacent exposed electrical conductors, the result is an electrical short circuit. This conservative assumption is made because shorting is a random event that had an unknown probability associated with it. Note however that due to contact resistance electrical shorts may not occur at lower voltage levels. In our first article we developed an empirical probability model for tin whisker shorting. In this paper, we develop a more comprehensive empirical model using a refined experiment with a larger sample size, in which we studied the effect of varying voltage on the breakdown of the contact resistance which leads to a short circuit. From the resulting data we estimated the probability distribution of an electrical short, as a function of voltage. In addition, the unexpected polycrystalline structure seen in the focused ion beam (FIB) cross section in the first experiment was confirmed in this experiment using transmission electron microscopy (TEM). The FIB was also used to cross section two card guides to facilitate the measurement of the grain size of each card guide's tin plating to determine its finish.

Courey, Karim J.↗

NASA NTRS2009

Estimating the Probability of Electrical Short Circuits from Tin Whiskers

To comply with lead-free legislation, many manufacturers have converted from tin-lead to pure tin finishes of electronic components. However, pure tin finishes have a greater propensity to grow tin whiskers than tin-lead finishes. Since tin whiskers present an electrical short circuit hazard in electronic components, simulations have been developed to quantify the risk of said short circuits occurring. Existing risk simulations make the assumption that when a free tin whisker has bridged two adjacent exposed electrical conductors, the result is an electrical short circuit. This conservative assumption is made because shorting is a random event that had an unknown probability associated with it. Note however that due to contact resistance electrical shorts may not occur at lower voltage levels. In our first article we developed an empirical probability model for tin whisker shorting. In this paper, we develop a more comprehensive empirical model using a refined experiment with a larger sample size, in which we studied the effect of varying voltage on the breakdown of the contact resistance which leads to a short circuit. From the resulting data we estimated the probability distribution of an electrical short, as a function of voltage.

Courey, Karim J.↗

DOE OSTI2022

Solar reduction of carbon dioxide on copper-tin electrocatalysts with energy conversion efficiency near 20%

Abstract Copper catalysts modified with tin have been demonstrated to be selective for the electroreduction of carbon dioxide to carbon monoxide. However, such catalysts require the precise control of tin loading amount. Here, we develop a copper/tin-oxide catalyst with dominant tin oxide surface being formed via a spontaneous exchange reaction between sputtered tin and copper oxide. Even though the surface of this catalyst is tin-rich, it achieves an excellent performance towards carbon monoxide production in a flow cell. This contrasts with copper/tin-oxide prepared via atomic layer deposition since it yields selectivity towards carbon monoxide only on a copper-rich surface. Mechanism studies reveal that the tin sites on the tin-rich copper/tin-oxide surface achieve a suitable binding with adsorbed carbon monoxide under the presence of copper. Powered by a triple-junction solar cell, the copper/tin-oxide based electrolyzer sets a new benchmark solar-to-chemical energy conversion efficiency of 19.9 percent with a Faradaic efficiency of 98.9 percent towards carbon monoxide under simulated standard air mass 1.5 global illumination.

14 SOLAR ENERGY↗

DOE OSTI2022

Tin removal by an annular surface wave plasma antenna in an extreme ultraviolet lithography source

Tin contamination of the collector mirror surface remains one of the crucial issues of EUV (Extreme Ultraviolet) sources, directly impacting the availability of the tool. Hydrogen plasma-based tin removal processes employ hydrogen radicals and ions to interact with tin deposits to form gaseous tin hydride (SnH 4 ), which can be removed through pumping. An annular surface wave plasma (SWP) source developed at the University of Illinois—Urbana Champaign is integrated into the cone and perimeter of the collection mirror for in situ tin removal. The SWP is characterized by high ion and radical densities, low electron temperature, and local generation where etching is needed. This method has the potential to significantly reduce downtime and increase mirror lifetime. Radical probe measurements show hydrogen radical densities in the order of 10 19 m -3 , while Langmuir probe measurements show electron temperatures of up to 6 eV and plasma densities on the order of 10 17–18 m -3 . The generated ions are essential to the tin cleaning and have sufficiently low energy to cause no damage to the collector capping layer. Tin etch rates of up to 270 nm/min were observed in a variety of experimental conditions, including various powers, pressures, flowrates, and temperatures. In conclusion, the high etch rates demonstrated in this study exceed the expected contamination rate of the EUV source.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

DOE OSTI2020

Study of a linear surface wave plasma source for tin removal in an extreme ultraviolet source

Tin deposition mitigation employs hydrogen radicals and ions, formed in a hydrogen plasma, to interact with tin to form tin hydride (SnH 4 ) in the gaseous state, which is then pumped away. Surface wave plasma (SWP) technology developed at Illinois generates hydrogen radicals and ions, resulting in tin etch rates that are high enough to keep extreme ultraviolet (EUV) lithographic tools clean. An advantage of an SWP antenna is the ability to generate a high density of hydrogen radicals and hydrogen ions directly at the desired etching location. In situ etching of tin enables high availability EUV tools by maintaining high reflectivity of the multilayer mirror of the collector. Additionally, the SWP is characterized with low ion energies and low electron temperature, such that the multilayer mirror does not suffer any damage from sputtering or implantation of hydrogen ions during operation. Here, experiments elucidating the fundamental processes of tin removal are conducted by varying pressure, power, surface temperature, and gas flow rate in order to observe the etch rate behavior. Our results have shown that the presence of hydrogen ions increases etch rates because ion bombardment weakens Sn–Sn bonds, which, in turn, allows for a higher rate of chemical etching by the radicals. The ion bombardment reduces the number of radicals needed to etch a single tin atom to the range of 10 2 –10 3 . The linear SWP antenna yields plasma densities on the order of 10 17 to 10 18 m -3 and radical densities on the order of 10 18 to 10 19 m -3 , allowing for greater utilization of ion etch enhancement. Etch rates of up to 200 nm/min have been achieved. The surface temperature of the samples is an important factor in the etching process such that the decrease in the surface temperature increases the etch rates and decreases the hydrogen desorption rates. In addition, a kinetic etch model is developed to explain the behavior of etch rates as a function of surface temperature. Furthermore, results from experiments performed in an Illinois NXE:3100 chamber will be discussed.

42 ENGINEERING↗

DOE OSTI2024

Plasmon assisted synthesis of TiN-supported single-atom nickel catalysts

We report the deposition of single atom nickel catalyst on refractory plasmonic titanium nitride (TiN) nanomaterials supports using the wet synthesis method under visible light irradiation. TiN nanoparticles efficiently absorb visible light to generate photoexcited electrons and holes. Photoexcited electrons reduce nickel precursor to deposit Ni atoms on TiN nanoparticles’ surface. The generated hot holes are scavenged by the methanol. We studied the Ni deposition on TiN nanoparticles by varying light intensity, light exposure time, and metal precursor concentration. These studies confirmed the photodeposition method is driven by hot electrons and helped us to find optimum synthesis conditions for single atoms deposition. We characterized the nanocatalysts using high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), energy dispersive X-ray spectroscopy (EDX), and X-ray photoelectron spectroscopy (XPS). We used density functional theory (DFT) calculations to predict favorable deposition sites and aggregation energy of Ni atoms on TiN. Surface defect sites of TiN are most favorable for single nickel atoms depositions. Interestingly, the oxygen sites on native surface oxide layer of TiN also exhibit strong binding with the single Ni atoms. Plasmon enhanced synthesis method can facilitate photodeposition of single atom catalysts on a wide class of metallic supports with plasmonic properties.

36 MATERIALS SCIENCE↗

DOE OSTI2022

Low Exciton Binding Energies and Localized Exciton–Polaron States in 2D Tin Halide Perovskites

We report aside from band gap reduction, little is understood about the effect of the tin-for-lead substitution on the fundamental optical and optoelectronic properties of metal halide perovskites (MHPs), especially when transitioning from 3D to lower dimensional structures. Herein, we take advantage of the spectro-scopic isolation of excitons in 2D MHPs to study the intrinsic differences between lead and tin MHPs. The exciton’s spectral fine structure indicates a larger polaron binding energy in tin MHPs. Additionally, the electroabsorption responses of the 2D MHPs demonstrates that tin MHPs have exciton binding energies 1.5–2× lower than that of their lead counterparts. Despite the lower binding energy, the excitons in tin MHPs are more Frenkel-like with small radii, small polarizabilities, and large dipole moments. These results are interpreted as consequences of small polaron formation and disorder-induced dipole moments. This work highlights the wide range of intrinsic differences between lead and tin MHPs as well as the complexity of excited states in these systems.

36 MATERIALS SCIENCE↗

DOE OSTI2021

Effect of thickness on metal-to-semiconductor transition in 2-dimensional TiN thin films

Titanium nitride thin films have been grown on c-plane sapphire substrates using a pulsed laser deposition technique in the thickness range of 6–45 nm. X-ray diffraction (XRD) analysis has demonstrated TiN (111) as the preferred orientation of growth on the sapphire substrates. The XRD measurements have also indicated that orientational alignment between the TiN and the sapphire improved with an increase in the TiN film thickness. A change in the resistivity behavior of the TiN thin films from metallic to semiconducting has been observed as the TiN film thickness is reduced below 15 nm. Analyzing and fitting of TiN films’ conductivity data have shown that while the Arrhenius law governs their conductivity in the temperature range of 300–350 K, conductivity values of the films follow the variable range hopping mechanism below 300 K.

36 MATERIALS SCIENCE↗

DOE OSTI2024

Self-Assembled TiN-Metal Nanocomposites Integrated on Flexible Mica Substrates towards Flexible Devices

The integration of nanocomposite thin films with combined multifunctionalities on flexible substrates is desired for flexible device design and applications. For example, combined plasmonic and magnetic properties could lead to unique optical switchable magnetic devices and sensors. In this work, a multiphase TiN-Au-Ni nanocomposite system with core–shell-like Au-Ni nanopillars embedded in a TiN matrix has been demonstrated on flexible mica substrates. The three-phase nanocomposite film has been compared with its single metal nanocomposite counterparts, i.e., TiN-Au and TiN-Ni. Magnetic measurement results suggest that both TiN-Au-Ni/mica and TiN-Ni/mica present room-temperature ferromagnetic property. Tunable plasmonic property has been achieved by varying the metallic component of the nanocomposite films. The cyclic bending test was performed to verify the property reliability of the flexible nanocomposite thin films upon bending. This work opens a new path for integrating complex nitride-based nanocomposite designs on mica towards multifunctional flexible nanodevice applications.

42 ENGINEERING↗

DOE OSTI2020

Equation of State of TiN at High Pressures and Temperatures: A Possible Host for Nitrogen in Planetary Mantles

Nitrogen, the most abundant element in Earth's atmosphere, is also a primary component of solid nitride minerals found in meteorites and on Earth's surface. If they remain stable to high pressures and temperatures, these nitrides may also be important reservoirs of nitrogen in planetary interiors. We used synchrotron X-ray diffraction to measure the thermal equation of state and phase stability of titanium nitride (TiN) in a laser-heated diamond anvil cell at pressures up to ~70 GPa and temperatures up to ~2500 K. TiN maintains the cubic B1 (NaCl-type) crystal structure over the entire pressure and temperature range explored. It has K 0 = 274(4) GPa, K 0 ' = 3.9(2), and γ 0 = 1.39(4) for a fixed V 0 = 76.516(30) Å 3 (based on experimental measurements), q = 1, and θ 0 = 579 K. Additionally, we collected Raman spectra of TiN up to ~60 GPa, where we find that the transverse acoustic (TA), longitudinal acoustic (LA), and transverse optical (TO) phonon modes exhibit mode Grüneisen parameters of 1.66(17), 0.54(15), and 0.93(4), respectively. Based on our equation of state, TiN has a density of ~5.6–6.4 g/cm 3 at Earth's lower mantle conditions, significantly more dense than both the mantle of the Earth and the estimated densities of the mantles of other terrestrial planets, but less dense than planetary cores. Furthermore, we find that TiN remains stable against physical decomposition at the pressures and temperatures found within Earth's mantle, making it a plausible reservoir for deep planetary nitrogen if chemical conditions allow its formation.

58 GEOSCIENCES↗

NASA NTRS2002

Superlative TINs

TIN is short for 'triangulated irregular network,' which is a piecewise planar model of a surface. If properly constructed, a TIN can be more than 30 times as efficient as a regular triangulation. In our project (a ground combat simulation to support U.S. Army training exercises), the TIN is used to represent the Earth's surface and is used primarily to determine whether line of sight is blocked by terrain. High efficiency requires accurate identification of ridgelines with as few triangles as possible. The work currently in progress is the implementation of a TINning process that we hope will produce superlative TINs. This presentation describes that process.

Triangulated Irregular Networks TIN Delaunay trian↗

DOE OSTI2020

Broadband Ultrafast Dynamics of Refractory Metals: TiN and ZrN

Transition metal nitrides have recently gained attention in the fields of plasmonics, plasmon-enhanced photocatalysis, photothermal applications, and nonlinear optics because of their suitable optical properties, refractory nature, and large laser damage thresholds. Here we report comparative studies of the transient response of films of titanium nitride (TiN), zirconium nitride (ZrN), and gold (Au) under femtosecond excitation. Broadband transient optical characterization helps to adjudicate earlier, somewhat inconsistent reports regarding hot electron lifetimes based upon single wavelength measurements. These pump–probe experiments show sub-picosecond transient dynamics only within the epsilon-near-zero window of the refractory metals. The dynamics are dominated by photoinduced interband transitions resulting from ultrafast electron energy redistribution. The enhanced reflection modulation in the epsilon-near-zero window makes it possible to observe the ultrafast optical response of these films at low pump fluences. These results indicate that electron–phonon coupling in TiN and ZrN is 25–100 times greater than in Au. Strong electron–phonon coupling drives the sub-picosecond optical response and facilitates greater lattice heating compared to Au, making TiN and ZrN promising for photothermal applications. The spectral response and dynamics of TiN and ZrN are only weakly sensitive to pump fluence and pump excitation energy. However, the magnitude of the response is much greater at higher pump photon energies and higher fluences, reaching peak observed values of 15% in TiN and 50% in ZrN in the epsilon-near-zero window.

36 MATERIALS SCIENCE↗

DOE OSTI2025

Controlling Selective C–O and C–H Bond Scission of Methanol by Supporting Pt on TiN and Mo 2 N Model Surfaces and Powder Catalysts

Transition metal nitrides (TMNs) have been explored as effective supports for Pt due to their Pt-like electronic properties. However, there is a lack of fundamental understanding regarding the behavior of Pt on different TMNs (Pt/TMN). Herein two TMNs, Mo 2 N and TiN, were modified with Pt and compared using methanol decomposition as a probe reaction via both ultrahigh vacuum (UHV) studies on thin films and ambient-pressure batch reactor studies of powder catalysts. Temperature-programmed desorption (TPD) and high-resolution electron energy loss spectroscopy (HREELS) measurements were conducted under UHV conditions with Mo 2 N and TiN thin films. Mo 2 N was shown to favor C–H bond scission to form CO with a 56.2% selectivity, while TiN favored C–O bond scission to form CH 4 with a 74.5% selectivity. The addition of 0.9 monolayers (MLs) of Pt increased C–H bond scission selectivity to 89.7% and 49.2% for Mo 2 N and TiN respectively. Density functional theory (DFT) calculations on model surfaces revealed that the binding energy of O (BE *O ) was significantly reduced on Pt/TMNs, from −4.02 eV on Mo 2 N to −1.31 eV on Pt/Mo 2 N and −4.74 eV on TiN to −1.37 eV on Pt/TiN. As a result, C–O bond scission pathways were suppressed, leading to the preferential C–H bond scission that was observed experimentally. The C–O and C–H bond scission trends observed on thin films were then extended to powder catalysts, which demonstrated similar trends toward methanol decomposition. In conclusion, results from the current study establish that by combining UHV studies and DFT calculations over model surfaces, one can effectively predict the catalytic behavior of realistic TMN powder catalysts.

08 HYDROGEN↗

DOE OSTI2025

Cage Balancing Enhances Optoelectronic and Lasing Performance in Stable Quasi-2D Tin Iodide Perovskites

Two-dimensional (2D) tin halide perovskites are highly tunable and low-toxicity semiconductors, promising for next-generation optoelectronics. However, achieving air stability and excellent photophysical properties simultaneously necessitates deliberate structure tuning using organic spacer cations and A-site cations. Here, we report a series of new quasi-2D Ruddlesden–Popper tin halide perovskites using a fluorinated aromatic spacer cation, 4-fluorophenethylammonium (4FPEA), and systematically investigate the impacts of layer thickness, spacer cation, and A-site cation on the crystal structures and optical properties of (4FPEA) 2 (A) n−1 S n I 3n+1 . These 4FPEA-based 2D tin perovskites, further tuned by the A-cations, exhibit uniquely undistorted 180° out-of-plane Sn–I–Sn bond angles and low octahedral distortions compared to other quasi-2D perovskites and demonstrate prolonged air stability, excellent photophysics, and amplified spontaneous emission and lasing in exfoliated microflakes. A comprehensive survey of reported n = 2 lead and tin iodide perovskites reveals that all structures can be classified into three types (tilted, balanced, and buckled) based on the structural distortion parameters of their perovskite cages. Notably, (4FPEA) 2 (A)Sn 2 I 7 are among the handful of “balanced” n = 2 perovskites with minimal distortion and excellent optoelectronic performance. Furthermore, the structural insights and cage-balancing approach revealed herein motivate the deliberate design of quasi-2D perovskites through the synergy of the spacer and cage cations, further paving the way for high-performance optoelectronic applications of stable tin halide perovskites.

Cations↗

NASA NTRS1976

The critical currents in superconducting tin films

The nonlinear current-voltage curves exhibited by tin films in the flux flow state have made studies of the amount of heating present in the sample necessary. The samples in this work consisted of an evaporated tin film on one side of a 2 mm thick crystal quartz substrate and a carbon film of the same configuration as the tin film on the back of the substrate. The carbon film was used as a thermometer to measure the temperature rise of the tin film above the bath temperature. The heating results indicate negligible effects in the samples. Temperature ratios as small as 0.80 for the tin samples have been investigated and the current-voltage characteristics are still nonlinear, indicating that the source of the nonlinearity is not Joule heating in the samples.

Payne, J. E.↗

NASA NTRS1982

Effects on stress rupture life and tensile strength of tin additions to Inconel 718

Because Inconel 718 represents a major use of columbium and a large potential source of columbium for aerospace alloys could be that of columbium derived from tin slags, the effects of tin additions to Inconel 718 at levels which might be typical of or exceed those anticipated if tin slag derived columbium were used as a melting stock were investigated. Tin was added to 15 pound Inconel 718 heats at levels varying from none added to approximately 10,000 ppm (1 wt%). Limited 1200 F stress rupture testing was performed at stresses from 68,000 to 115,000 psi and a few tensile tests were performed at room temperature, 800 and 1200 F. Additions of tin in excess of 800 ppm were detrimental to ductility and stress rupture life.

Dreshfield, R. L.↗

NASA NTRS1982

Infrared emission spectrophotometric study of the changes produced by TiN coating of metal surfaces in an operating EHD contact

Infrared emission spectra and related measurements were obtained from an operating ball/plate EHD sliding contact under a variety of operating conditions. In order to be able to compare the effect of the ball surface, some of the steel balls were coated with a thin layer of titanium nitride (TiN) by vapor deposition. Polyphenyl ether (5P4E) was used as the lubricant and 1 percent of 1,1,2-trichloroethane TCE) as an additive with a high affinity for steel but a low affinity for TiN. TiN is chemically inert, but its thermal conductivity is lower than that of steel. Therefore, the overall temperatures with TiN-coated balls were higher. Nevertheless, no scuffng was observed with the coated balls under conditions giving rise to scuffing with the uncoated balls. Tractions were lower with the TiN-coated balls and with the steel balls when TCE was added to the 5P4E. These findings were found to be inversely related to the degree of polarization of the spectral emission bands. The intensity and the dichroism of these bands were related to shear rates and inlet conditions of the EHD contact.

Keller, L. E.↗