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At least 127 records · Page 7

Aqueous phase deposition of dense tin oxide films with nano-structured surfaces

Dense tin oxide films were successfully fabricated in an aqueous solution. The pH of the solutions was controlled to pH 1.3 by addition of HCl. Precise control of solution condition and crystal growth allowed us to obtain dense tin oxide films. Concave–convex surface of fluorine-doped tin oxide (FTO) substrates was entirely-covered with the continuous films. The films were about 65 nm in thickness and had nano-structured surfaces. Morphology of the films was strikingly different from our previous reported nano-sheet assembled structures. The films were not removed from the substrates by strong water flow or air blow to show strong adhesion strength. The aqueous solution process can be applied to surface coating of various materials such as nano/micro-structured surfaces, particles, fibers, polymers, metals or biomaterials. - Graphical abstract: Dense tin oxide films of 65 nm were successfully fabricated in an aqueous solution. They had nano-structured surfaces. Concave-convex substrates were entirely-covered with the continuous films. - Highlights: • Dense tin oxide films of 65 nm were successfully fabricated in an aqueous solution. • They had nano-structured surfaces. • Concave–convex substrates were entirely-covered with the continuous films.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mitigation of tin whisker growth by inserting Ni nanocones

Highlights: • Tin whisker growth is mitigated effectively by inserting Ni nanocones. • Ni nanocones impede Sn dynamic recrystallization by blocking dislocation motions. • The inhibition method and mechanism are important to the study of tin whisker. - Abstract: An innovative controllable way has been proposed to mitigate tin whisker growth by inserting Ni nanocones prepared by electrodeposition. The results reveal that, after inserting Ni nanocones, tin whisker formation is mitigated effectively for 1.6 μm Sn coating but there is no inhibition effect for 4.5 μm Sn coating. The coatings are characterized by X-ray diffraction, scanning electron microscopy, energy dispersive spectrometer and electron backscatter diffraction (EBSD). The EBSD results show that Sn grain size without Ni nanocones increases significantly after indentation test compared with Sn grains with Ni nanocones. The inhibition effect of Ni nanocones on whisker growth can be ascribed to its specific structure which prevents dynamic recrystallization and produces horizontal grain boundaries of Sn grains. The structural inhibition method and mechanism proposed are of great importance to the research of tin whisker.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

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↗

Carrier interactions and porosity initiated reversal of temperature dependence of thermal conduction in nanoscale tin films

Recently, tin has been identified as an attractive electrode material for energy storage/conversion technologies. Tin thin films have also been utilized as an important constituent of thermal interface materials in thermal management applications. In this regards, in the present paper, we investigate thermal conductivity of two nanoscale tin films, (i) with thickness 500 ± 50 nm and 0.45% porosity and (ii) with thickness 100 ± 20 nm and 12.21% porosity. Thermal transport in these films is characterized over the temperature range from 40 K–310 K, using a three-omega method for multilayer configurations. The experimental results are compared with analytical predictions obtained by considering both phonon and electron contributions to heat conduction as described by existing frequency-dependent phenomenological models and BvK dispersion for phonons. The thermal conductivity of the thicker tin film (500 nm) is measured to be 46.2 W/m-K at 300 K and is observed to increase with reduced temperatures; the mechanisms for thermal transport are understood to be governed by strong phonon-electron interactions in addition to the normal phonon-phonon interactions within the temperature range 160 K–300 K. In the case of the tin thin film with 100 nm thickness, porosity and electron-boundary scattering supersede carrier interactions, and a reversal in the thermal conductivity trend with reduced temperatures is observed; the thermal conductivity falls to 1.83 W/m-K at 40 K from its room temperature value of 36.1 W/m-K. In order to interpret the experimental results, we utilize the existing analytical models that account for contributions of electron-boundary scattering using the Mayadas-Shatzkes and Fuchs-Sondheimer models for the thin and thick films, respectively. Moreover, the effects of porosity on carrier transport are included using a previous treatment based on phonon radiative transport involving frequency-dependent mean free paths and the morphology of the nanoporous channels. The systematic modeling approach presented in here can, in general, also be utilized to understand thermal transport in semi-metals and semiconductor nano-porous thin films and/or phononic nanocrystals.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Thermally evaporated mechanically hard tin oxide thin films for opto-electronic apllications

Tungsten doped tin oxide (WTO) and Molybdenum doped tin oxide (MoTO) thin film were deposited on corn glass by thermal evaporation method. The films were annealed at 350°C for one hour. Structural analysis using Xray diffraction data shows both the films are polycrystalline in nature with monoclinic structure of tin oxide, Sn{sub 3}O{sub 4}, corresponding to JCPDS card number 01-078-6064. SEM photograph showed that both the films have spherical grains with size in the range of 20–30 nm. Compositional analysis was carried out using EDS which reveals the presence of Sn, O and the dopant Mo/W only thereby indicating the absence of any secondary phase in the films. The films are found to contain nearly 6 wt% of Mo, 8 wt% of W as dopants respectively. The transmission pattern for both the films in the spectral range 200 – 2000 nm shows that W doping gives a transparency of nearly 80% from 380 nm onwards while Mo doping has less transparency of 39% at 380nm. Film hardness measurement using Triboscope shows a film hardness of about 9–10 GPa for both the films. It indicates that W or M doping in tin oxide provides the films the added advantage of withstanding the mechanical wear and tear due to environmental fluctuations By optimizing the optical and electrical properties, W/Mo doped tin oxide films may be explored as window layers in opto-electronic applications such as solar cells.

36 MATERIALS SCIENCE↗

Broad spectral response photodetector based on individual tin-doped CdS nanowire

High purity and tin-doped 1D CdS micro/nano-structures were synthesized by a convenient thermal evaporation method. SEM, EDS, XRD and TEM were used to examine the morphology, composition, phase structure and crystallinity of as-prepared samples. Raman spectrum was used to confirm tin doped into CdS effectively. The effect of impurity on the photoresponse properties of photodetectors made from these as-prepared pure and tin-doped CdS micro/nano-structures under excitation of light with different wavelength was investigated. Various photoconductive parameters such as responsivity, external quantum efficiency, response time and stability were analyzed to evaluate the advantage of doped nanowires and the feasibility for photodetector application. Comparison with pure CdS nanobelt, the tin-doped CdS nanowires response to broader spectral range while keep the excellect photoconductive parameters. Both trapped state induced by tin impurity and optical whispering gallery mode microcavity effect in the doped CdS nanowires contribute to the broader spectral response. The micro-photoluminescence was used to confirm the whispering gallery mode effect and deep trapped state in the doped CdS nanowires.

36 MATERIALS SCIENCE↗

Spin current transport in ceramic: TiN thin film

The spin current transport property in a ceramic material TiN has been investigated at room temperature. By attaching TiN thin films on Ni{sub 20}Fe{sub 80} with different thicknesses of TiN, the spin pumping experiment has been conducted, and the spin diffusion length in TiN was measured to be around 43 nm. Spin-torque ferromagnetic resonance has also been taken to investigate the spin Hall angle of TiN, which was estimated to be around 0.0052. This study on ceramic material provides a potential selection in emerging materials for spintronics application.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

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↗

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↗

Effect of TiN Addition on 3Y-TZP Ceramics with Emphasis on Making EDM-Able Bodies

In this study, to produce electrically conductive ceramics, rapid hot press (RHP) sintering of 3 mol.% yttria-stabilized tetragonal zirconia polycrystal (3Y-TZP) and 3Y-TZP/TiN composites with TiN amounts of 25, 35, and 45 vol.% was performed at 1300, 1350, and 1400 °C. Interestingly, the toughness and hardness were improved in the presence of TiN up to 35 vol.% and maximum fracture toughness and hardness of 5.40 ± 0.05 MPa m{sup 1/2} and 14.50 ± 0.06 GPa, respectively, were obtained. However, the bending strength was decreased which could be attributed to the rather weak interfaces of nitride and oxide phases. Regarding the zirconia matrix, the effect of grain size on fracture toughness of the samples has been studied using x-ray diffraction and field emission scanning electron microscope (FESEM) analysis. It was also found that electrical resistivity decreased to the value of 6.88 × 10{sup −6} Ω m at 45 vol.% of TiN. It seems the TiN grains form a network to impose conductivity on the ZrO{sub 2} body; however, below 35 vol.% TiN, due to lack of percolation effect, this conductivity could not be maintained according to FESEM studies. Finally, electrically conductive samples were successfully machined by electrical discharge machining (EDM).

36 MATERIALS SCIENCE↗

TiN diffusion barrier for stable W/SiC(0001) interfaces in inert ambient at high temperature

The effect of high-temperature annealing on tungsten (W) films deposited on silicon carbide (SiC) with and without a titanium nitride (TiN) diffusion barrier was examined as a function of time. Evolutions in phase composition, surface morphology, and roughness from annealing at 1273 K were investigated for up to 24 h. Without a TiN diffusion barrier, solid state reactions between the W film and SiC substrate led to the formation of W 5 Si 3 , W 2 C, and WC species and the rise of an inhomogeneous surface structure that was initially web-like and later discontinuous. Severe roughening on the order of the initial film thickness was observed. Incorporation of a 100 nm TiN diffusion barrier suppressed the formation of W 5 Si 3 and W 2 C and only trace WC could be detected due to species diffusion through TiN grain boundaries. Changes in the surface structure and roughness were minimal. Our results warrant consideration of TiN as an effective diffusion barrier for W on SiC systems where structural stability at high temperatures is highly desired.

36 MATERIALS SCIENCE↗

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↗

Influence of Dopant Distribution on the Plasmonic Properties of Indium Tin Oxide Nanocrystals

Doped metal oxide nanocrystals represent an exciting frontier for colloidal synthesis of plasmonic materials, displaying unique optoelectronic properties and showing promise for a variety of applications. However, fundamental questions about the nature of doping in these materials remain. In this article, the strong influence of radial dopant distribution on the optoelectronic properties of colloidal indium tin oxide nanocrystals is reported. Comparing elemental depth-profiling by X-ray photoelectron spectroscopy (XPS) with detailed modeling and simulation of the optical extinction of these nanocrystals using the Drude model for free electrons, a correlation between surface segregation of tin ions and the average activation of dopants is observed. A strong influence of surface segregation of tin on the line shape of the localized surface plasmon resonance (LSPR) is also reported. Samples with tin segregated near the surface show a symmetric line shape that suggests weak or no damping of the plasmon by ionized impurities. It is suggested that segregation of tin near the surface facilitates compensation of the dopant ions by electronic defects and oxygen interstitials, thus reducing activation. A core shell model is proposed to explain the observed differences in line shape. These results demonstrate the nuanced role of dopant distribution in determining the optoelectronic properties of semiconductor nanocrystals and suggest that more detailed study of the distribution and structure of defects in plasmonic colloidal nanocrystals is warranted.

Lounis, SD↗

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↗

Dopant-Free Tetrakis-Triphenylamine Hole Transporting Material for Efficient Tin-Based Perovskite Solar Cells

Developing dopant-free hole transporting layers (HTLs) is critical in achieving high-performance and robust state-of-the-art perovskite photovoltaics, especially for the air-sensitive tin-based perovskite systems. The commonly used HTLs require hygroscopic dopants and additives for optimal performance, which adds extra cost to manufacturing and limits long-term device stability. Here we demonstrate the use of a novel tetrakis-triphenylamine (TPE) small molecule prepared by a facile synthetic route as a superior dopant-free HTL for lead-free tin-based perovskite solar cells. The best-performing tin iodide perovskite cells employing the novel mixed-cation ethylenediammonium/formamidinium with the dopant-free TPE HTL achieve a power conversion efficiency as high as 7.23%, ascribed to the HTL’s suitable band alignment and excellent hole extraction/collection properties. This efficiency is one of the highest reported so far for tin halide perovskite systems, highlighting potential application of TPE HTL material in low-cost high-performance tin-based perovskite solar cells.

14 SOLAR ENERGY↗

Analysis of Al diffusion processes in TiN barrier layers for the application in silicon solar cell metallization

An evaporated Al layer is known as an excellent rear metallization for highly efficient solar cells, but suffers from incompatibility with a common solder process. To enable solar cell-interconnection and module integration, in this work the Al layer is complemented with a solder stack of TiN/Ti/Ag or TiN/NiV/Ag, in which the TiN layer acts as an Al diffusion barrier. X-ray photoelectron spectroscopy measurements prove that diffusion of Al through the stack and the formation of an Al{sub 2}O{sub 3} layer on the stack's surface are responsible for a loss of solderability after a strong post-metallization anneal, which is often mandatory to improve contact resistance and passivation quality. An optimization of the reactive TiN sputter process results in a densification of the TiN layer, which improves its barrier quality against Al diffusion. However, measurements with X-ray diffraction and scanning electron microscopy show that small grains with vertical grain boundaries persist, which still offer fast diffusion paths. Therefore, the concept of stuffing is introduced. By incorporating oxygen into the grain boundaries of the sputtered TiN layer, Al diffusion is strongly reduced as confirmed by secondary ion mass spectroscopy profiles. A quantitative analysis reveals a one order of magnitude lower Al diffusion coefficient for stuffed TiN layers. This metallization system maintains its solderability even after strong post-metallization annealing at 425 °C for 15 min. This paper thus presents an industrially feasible, conventionally solderable, and long-term stable metallization scheme for highly efficient silicon solar cells.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Investigation of Surface Phenomena in Shocked Tin in Converging Geometry

There is great interest in the behavior of the free surface of tin under shock loading. While it is known that meso-scale surface imperfections can seed the Richtmyer-Meshkov Instability (RMI) for a surface that is melted on release, much less is known about a tin surface that is solid, but plastically deforming. Here material properties such as shear and yield strength come into play especially in converging geometry. Previous experiments have been driven by direct contact HE. Usually a thin, flat target coupon is fielded with various single-mode, sinusoidal, machined, profiles on the free surface. The free surface is adjacent to either vacuum or an inert receiver gas. Most of these previous driver/target configurations have been nominal planer geometry. With modern HE it has been straightforward to shock tin into melt on release. However it has been challenging to achieve a low enough pressure for solid state on release. Here we propose to extend the existing base of knowledge to include the behavior of the free surface of tin in cylindrical converging geometry. By shock loading a cylindrical tin shell with a magnetically driven cylindrical liner impactor, the free surface evolution can be diagnosed with proton radiography. With the PHELIX capacitor bank, the drive can easily be varied to span the pressure range to achieve solid, mixed, and liquid states on release.

36 MATERIALS SCIENCE↗

Investigation of Surface Phenomena in Shocked Tin in Converging Geometry

There is great interest in the behavior of the free surface of tin under shock loading. While it is known that meso-scale surface imperfections can seed the Richtmyer- Meshkov Instability (RMI) for a surface that is melted on release, much less is known about a tin surface that is solid, but plastically deforming. Here material properties such as shear and yield strength come into play especially in converging geometry. Previous experiments have been driven by direct contact HE. Usually a thin, flat target coupon is fielded with various single-mode, sinusoidal, machined, profiles on the free surface. The free surface is adjacent to either vacuum or an inert receiver gas. Most of these previous driver/target configurations have been nominal planer geometry. With modern HE it has been straightforward to shock tin into melt on release. However it has been challenging to achieve a low enough pressure for solid state on release. Here we propose to extend the existing base of knowledge to include the behavior of the free surface of tin in cylindrical converging geometry. By shock loading a cylindrical tin shell with a magnetically driven cylindrical liner impactor, the free surface evolution can be diagnosed with proton radiography. With the PHELIX capacitor bank, the drive can easily be varied to span the pressure range to achieve solid, mixed, and liquid states on release. A conceptual cylindrical liner and target is shown in Figure 1.

36 MATERIALS SCIENCE↗