Aerosol assisted fabrication of metallic film/carbon fiber and heat treatment to form crystalline alloy film

Carbon fiber (CF) was catalytically activated with spark generated Pd aerosol nanoparticles. Metal (Ag, Au, Cu, and Pd) and alloy (Ni-P, Ni-Cu-P) electroless films were deposited on Pd aerosol activated CF using a range of deposition parameters including deposition rate in an electroless deposition bath. Sintering was applied to the alloy films on the CF to examine the crystallization behavior at 400 °C in a nitrogen atmosphere. Ni-Cu-P had a higher crystallinity than Ni-P after the treatment.     

A facial microwave-assisted polyol activation process for fabrication of Ni@PMMA microspheres

A simple and efficient activation process was conducted by deposition of palladium (Pd) nanoparticles on PMMA surface using a microwave-assisted polyol method with ethanol used as the reductant. The newly synthesized Pd nanoparticles were utilized as an activator for electroless nickel deposition. TEM images revealed that Pd nanoparticles of size 4-6 nm are formed evenly over the PMMA surface. A tight, smooth and continuous Ni plating layer was coated on these Pd nanoparticle activated PMMA microspheres. In contrast, a rough and discontinuous Ni film was obtained for the sample activated with a conventional sensitization/activation procedure.     

Synthesis and photoluminescence of ultra-pure germanium nanoparticles

We have used aerosol deposition to synthesize defect and micro-strain free, ultra-pure germanium nanoparticles. Transmission electron microscopy images show a core-shell configuration with highly crystalline core material. Powder X-ray diffraction measurements verify the presence of highly pure, nano-scale germanium with average crystallite size of 30 nm and micro-strain of 0.058%. X-ray photoelectron spectroscopy demonstrates that GeO_x (x ? 2) shells cover the surfaces of the nanoparticles. Under optical excitation, these nanoparticles exhibit two separate emission bands at room temperature: a visible emission at 500 nm with 0.5-1 ns decay times and an intense near-infrared emission at 1575 nm with up to ∼20 μs lifetime.     

Templated synthesis of polyaniline nanotubes with Pd nanoparticles attached onto their inner walls and its catalytic activity on the reduction of p-nitroanilinum

In this paper, polyaniline (PANI) nanotubes with palladium nanoparticles (NPs) attached onto their inner walls were synthesized via a templating method which contains three steps. First, electrospun polystyrene (PS) nanofibers were coated with nearly monodispersed Pd NPs (d = 3.411 nm, σ = 0.687 nm, d is the average diameter of Pd NPs and σ is the standard deviation of their diameters) through in situ reduction of Pd²⁺ ions on the surface of sulfonated PS nanofibers. Then we used a self-assembly method to coat the composite with a PANI layer. The final product was obtained after the removal of PS nanofibers by diluting them in tetrahydrofuran. The morphology of samples was analyzed by scanning electron microscopy and transmission electron microscopy and the structure was characterized by Fourier transform infrared, ultraviolet–visible spectra, X-ray diffraction patterns and X-ray photoelectron spectroscopic patterns. Inductively coupled plasma atomic spectra were used to show the weight percentage of Pd nanoparticles. Its catalytic activity on the reduction of p-nitroanilinum was also investigated and compared to Pd/C catalyst and Pd/MWNTs.     

Carbon fiber coating with silver using intervening Au/Pd nanoparticle films produced using a spark discharge

A low roughness conductive silver film on a fiber substrate was fabricated via a catalytic surface activation (needed to initiate electroless silver deposition) with spark produced gold aerosol nanoparticles. Gold had a similar lattice parameter with silver in crystallinity and thus a crystallographic misfit between gold activated substrate and silver was minimized during the deposition, resulting in formation of a flat silver film. Properties were compared with those obtained with palladium aerosol activation, the gold activation enhanced thin-metallic film properties in surface root-mean-square roughness (nm: 8, gold vs 44, palladium) and electrical resistivity (μΩ cm: 64, gold vs 498, palladium) at 88 mg/g (silver/substrate) in deposition amount.     

Synthesis and surface plasmon resonance properties of carbon-coated Cu and Co nanoparticles

Carbon-coated Cu and Co nanoparticles were synthesized by the carbonization of PVA-metal hydroxide complexes. The possible reaction process and surface plasmon resonance (SPR) properties of the Cu and Co nanoparticles enwrapped in carbon layer were explored. The XRD results showed that no byproducts, such as oxides and carbides, were formed in the products, and the Cu and Co nanoparticles were effectively protected against oxidation by the carbon layer. The size ranges of the metal nanoparticles were 20-50 nm for Cu and 15-65 nm for Co, respectively. UV-vis absorption spectra showed that the SPR bands of the Cu and Co nanoparticles coated with carbon were red-shifted mainly due to the increase of the effective dielectric constant of the surrounding medium induced by the carbon layer.     

Wet chemical route to transparent BiFeO3 films on SiO2 substrates

BiFeO₃ nanoparticles were prepared by a wet chemical synthesis method. Transparent films were deposited on glass and quartz substrates by dip and spin coating processes from the synthesized sol. We obtained thicker films (~ 2 µm) by dip coating process and thinner films (~ 200 nm) by spin coating process. Transmission electron microscopy images confirmed that the particles are nanocrystalline in size. From the optical transmittance spectra the band gap of the BiFeO₃ nanoparticles was determined in the range of ~ 3.03-2.88 eV (~ 410-430 nm). Electrical resistivity, polarization, zero-field-cooled and field-cooled magnetizations versus temperature characteristics were also studied for these films.     

Thermal evolution and optical properties of Cu nanoparticles in SiO2 by ion implantation

SiO₂ samples were implanted by 45 keV Cu ions at a dose of 1 × 10¹⁷ /cm², and subjected to furnace annealing at temperatures ranging from 200 to 600 °C in nitrogen atmosphere. The results indicate that the Cu nanoparticles have been synthesized by Cu ion implantation, and subsequent annealing induces the diffusion and nucleation of nanoparticles partially. The results from XPS measurements show that the Cu⁰ is the dominate charge state in the implanted and subsequent annealed samples. With increasing annealing temperature, the size and distribution of Cu nanoparticles have been modified gradually. The surface plasmon resonance (SPR) of Cu nanoparticles at 570 nm has been observed by optical transmission spectroscopy. The strongest SPR signal at 400-600 °C indicates that lots of Cu nanoparticles have grown and show good optical properties. Moreover, the luminescence has been investigated in Cu implanted and subsequent annealed samples. Possible luminescence mechanisms, such as radiation induced defects, Cu (ions or atoms) related luminescence centers, etc., have been discussed.     

Simple fabrication of a Pd-P film on a polymer membrane and its catalytic applications

Composites were prepared by a surface activation by aerosol deposition of Pd nanoparticles (Pd nano seeds) on a poly(tetrafluoroethylene) membrane and subsequent Pd-P film formation by electroless deposition. Activation of the membrane processed by an ambient Pd spark discharge and subsequent fixation of the spark produced Pd nano seeds. Characterizations for electroless Pd-P films indicated that P entered into the crystal lattice of Pd and formed an alloy. The fabricated composites were applied to catalytic applications of formic acid oxidation (FAO) and toluene conversion (TC). The composite catalysts from the simple activation had more stable performances of FAO and TC than those from the conventional Sn-Pd activation, and their better performances might have originated from better purity due to the simple activation that only introduced pure Pd nano seeds.     

Synthesis and characterizations of Ni-Fe@spinel oxide core-shell nanoparticles

Core-shell Ni-Fe@ferrite nanoparticles with an average diameter of 14 nm and shell thickness of 3 nm were synthesized through a redox-transmetalation process. The alloy core and spinel oxide shell were verified by X-ray photoelectron spectroscopy, X-ray diffraction, and transmission electron microscopy. The hydrophobic oleylamine molecules on the surface were replaced by hydrophilic meso-2,3-Dimercaptosuccinic acid to make the nanoparticles to be water-soluble. X-ray diffraction study of the as-prepared core-shell nanoparticles indicates that they remained face centered cubic alloy core and spinel shell form in air. Magnetic measurements indicate that the core-shell nanoparticles exhibit superparamagnetic and exchange bias characteristics at 300 K and 5 K, respectively.     

Titanium monoxide ultra-thin coatings evaporated onto polycrystalline copper films

We evaporated polycrystalline copper thin films of thickness between 10 and 100 nm on silicon substrates with their native oxide under ultra-high-vacuum conditions. Some of them were exposed to air for a period ranging from 1 day to 2 weeks. X-ray photoelectron spectroscopy (XPS) revealed a clean copper surface with a trace of oxygen. These films that were exposed to air presented oxides in the state Cu(II), the amount of CuO depended on the time that the film was exposed to air. Subsequently, we deposited TiO ultra-thin films on polycrystalline copper substrates. Both these thin films were formed by electron beam evaporation. XPS spectra showed that the surface of the titanium monoxide (TiO) films was contamination-free. An evaporation of 0.3 nm of TiO reduced the native oxide of the copper substrates from Cu(II) to Cu(I) or Cu(0) and transformed the TiO into TiO₂ at the interface. Low-energy ion spectroscopy showed that the complete coverage of the substrates depends on the thickness of the copper films. For 10 nm copper thin films the complete coverage occurred at 1.5 nm of TiO, and for 100 nm it occurred at 2.0 nm of TiO. In samples exposed to air, the complete coverage occurred at a film thickness slightly higher than those treated under ultra-high-vacuum conditions.     

Textured surface boron-doped ZnO transparent conductive oxides on polyethylene terephthalate substrates for Si-based thin film solar cells

Textured surface boron-doped zinc oxide (ZnO:B) thin films were directly grown via low pressure metal organic chemical vapor deposition (LP-MOCVD) on polyethylene terephthalate (PET) flexible substrates at low temperatures and high-efficiency flexible polymer silicon (Si) based thin film solar cells were obtained. High purity diethylzinc and water vapors were used as source materials, and diborane was used as an n-type dopant gas. P-i-n silicon layers were fabricated at ~ 398 K by plasma enhanced chemical vapor deposition. These textured surface ZnO:B thin films on PET substrates (PET/ZnO:B) exhibit rough pyramid-like morphology with high transparencies (T ~ 80%) and excellent electrical properties (Rs ~ 10 Ω at d ~ 1500 nm). Finally, the PET/ZnO:B thin films were applied in flexible p-i-n type silicon thin film solar cells (device structure: PET/ZnO:B/p-i-n a-Si:H/Al) with a high conversion efficiency of 6.32% (short-circuit current density J_SC = 10.62 mA/cm², open-circuit voltage V_OC = 0.93 V and fill factor = 64%).     

Structural, optical and electrical properties of AZO/Cu/AZO tri-layer films prepared by radio frequency magnetron sputtering and ion-beam sputtering

Highly conducting tri-layer films consisting of a Cu layer sandwiched between Al-doped ZnO (AZO) layers (AZO/Cu/AZO) were prepared on glass substrates at room temperature by radio frequency (RF) magnetron sputtering of AZO and ion-beam sputtering of Cu. The tri-layer films have superior photoelectric properties compared with the bi-layer films (Cu/AZO, AZO/Cu) and single AZO films. The effect of AZO thickness on the properties of the tri-layer films was discussed. The X-ray diffraction spectra show that all films are polycrystalline consisting of a Cu layer with the cubic structure and two AZO layers with the ZnO hexagonal structure having a preferred orientation of (0 0 2) along the c-axis, and the crystallite size and the surface roughness increase simultaneously with the increase of AZO thickness. When the AZO thickness increases from 20 to 100 nm, the average transmittance increases initially and then decreases. When the fixed Cu thickness is 8 nm and the optimum AZO thickness of 40 nm was found, a resistivity of 7.92 × 10⁻⁵ Ω cm and an average transmittance of 84% in the wavelength range of visible spectrum of tri-layer films have been obtained. The merit figure (F_TC) for revaluing transparent electrodes can reach to 1.94 × 10⁻² Ω⁻¹.     

Green synthesis of silver nanoparticles using marine polysaccharide: Study of in-vitro antibacterial activity

The present contribution deals with one pot method for synthesis of silver nanoparticles through green route using sulfated polysaccharide isolated from marine red algae (Porphyra vietnamensis). The obtained silver nanoparticles showed surface plasmon resonance centered at 404 nm with average particle size measured to be 13 ± 3 nm. FTIR spectra revealed the involvement of sulfate moiety of polysaccharide for reduction of silver nitrate. The capping of anionic polysaccharide on the surface of nanoparticles was confirmed by zeta potential measurement (−35.05 mV) and is responsible for the electrostatic stability. The silver nanoparticles were highly stable at wide range of pH (2-10) and electrolyte concentration (up to 10⁻² M of NaCl). The dose dependent effect of synthesized silver nanoparticles revealed strong antibacterial activity against gram negative bacteria as compared to gram positive bacteria.     

Physicochemical and catalytic properties of palladium supported on poly(o-methoxyaniline)

Palladium was introduced into a conjugated polymer poly(o-methoxyaniline) (POM) by reacting the powdered polymer with aqueous solution of PdCl₂ of low acidity (PdCl₂: 2.3 × 10⁻³ mol/dm³, HCl: 0.66 × 10⁻³ mol/dm³). Various Pd²⁺ complexes with Cl⁻, H₂O, OH⁻ ligands coexisted in this solution but predominated [PdCl₂(H₂O)₂] ones. Several techniques like X-ray powder diffraction, scanning electron microscopy, X-ray photoelectron and Raman spectroscopy, extended X-ray absorption fine structure have been used to characterize the poly(o-methoxyaniline)-Pd systems. In particular, the state of Pd species in the Pd/POM of various content of palladium (2-8 wt.% Pd) and chemical changes in the polymer matrix induced by insertion of palladium were studied. The protonation and redox reactions involved on palladium incorporation resulted in palladium ions and Pd metal in the final samples. Metallic Pd produced due to spontaneous reduction of palladium ions by the polymer formed large crystalline particles 200-1000 nm in size. The Pd²⁺ species in the form of anionic complexes like [PdCl₄]²⁻ acted as the counterions at low content of palladium (2-4 wt.% Pd). At high palladium content (8 wt.% Pd), several atoms like Cl, N and/or O were identified by extended X-ray absorption fine structure (EXAFS) technique in the nearest environment of Pd atoms. The structural groups of POM (like N groups and/or OCH₃) as well as H₂O, OH⁻ molecules are, therefore, considered as probable species in the coordination sphere of palladium. The catalytic properties were studied for the as-prepared Pd/POM and the samples additionally reduced with aqueous solution of NaH₂PO₂. They were used in the hydrogenation of CC bonds in maleic acid (MAC) and CO groups in 2-ethylanthraquinone (eAQ) at 60 °C and atmospheric pressure of hydrogen using xylene-octanol-2 or water medium. The correlation between Pd/POM activities and the content of Pd metal was found. Activation of the as-prepared Pd/POM with NaH₂PO₂ improved their catalytic properties. Much higher and much stable activities were then obtained in both MAC and eAQ hydrogenation reactions.     

In-situ X-ray diffraction study of the initial dealloying of Cu3Au(001) and Cu0.83Pd0.17(001)

Dealloying and selective dissolution are serious corrosion processes, but also employed in technology. We studied the surface structure of Cu_0.83Pd_0.17(001) and Cu₃Au(001) during electrochemical selective Cu dissolution below the critical potential in-situ in 0.1 M H₂SO₄ (pH = 1) electrolyte. In both cases we observe the formation of an epitaxial layer of nano-scale islands of the noble component of the original alloy (Au or Pd). These islands form a metallic passivation layer suppressing massive dissolution of Cu. The Au islands developed {111} facets. By re-deposition of Cu ions from the electrolyte solution onto Pd islands, an epitaxial Cu layer is formed.     

Self-assembling (nano-)wrinkling topography formation in low-temperature vacuum deposition on soft polymer surfaces

Nano-topography formation on material surfaces gains increasing interest in sensor, biomedical, optical, tribological applications by the wide options of introducing functionalities to the surface. While top-down structuring processes are not useable for large surfaces, bottom-up techniques, utilizing even material properties for targeted nanostructure formation control, become highly valuable. Self-assembling, fractal-like nano- and microtopography formed by bottom-up processes (physical vapor deposition techniques, magnetron sputtering, pulsed laser deposition) on polymers are presented in this work. Wrinkling effects are due to high stresses in the deposited thin films of different inorganic coating materials - titanium and titanium nitride in the current work - with high adhesion on the polymer substrates (polycarbonate, polyimide, polyamide, thermoplastic polyurethane). The feature size of the nano-hills and vermicular-like structures in the size between 10 nm and 100 μm distance and up to 300 nm height is controlled by the mechanical properties in the formed compound material.     

Investigations of failure mechanisms at Ta and TaO diffusion barriers by secondary neutral mass spectrometry

One of the most important processes in Cu metallization for highly integrated circuits is to fabricate reliable diffusion barriers. Recently, thin films made of refractory metals and their compounds have been widely used in solid-state electronics as barriers because of their good electric properties, favourable thermal properties and chemical stability. Thermal stability of Tantalum (Ta) and Tantalum-oxide (TaO_x) layers as a diffusion barrier in Si/Ta/Cu, Si/TaO_x/Cu and Si/Ta-TaO_x/Cu systems have been investigated. Si/Ta (10 nm)/Cu (25 nm)/W (10 nm), Si/TaO_x (10 nm)/Cu (25 nm)/W (10 nm) and Si/Ta (5 nm)TaO_x (5 nm)/Cu (25 nm)/W (10 nm) thin layers were prepared by DC magnetron sputtering. A tungsten cap layer was applied to prevent the oxidation of the samples during the annealing process. The samples were annealed at various temperatures (473 K-973 K) in vacuum. Transmission Electron Microscopy, X-ray diffraction, X-Ray Photoelectron Spectroscopy and Secondary Neutral Mass Spectrometry were used to characterize the microstructure and diffusion properties of the thin films. Our results show that at the beginning phase of the degradation of the Si/Ta/Cu system Ta atoms migrate through the copper film to the W/Cu interface. In the Si/TaO_x/Cu system the crystallization of TaO and the diffusion of Si through the barrier determine the thermal stability. The Ta-TaO bilayer proved to be an excellent barrier layer between the Si and Cu films up to 1023 K. The observed outstanding performance of the combined film is explained by the continuous oxidation of Ta film in the TaO_x-Ta bilayer.     

Surface poisoning in the nucleation and growth of palladium atomic layer deposition with Pd(hfac)2 and formalin

Palladium (Pd) atomic layer deposition (ALD) can be performed with Pd(hfac)₂ (hfac = hexafluoroacetyl-acetone) and formalin as the reactants. For Pd ALD on oxide surfaces, the nucleation of Pd ALD has been observed to require between 20 and 100 ALD cycles. To understand the long nucleation periods, this study explored the surface reactions occurring during Pd ALD nucleation and growth on hydroxylated Al₂O₃ substrates. In situ Fourier transform infrared (FTIR) spectroscopy on high surface area nanopowders was used to observe the surface species. The adsorption of Pd(hfac)₂ on hydroxylated Al₂O₃ substrates was found to yield both Pd(hfac)* and Al(hfac)* surface species. The identity of the Al(hfac)* species was confirmed by separate FTIR studies of hfacH adsorption on the hydroxylated Al₂O₃ substrates. Isothermal loss of the Al(hfac)* species revealed second-order kinetics at 448-523 K with an activation barrier of E_d = 39.4 kcal/mol. The lack of correlation between Al(hfac)* and AlOH* species during the loss of Al(hfac)* species suggested that the Al(hfac)* species may desorb as Al(hfac)₃. After Pd(hfac)₂ exposure and the subsequent formalin exposure on hydroxylated Al₂O₃ substrates, only hfac ligands from Pd(hfac)* species were removed from the surface. In addition, the formalin exposure added formate species. The Al(hfac)* species was identified as the cause of the long nucleation period because Al(hfac)* behaves as a site blocker. The surface poisoning by Al(hfac)* species was corroborated by adsorbing hfacH prior to the Pd(hfac)₂ exposures. The amount of Pd(hfac)* species after Pd(hfac)₂ exposures decreased progressively versus the previous hfacH exposure. Pd ALD occurred gradually during the subsequent Pd ALD cycles as the Al(hfac)* species were slowly removed from the Al₂O₃ surface. Ex situ transmission electron microscopy analysis revealed Pd nanoclusters that grew in size and dispersion with increasing number of Pd ALD cycles. These nanoclusters eventually coalesced to form a continuous Pd ALD film. Surface poisoning by the hfac ligands may help to explain the nucleation difficulties for metal ALD on oxide substrates using β-diketonate reactants.     

Optical properties of Cu and Ag nanoparticles synthesized in glass by ion implantation

Metal nanoparticles synthesized by sequentially ion-implanted Ag and Cu into silica glasses have been studied. The implantation doses (×10¹⁶ ions/cm²) were 5Ag, 5Cu and 5Ag/5Cu, respectively. The optical and microstructural properties of the nanoparticles were characterized by optical absorption spectra and transmission electron microscopy (TEM), respectively. Fast nonlinear optical refraction and nonlinear optical absorption coefficients were measured at 1064 nm of wavelength using Z-scan technique. Results in this paper indicate that the nonlinear refractive index for the Ag/Cu implanted system has a higher value compared to single Ag or Cu implantation nanoparticles.