Behavior of mixed multi-walled carbon nanotube/P3HT monolayer at the air/water interface

The sidewall structure of multi-walled carbon nanotubes (MWNTs) was successfully functionalized with poly(3-hexylthiophene) (P3HT) by a non-covalent bond method. P3HT plays an important role in dispersing MWNTs, and assists them to have a stable existence at the air/water interface. The behavior of mixed MWNT/P3HT monolayer at the air/water interface was investigated after obtaining a homogeneously dispersed solution. The effect of MWNT concentration on the mixed MWNT/P3HT monolayer was investigated using the pressure–area (π–A) isotherm, relaxation curve and transmission electron microscopy (TEM). The mixed MWNT/P3HT monolayer was transferred onto a solid substrate using the Langmuir–Blodgett (LB) technique with horizontal or vertical deposition. The multilayer film was delicately fabricated by repeated deposition of the ultra-thin film. Scanning electron microscopy (SEM) images revealed non-uniformity in morphology of the ultra-thin MWNT/P3HT films. The absorption intensity at 250 nm by UV/vis spectroscopy illustrates that a uniform formation of mixed MWNT/P3HT monolayer into multilayer film was successfully obtained by horizontal deposition. The current–voltage characteristic of the ultra-thin MWNT/P3HT film shows that the current increases linearly with the increasing voltage, which indicates that MWNT/P3HT film forms an ohmic contact with gold. And, the electric current was estimated to be mainly contributed by MWNTs.     

Preparation and characterization of polyelectrolyte multilayer films containing in-situ synthesized nanoparticles of Cu(OH)2

Copper ions-loaded polyelectrolyte multilayer films (PEMs) of poly(acrylic acid), coded as PAA, and poly(diallyldimethylammonium chloride), coded as PDDA, were constructed on silicon substrate via layer-by-layer (LBL) self-assembly, using CuCl₂ blended in the electrolyte solution as the source of Cu²⁺. Cu(OH)₂ nanoparticles were then in-situ synthesized in the multilayer films by immersion of the copper ions-loaded PEMs into 0.1 M NaOH solution. The Cu²⁺-loaded PAA/PDDA multilayer films and those doped with in-situ Cu(OH)₂ nanoparticles were characterized by means of ultraviolet-visible light (UV-vis) absorption spectrometry, X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and scanning electron microscopy (SEM). The friction and wear behaviors of the multilayer films sliding against 440C stainless steel counterparts were evaluated using a UMT-2 multifunctional micro tribometer. Results indicate that the Cu²⁺-loaded PAA/PDDA multilayers with a bilayer number of 2-8 show similar UV-vis absorbance features, and no noticeable accumulation in the amount of Cu²⁺ occurs during the fabrication of the multilayers, possibly owing to a weak bonding between Cu²⁺ and -COO⁻. The blue-shift of the absorption peak of -COO⁻-Cu²⁺ band, observed for PAA/PDDA multiplayer films, becomes more obvious after being doped with in-situ Cu(OH)₂ nanoparticles. The final Cu(OH)₂ nanoparticles-doped PAA/PDDA multilayer films have excellent friction-reducing and antiwear abilities, possibly owing to the modification and refining of their morphology and microstructure by the in-situ doped Cu(OH)₂ nanoparticles. The present approach could be extended to incorporate nanoparticles of other types of metal ions into the final PEMs to realize multifunctionalization.     

Stainless Steel Bipolar Plates Deposited with Multilayer Films for PEMFC Applications

A chromium nitride (CrN, Cr₂N)/chromium (Cr)/indium-tin-oxide (ITO) system and a gold (Au)/titanium (Ti) system were separately deposited using a sputtering method and an E-beam method, respectively, onto stainless steel 316 and 304 plates. The XRD patterns of the deposited stainless steel plates showed the crystalline phase of typical indium-tin oxide and of metallic phases, such as chromium, gold, and the metal substrate, as well as those of external chromium nitride films. The nitride films were composed of two metal nitride phases that consisted of CrN and Cr₂N compounds. The surface morphologies of the modified stainless steel bipolar plates were observed using atomic force microscopy and FE-SEM. The chromium nitride (CrN, Cr₂N)/chromium (Cr)/indium-tin-oxide (ITO) multilayer that was formed on the stainless steel plates had a surface microstructural morphology that consisted of fine columnar grains 10 nm in diameter and 60 nm in length. The external gold films that were formed on the stainless steel plates had a grain microstructure approximately 100 nm in diameter. The grain size of the external surface of the stainless steel plates with the gold (Au)/titanium (Ti) system increased with increasing gold film thickness. The electrical resistances and water contact angles of the stainless steel bipolar plates that were covered with the multilayer films were examined as a function of the thickness of the ITO film or of the external gold film. In the corrosion test, ICP-MS results indicated that the gold (Au)/titanium (Ti) films showed relatively excellent chemical stability after exposure to H₂SO₄ solution with pH 3 at 80 °C.     

Enhanced optical modulation due to SPR in gold nanoparticles embedded WO3 thin films

Surface plasmon resonance (SPR) phenomenon of metal-dielectric composite thin films formed by embedding the noble metal nanoparticles in a dielectric matrix offers a high degree of flexibility and enables many applications such as surface enhanced spectroscopes, numerous biological and chemical sensing fields. A remarkable enhancement in optical modulation after embedding the gold nanoparticles in a reticulated mesh like matrix of WO₃ thin films was observed. WO₃ films were prepared onto the conducting ITO coated glass substrates by a novel pulsed spray pyrolysis technique (PSPT). A reticulated mesh like morphology of WO₃ was achieved by optimizing the deposition parameters of PSPT and the gold nanoparticles were embedded in the WO₃ matrix by a drop casting method. Enhancements in electrochromic properties of WO₃ in terms of optical modulation (ΔOD), coloration efficiency (η) and response times (t_c and t_b) were attributed to the assistance of SPR in gold nanoparticles during coloration and electric field induced quenching of SPR during bleaching.     

Improvement of the Electrochemical Behavior of Steel Surfaces Using a [Ti-Al/Ti-Al-N] n Multilayer System

The aim of this work is to improve the corrosion resistance of AISI D3 steel surfaces using a [Ti-Al/Ti-Al-N] _n multilayer system deposited with different periods (Λ) and bilayer numbers (n), via magnetron co-sputtering pulsed d.c. procedure, from a metallic (Ti-Al) binary target. The multilayer coatings were characterized by cross-sectional scanning electron microscopy that showed the modulation and microstructure of the [Ti-Al/Ti-Al-N] _n multilayer system. The composition of the single Ti-Al and Ti-Al-N layer films was studied via x-ray photoelectron spectroscopy, where typical signals for Ti_2p1/2, Ti_2p, N_1s, and Al_2p3/2 were detected. The electrochemical properties were evaluated by electrochemical impedance spectroscopy and Tafel polarization curves. The optimal electrochemical behavior was obtained for the [Ti-Al/Ti-Al-N] _n multilayered period of Λ = 25 nm (100 bilayers). At these conditions, the maximum polarization resistance (1719.32 kΩ cm²) and corrosion rate (0.7 μmy) were 300 and 35 times higher than that of uncoated AISI D3 steel substrate (5.61 kΩ cm² and 25 μmy, respectively). Finally, scanning electron microscopy was used to analyze the [Ti-Al/Ti-Al-N] _n multilayered surface after the corrosive attack. The improvement effects in the electrochemical behavior of the AISI D3 coated with the [Ti-Al/Ti-Al-N] _n multilayered coatings could be attributed to the number of interfaces that act as obstacles for the inward and outward diffusions of Cl^? ions, generating an increment in the energy or potential required for translating the corrosive ions across the coating/substrate interface.     

Microstructure and physical properties of PVD TiN/（Ti, Al）N multilayer coatings

Magnetron sputtered （Ti, Al） N monolayer and TiN/（Ti, Al） N multilayer coatings grown on cemented carbide substrates were studied by using energy dispersive X-ray spectroscopy （EDX）, scanning electron microscopy （SEM）, nanoindentation, Rockwell A indentation test, strength measurements and cutting tests. The results show that the （Ti, Al）N monolayer and TiN/（Ti, Al）N multilayer coatings perform good affinity to substrate, and the TiN/（Ti, Al）N multilayer coating exhibits higher hardness, higher toughness and better cutting performance compared with the （Ti, Al）N monolayer coating. Moreover, the strength measurement indicates that the physical vapour deposition （PVD） coating has no effect on the substrate strength.     

On the role of Fe in the growth of single crystalline heteroepitaxial Au thin films on sapphire

Thin Au–Fe bilayers were deposited on c-plane sapphire (α-Al₂O₃) substrates at room temperature employing the electron beam deposition method. The layers were found to be single crystalline (i.e. the grain size was much larger than the film thickness), with a [1 1 1] and [1 1 0] texture for Au and Fe, respectively, and strong heteroepitaxy to the substrate. Au films deposited on sapphire and Au–Fe bilayers deposited on amorphous SiO₂ were polycrystalline and exhibited random in-plane orientation of the grains. The effects of Fe and the Fe–sapphire interface on the microstructure of the Au film were investigated and discussed in terms of the orientation relationships, in-plane strain, interface energy and adhesion. The microstructures of annealed and as-deposited films were very similar, indicating that as-deposited films are close to thermodynamic equilibrium in terms of the orientation relationship with the substrate. This is uncommon for non-equilibrium thin film deposition processes, which usually result in a high density of defects in the as-deposited films.     

Electron microscopy studies of the thermal stability of gold nanoparticle arrays

A series of monolayer protected gold nanoparticle colloidal solutions have been prepared with average sizes in the 2–15nm range. If a drop of such a colloidal suspension is deposited onto a Si₃N₄ substrate and the solvent allowed to evaporate, the particles have a tendency to self-assemble into monolayer rafts with varying degrees of structural order depending on the initial mono-dispersity of the particles. The thermal stability of these selfassembled gold nanoparticle rafts as a function of particle size, heating method, heating rate and ligand identity have been assessed in this study. In-situ TEM studies show that sub-8nm Au nanoparticles on Si₃N₄ have a tendency to coarsen upon slow heating, whereas those comprised of larger particles exhibit densification. Increasing the heating rate for the smaller particles promoted densification, forcing them to form highly interconnected string-like structures. Finally, rafts of sub-4nm alkanethiol protected Au nanoparticles are shown to sinter spontaneously under ambient conditions at room temperature on the timescale of several months. This unexpected effect may have important implications for the long term structural stability of any device constructed from sub-4nm gold nanoparticles.     

Morphological changes of Au nanoparticles in Au–polystyrene nanocomposites: A combined spectroscopy,atomic force microscopy and X-ray scattering study

Au nanoparticles sputter deposited on polystyrene-coated Si and fused quartz substrates have been studied using optical spectroscopy, atomic force microscopy and X-ray reflectivity. Under the same deposition conditions, both spectroscopy and atomic force microscopy indicate clearly that the nanoparticles undergo a shape transition from near-spherical to progressively ellipsoidal as the polystyrene film becomes thinner than 4R_g, R_g being the radius of gyration of the polymer. There is a gradual increase in the in-plane ellipticity a/b, a(b) = semi-major (semi-minor) axis, with decrease in polystyrene film thickness from 230 to 20 nm, where b remains almost invariant for a particular deposition time while the semi-major axis increases in dimension. Electron density profiles along the depth of the films, extracted from X-ray reflectivity data, show that the Au nanoparticles sit on the top of the polystyrene film with c, the third ellipsoid axis having a dimension of about 3.0 nm irrespective of film thickness or deposition times used (7, 10, 12 and 15 s).     

Analysis of Chemical Bonding and Structural Network of Gold Silicide in Core–Shell Silicon Nanowire

The Au-catalyzed core–shell silicon nanowires (Si-NWs) were synthesized by chemical vapor deposition by using SiH₄ and H₂ precursor gases. The TEM and FTIR studies revealed that the Si-NWs consist of core silicon surrounded by a thick oxide sheath and Au distributed at the a-SiOx/Si interface. The x-ray photoelectron spectroscopy (XPS) was used to study the chemical composition and electronic environments of gold silicide in the a-SiO _x /Si-NWs. The elemental analysis and chemical network of gold silicide of core–shell Si-NWs were explained on the basis of the random atomic distribution of Si, O and Au atoms. The Raman spectra and XRD peak reveal the crystalline core of Si-NWs. The individual contribution to the Au (4d) core orbital was deconvoluted to Au-Si-Au, Au-Si-O, Au-Au, Au-O-Au, Au-O-Si and Au=O/Au-O₂ bonding structure. The analysis shows that the O linked with Si and Au has also contributed to growth of Si-NWs.     

Comparison in mechanical and tribological properties of Cr-W-N and Cr-Mo-N multilayer films deposited by DC reactive magnetron sputtering

Cr-W-N and Cr-Mo-N films were deposited on high speed steel substrate by unbalanced DC reactive magnetron sputtering. Cross-sectional scanning electron microscopy (SEM) morphologies of the films confirmed that the bilayer thickness of multilayer became thinner, and then structural transformation occurred from multilayer to composite with increasing the rotation velocity of substrate holder. X-ray diffraction (XRD) patterns indicated that the Cr-W-N films were composed of CrN and W₂N crystalline phases, and the Cr-Mo-N films consisted of crystalline CrN and amorphous/nanocrystalline Mo₂N. Mechanical and tribological properties were investigated by using a nanoindentor and a ball-on-disk tribometer, respectively. The Cr-W-N films exhibited excellent mechanical properties and wear resistance, while Cr-Mo-N films showed lower friction coefficient. Optimal mechanical and tribological properties were obtained in the Cr-W-N multilayer film with a bilayer period of 12 nm.     

Surface properties of Langmuir films of mono-, di-, and tetra-n-octyl adducts of C60 at the water–air interface

Relatively stable Langmuir films of mono-, di-, and tetra-n-octyl adducts of C₆₀ were prepared at the water–air interface. The adducts were obtained by selective bulk electrosynthesis at controlled potential. For the films, surface pressure (π) and a surface potential change (ΔV) were simultaneously measured as a function of surface area per molecule (A) during the film compression. The spreading properties of the adducts strongly depend on the number of n-octyl chains linked to the C₆₀ cage and nature of the spread solution. The determined zero-pressure limiting area per molecule (A₀) is larger the more n-octyl chains are attached to the C₆₀ cage. Aggregated multilayer films are formed for the toluene and tetrahydrofuran spread solutions while liquid monolayer films for the chloroform solutions. Remarkably, relatively stable liquid monolayer films of pristine C₆₀ are obtained also from the chloroform solutions. For relatively concentrated chloroform solutions, plateaus are developed in the π–A adduct isotherms. Isotherms for both concentrated and diluted chloroform solutions show reversible compression and expansion with virtually no hysteresis. Comparison of the estimated and determined A₀ values indicates that all adduct molecules are horizontally oriented in the monolayer films. Unexpectedly, large mean dipole moment components normal to the water–air interface, determined from inflection points of the ΔV–A isotherms, are presumably due to preferential orientation of water molecules adjacent to the interface of the water subphase and the floating adduct film.     

Pattern replication in polyaniline–polystyrene thin films

Blends of polyaniline doped with camphorsulfonic acid (PANI(CSA)) and polystyrene (PS) were spin-cast from chloroform onto gold substrate patterned with a hydrophobic self-assembled monolayer (CH₃-SAM). As a result, the replication of the substrate pattern into the formed thin films was obtained, observed as pattern-directed variation of both film thickness and polyaniline distribution. The thin films were examined by means of optical microscopy, atomic force microscopy (AFM) and secondary ion mass spectrometry (SIMS).     

Electrodeposition of cerium oxide films and composites

Nanostructured CeO₂ films were prepared by cathodic electrolytic deposition (ELD) and electrophoretic deposition (EPD). Benzoic acid has been utilized for the dispersion and charging of CeO₂ nanoparticles for EPD. The kinetics of ELD and EPD was investigated. Electrodeposition method has been developed for the deposition of poly(2-vinylpyridine) (PVP) films. The thickness of the films was varied in the range of 0.1-3 μm. The deposition mechanism was based on the pH increase in the cathodic reactions, electrophoresis of the protonated PVP macromolecules, neutralization of their charge and film formation at the cathode surface. The deposition yield was studied by the quartz crystal microbalance method. Two electrochemical strategies were developed for the fabrication of composite PVP-CeO₂ films, which were based on the electrodeposition of PVP and ELD or EPD of CeO₂. The composite films were studied by electron microscopy, X-ray diffraction, thermogravimetric and differential thermal analysis. The CeO₂ content in the composite films was varied by the variation of bath composition. The deposition methods allowed the fabrication of crack-free PVP-CeO₂ films, which provided corrosion protection of stainless steel substrates in aqueous NaCl solutions.     

The effect of evaporation on size and shape evolution of faceted gold nanoparticles on sapphire

We studied the size and shape evolution of about 180 faceted gold nanoparticles attached to a sapphire substrate during annealing at 950 °C in air. We employed the scanning force microscopy and interrupted annealing techniques to track the changes in size and shape of individual nanoparticles. The height of all single-crystalline nanoparticles was constant up to the longest cumulative annealing time of 65 h. The lateral dimensions of ∼20% of all nanoparticles shrunk during anneals, while all three dimensions of the remaining 80% of nanoparticles remained constant. Only the nanoparticles with the height below the average (for all particles) were laterally shrinking. We formulated a kinetic model relating the lateral shrinkage of the nanoparticles to the evaporation of Au atoms adsorbed on sapphire. We also assumed that the process controlling particles shrinkage is the slow self-diffusion of Au atoms along the lateral facets of the nanoparticles toward the substrate. The model predicted a power law dependence of the shrinkage rate on the particle height, with the exponent n = 3. The corresponding exponent determined from the experimental data was n = −2.9 ± 0.3, in excellent agreement with the theory. The low value of the effective self-diffusion coefficient along the lateral facets determined with the aid of our model (3.2 ± 0.2 × 10⁻¹⁷ m² s⁻¹) was attributed to the difficulties of step nucleation on atomically flat facets.     

脉冲激光沉积WSx/a-C复合薄膜的结构与摩擦学性能

采用脉冲激光烧蚀石墨/WS₂组合靶,在硅基片上沉积不同碳质量分数的WSx/a-C复合膜。用能谱仪、扫描电子显微镜和X射线衍射仪对薄膜的成分、形貌和微观组织进行了表征。采用纳米压痕仪、涂层附着力划痕仪和球-盘式摩擦磨损试验机对薄膜的硬度、结合力和大气中(相对湿度50~55%)的摩擦学性能进行了测试。结果表明,薄膜的S/W比稳定在2.0左右且形成了(002)择优取向的WS₂相。随着薄膜中碳质量分数的增加,薄膜的硬度在36.1%C时出现最高值,结合力随之增大且在52.4%C时达到最高值,摩擦因数先降低后增加,在41.2%C时有最小值0.144。薄膜磨损率在(0.91~1.61)×10_-15 m₃N_-1m_-1范围内变化,36.1%C的WSx/a-C复合膜具有最佳耐磨性能。     

A reaction-layer mechanism for the delayed failure of micron-scale polycrystalline silicon structural films subjected to high-cycle fatigue loading

A study has been made to discern the mechanisms for the delayed failure of 2-μm thick structural films of n⁺-type, polycrystalline silicon under high-cycle fatigue loading conditions. Such polycrystalline silicon films are used in small-scale structural applications including microelectromechanical systems (MEMS) and are known to display ‘metal-like’ stress-life (S/N) fatigue behavior in room temperature air environments. Previously, fatigue lives in excess of 10¹¹ cycles have been observed at high frequency (~40 kHz), fully-reversed stress amplitudes as low as half the fracture strength using a surface micromachined, resonant-loaded, fatigue characterization structure. In this work the accumulation of fatigue-induced oxidation and cracking of the native SiO₂ of the polycrystalline silicon was established using transmission electron and infrared microscopy and correlated with experimentally observed changes in specimen compliance using numerical models. These results were used to establish that the mechanism of the apparent fatigue failure of thin-film silicon involves sequential oxidation and environmentally-assisted crack growth solely within the native SiO₂ layer. This ‘reaction-layer fatigue’ mechanism is only significant in thin films where the critical crack size for catastrophic failure can be reached by a crack growing within the oxide layer. It is shown that the susceptibility of thin-film silicon to such failures can be suppressed by the use of alkene-based monolayer coatings that prevent the formation of the native oxide.     

Protonation-induced rearrangements in Langmuir films and redox properties of Langmuir–Blodgett films of 2-(n-alkyl)fulleropyrrolidines

The effect of protonation of the pyrrolidine ring nitrogen of 2-(n-alkyl)fulleropyrrolidines, C₆₀pyr–C_m (m=4, 6, 8, 10 and 12), on the properties of the Langmuir and Langmuir–Blodgett (LB) films was investigated. The isotherms of both surface pressure (π) and surface potential change (ΔV) versus area per molecule (A) for the Langmuir films of C₆₀pyr–C_m were determined simultaneously. It was found that the longer the alkyl chain of the fulleropyrrolidine the larger is the film compressibility, κ, i.e., κ(C₆₀pyr–C₄)=(2.1±0.4)×10⁻² m mN⁻¹, κ(C₆₀pyr–C₈)=(3.5±0.4)×10⁻² m mN⁻¹ and κ(C₆₀pyr–C₁₂)=(4.1±0.5)×10⁻² m mN⁻¹, as expected for the liquid surface films. The values of surface area at zero surface pressure (A₁) differ in the range 0.6 nm² molecule⁻¹ (for m=4–8) to 1.4 nm² molecule⁻¹ (for m=10–12), indicating that all 2-(n-alkyl)fulleropyrrolidines form multilayer or aggregated films on neutral water subphase. However, acidification of the water subphase increases the A₁ values for all investigated fulleropyrrolidines up to ca. 1.9 nm² molecule⁻¹, i.e., the value corresponding to maximum area occupied by a fulleropyrrolidine at horizontal orientation in a monolayer film. Apparently, 2-(n-alkyl)fulleropyrrolidinium cations formed at low pH are markedly de-aggregated in the films and their orientation is changed due to protonation of the pyrrolidine nitrogen. Similarly, however, less pronounced effects are observed if ionic strength of the subphase solution, I, is increased in the range 0≤I≤1.0 mol dm⁻³ NaCl. The Langmuir films formed on a water subphase were the most stable with respect to the LB transfer onto 5 MHz Au–quartz crystal vibrators. Simultaneous cyclic voltammetry and piezoelectric microgravimetry at an electrochemical quartz crystal microbalance of these films showed at least two electroreductions where the fulleropyrrolidine mono anions were stable with respect to dissolution.     

Preparation and high-frequency soft magnetic property of FeCo-based thin films

A series of FeCo-based thin films were prepared by magnetron sputtering without applying an induced magnetic field.The microstructure,electrical properties,magnetic properties and thermal stability of FeCo,FeCoSiN monolayer thin film and[FeCoSiN/SiN_x]_n multilayer thin film were investigated systematically.When FeCo thin film was doped with Si and N,the resistivity and soft magnetic properties of the obtained FeCoSiN thin film can be improved effectively.The coercivity(H_c),resistivity(ρ) and ferromagnetic resonance frequency(f_r) can be further optimized for the[FeCoSiN/SiN_x]_n multilayer thin film.When the thickness of FeCoSiN layer and SiN_x layer is maintained at 7 and 2 nm,the H_c,p and f_r for[FeCoSiN/SiN_x]_n multilayer thin film are 225 A·m~(-1)392 μΩ·cm~(-1) and 4.29 GHz,respectively.In addition,the low coercivity of easy axis(H_(ce) ≈ 506 A·m~(-1)) of[FeCoSiN/SiN_x]_n multilayer thin film can be maintained after annealing at 300 ℃ in air for 2 h.     

Growth of HT-LiCoO2 thin films on Pt-metalized silicon substrates

Layered LiCoO2 （HT-LiCoO2） films were grown on Pt-metalized silicon （PMS） substrates and polished bulk nickel （PBN） substrates by pulsed laser deposition. The effects of substrate temperature, oxygen pressure, and substrate surface roughness on the microstructure of LiCoO2 films were investigated. It has been found that a higher substrate temperature and a higher oxygen pressure favor the formation of better crystallized and less lithium-deficient HT-LiCoO2 films. The HT-LiCoO2 film deposited on PBN substrates consists of large randomly orientated equiaxial grains, whereas on PMS substrate, it is made up of loosely packed highly [001] preferential orientated triangular shaped grains with the average grain size less than 100 nm. Electrochemical measurements show that the highly [001] preferentially orientated nanostructured HT-LiCoO2 thin film grown on PMS substrate has good structural stability upon lithium insertion/extraction and can deliver an initial discharge capacity of approximately 45μA·h·cm^-2·μm^-1 with a cycling efficiency of above 99% at the charge/discharge rate of 0.5 C.