Tunable micropatterned substrates based on poly(dopamine) deposition via microcontact printing

A simple technique was developed to fabricate tunable micropatterned substrates based on mussel-inspired surface modification. Polydopamine (PDA) was developed on polydimethylsiloxane (PDMS) stamps and was easily imprinted to several substrates such as glass, silicon, gold, polystyrene, and poly(ethylene glycol) via microcontact printing. The imprinted PDA retained its unique reactivity and could modulate the chemical properties of micropatterns via secondary reactions, which was illustrated in this study. PDA patterns imprinted onto a cytophobic and nonfouling substrates were used to form patterns of cells or proteins. PDA imprints reacted with nucleophilic amines or thiols to conjugate molecules such as poly(ethylene glycol) for creating nonfouling area. Gold nanoparticles were immobilized onto PDA-stamped area. The reductive ability of PDA transformed silver ions to elemental metals as an electroless process of metallization. This facile and economic technique provides a powerful tool for development of a functional patterned substrate for various applications.     

Synthesis of self-standing Pd nanowires via galvanic displacement deposition

This work shows that it is possible to obtain self-standing Pd nanowires into anodic alumina membranes by a simple metal displacement deposition. By using a proper arrangement, specifically designed in order to optimize the process, polycrystalline Pd nanowires were deposited from a solution containing Pd(NH₃)₄(NO₃)₂ as precursor. Morphological analysis showed the formation of perfectly aligned nanowires with a uniform diameter throughout the entire length. This last parameter was controlled by both the deposition time and the ratio between the anodic area (active metal) and the cathodic area (pore bottom).     

Particle deposition onto micropatterned charge heterogeneous substrates: trajectory analysis

A trajectory analysis of particles near a micropatterned charged substrate under radial impinging jet flow conditions is presented to investigate the effect of surface charge heterogeneity on particle trajectory and deposition efficiency. The surface charge heterogeneity is modeled as concentric bands of specified width and pitch having positive and negative surface potentials. The flow distribution is obtained using finite element analysis of the governing Navier-Stokes equations. The particle trajectory analysis takes into consideration the hydrodynamic interactions, gravity, van der Waals and electrostatic double layer interactions. The presence of surface charge heterogeneity on the substrate gives rise to an oscillating particle trajectory near the collector surface due to repulsive and attractive forces. As a result of the coupled effects of hydrodynamic and colloidal forces, the particle trajectories and deposition efficiencies are increasingly affected by surface charge heterogeneity as one moves radially away from the stagnation point. The results indicate that it is possible to render collectors with up to 50% favorable surface fraction completely unfavorable by modifying the ratio of the radial to normal fluid velocity. Utilizing the real favorable area fraction of the collector, the patch model expression for calculating the deposition efficiency is modified for impinging jet flow geometry.     

Synthesis and characterization of silicon nanowires on mesophase carbon microbead substrates by chemical vapor deposition

Silicon nanowires (SiNWs) have been fabricated by chemical vapor deposition at ambient pressure using SiCl(4) as a silicon source and mesophase carbon microbead powder as a substrate without any templates and/or metal catalysts. The SiNWs have a crystalline core with a very thin amorphous SiO(x) sheath. The obtained SiNWs are homogeneous with average diameters below 50 nm and lengths up to micrometers. Temperature and time effects on the growth of SiNWs were systematically studied. Higher reaction temperatures and longer reaction times resulted in larger diameters and higher yields of SiNWs. SiNWs with a better crystallinity can be obtained at higher temperatures and longer reaction times. The obtained SiNWs were characterized by field-emission scanning electron microscopy, X-ray diffraction, Raman spectroscopy, and transmission electron microscopy.     

Effect of 3-S isothiuronium propyl sulfonate on electroless nickel deposition

The effects of organic additive, 3-S isothiuronium propyl sulfonate (UPS) on bath stability, deposition rate, reaction activation energy, and Ni-P coating composition in acidic electroless nickel (EN) plating were investigated. The study was performed by measuring the polarization curves and X-ray fluorescence spectrometer (XRF) in combination with X-ray photoelectron spectroscopy (XPS) analysis. The results show that UPS improves bath stability and increases the reaction activation energy. At lower concentration, UPS is an effective accelerator for EN deposition; whereas, at higher concentration, it decreases deposition rate. It also reveals that UPS inhibits the anodic oxidation of hypophosphite and accelerates the cathodic reduction. In addition, UPS decreases the phosphorus content in Ni-P deposit and can be adsorbed on the deposit surface and compound with Ni²⁺. On the basis of these results, the effect mechanism of UPS on electroless nickel deposition was deduced.     

Process analysis of electroless nickel deposition baths using optical spectroscopies

Summary The analytical techniques of Vis-spectrophotometry and FTIR spectroscopy have been applied to the quantitative determination of important plating bath constituents of an electroless nickel-phosphorus electrolyte under realistic bath operation conditions. In combination with multivariate calibration methods (partial-least squares (PLS)- and principal component (PCR) regression) Ni²⁺, the reducing agent H₂PO ₂ ^– and its oxidation product HPO ₃ ^– could be directly determined even in the presence of other bath constituents like malic, lactic and adipic acids. For Ni²⁺, absorbance spectra in the 500–900 nm wavelength range were used to develop a PLS calibration model that allows to compensate matrix influences on the Ni²⁺ spectrum. PLS regression was carried out in the concentration range 0.5–6 g l^–1 Ni²⁺ with independently varying bath parameters (concentration of other bath constituents, pH and temperature). Evaluation of the model by predicting the concentrations of test samples which had been drawn from real process solutions of a Ni plating bath yielded a root-mean-squared error of 0.06 g l^–1. The metal concentration of the nickel electrolyte in a compact electroplating unit was monitored in-line by measuring spectra by means of a Vis-spectrometer adapted to the process via quartz glass fiber optical cables of 50 m length. A comparison of the in-line data with potentiometric off-line reference analyses showed good agreement of both data sets with a root mean-squared error of 0.15 g l^–1. The potential of FTIR spectroscopy for process analysis of plating bath solutions could be demonstrated by measuring off-line the concentrations of H₂PO ₂ ^– and HPO ₃ ^– . For these two components calibration samples containing all other main bath constituents were used to set up a PCR calibration model with IR spectra measured in the range from 850 to 1800 cm^–1 with an ATR trough technique. The data showed — within the error of the method of about 10% — generally a good accordance with the stoichiometry of the Ni²⁺/H₂PO ₂ ^– reduction process. The correlation of both parameters which was confirmed in these experiments could allow effective bath control with minimum analytical instrumentation, e.g. only a Vis-spectrophotometer.Dedicated to Professor Dr. Wilhelm Fresenius on the occasion of his 80th birthday     

Investigation of the mechanism of nickel electroless deposition on functionalized self-assembled monolayers

We have investigated the seedless electroless deposition (ELD) of Ni on functionalized self-assembled monolayers (SAMs) using scanning electron and optical microscopies, X-ray photoelectron spectroscopy, and time-of-flight secondary ion mass spectrometry. For all SAMs studied, the Ni deposition rate is dependent on the bath pH, deposition temperature, and complexing agent. In contrast to the physical vapor deposition of Ni on SAMs, electrolessly deposited Ni does not penetrate through the SAM. This behavior indicates that ELD is a suitable technique for the deposition of low-to-moderate reactivity on organic thin films. We demonstrate that Ni can be selectively deposited on SAMs using two different methods. First, selectivity can be imparted by the formation of Ni(II)-surface complexes. As a demonstration, we selectively deposited Ni on the -COOH terminated SAM areas of patterned -COOH/-CH(3) or -COOH/-OH terminated SAMs. Here, Ni(2+) ions form Ni(2+)-carboxylate complexes with the -COOH terminal group, which comprise the nucleation sites for subsequent metal deposition. Second, we demonstrate that nickel is selectively deposited on the -CH(3) terminated SAM areas of a patterned -OH/-CH(3) terminated SAM. In this case, the Ni(2+) ion does not specifically interact with the -CH(3) terminal group. Rather, selectivity is imparted by the interaction of the reductant, dimethylamine borane (DMAB), with the -OH and -CH(3) terminal groups.     

Selective growth of ag nanowires on Si(111) surfaces by electroless deposition

Electroless deposition of Ag on atomically flat H-terminated Si(111) surfaces in aqueous alkaline solutions containing Ag ions produced two different sizes of Ag nanowires along atomic step edges: (1) a narrow nanowire of 10 nm in width and 0.5 nm in height and (2) a wide nanowire of 35 nm in width and 11 nm in height. The narrow and wide nanowires were formed by immersion in the solutions containing less than 1 ppb and 8 ppm dissolved-oxygen concentrations, respectively. This result indicates that the dissolved oxygen initiates the formation of Ag nucleation sites and that the fabrication method has a possibility of controlling the size of Ag nanowires.     

Kinetics of the formation of solid phase in electrolyte for electroless nickel deposition

The effect of 1-(3-methyl-4-phenylpyrazolyl)-3-phenylthiourea (PPTU) on the kinetics of formation of particles of the solid phase in the bulk of electrolyte for nickel plating is investigated by photocolorimetry and photon correlation spectroscopy. It is established that PPTU favors the formation of larger particles as compared to the solution containing no additive and, depending on the concentration, can accelerate or slow down the formation and growth of metal particles and affect the location of the process.     

Annealing-free adhesive electroless deposition of a nickel/phosphorous layer on a silane-compound-modified Si wafer

In this study, a post-annealing-free, adhesive nickel/phosphorous (Ni/P) layer was deposited on a 3-[2-(2-aminoethylamino)ethylamino] propyl-trimethoxysilane-modified (ETAS-modified) silicon (Si) surface through an electroless deposition process catalyzed by a novel polyvinylpyrrolidone-capped palladium nanocluster (PVP-nPd). ETAS was covalently bonded on the Si surface, whereas the amino groups on ETAS bridged with the palladium core in the PVP-nPd clusters. Because of the mentioned two effects, the deposited Ni/P layer showed superior adhesion on the Si wafer without the requirement of conventional annealing treatment. Compared with the Ni/P films deposited on bare and ETAS-modified Si surfaces by using commercial Sn/Pd colloids, the adhesion of the Ni/P film catalyzed by PVP-nPd on the ETAS-modified Si wafer improved 4- and 2-fold, respectively.     

Effects of catalyst introduction methods using PAMAM dendrimers on selective electroless nickel deposition on polyelectrolyte multilayers

We studied the effects of catalyst introduction methods using poly(amidoamine) (PAMAM) dendrimers on the nickel patterning of polyelectrolyte multilayer (PEM)-coated substrates. Three different approaches to palladium catalyst introduction using microcontact printing as the patterning technique were utilized and compared. The catalyst introduction methods are (1) direct catalyst stamping, (2) directed assembly using PAMAM dendrimer stamping, and (3) catalyst encapsulation and reduction to nanoparticles within PAMAM dendrimers before stamping. After patterning, the sample surfaces were placed in an electroless bath where nickel was selectively plated onto the patterns. The patterned surfaces were characterized using optical microscopy, atomic force microscopy, scanning electron microscopy, and energy-dispersive X-ray spectroscopy. The metal plating rates on different homogeneous surfaces that simulate the patterned surfaces were measured using a quartz crystal microbalance. In addition, the effect of PEM film thickness (i.e., number of bilayers) on the selectivity of nickel patterning was investigated.     

Copper nanoparticles seeded functionalized‐PVC plastic surface for electroless nickel deposition

A novel and facile activation process for electroless nickel deposition was developed. The semi‐interpenetrating polymer network hydrogel biofilm was used to functionalize the inert poly(vinyl chloride) (PVC) surface, and then Cu nanoparticles, which can initial the subsequent electroless nickel deposition successfully seeded on the functionalized‐PVC surface. The samples were characterized by scanning electron microscopy, X‐ray photoelectron spectroscopy, X‐ray diffraction, and transmission electron microscopy. The results show that the hydrogel film provided the PVC surface with amino groups and Cu nanoparticles of 20–50 nm in size could be functioned as the catalytic nuclei for the subsequent electroless metal deposition on PVC plastic. It can be concluded that the novel Cu activation was effective for the nickel deposition on PVC surface, because of more chemisorption sites for Cu nanoparticles generated on PVC surface. Copyright © 2013 John Wiley & Sons, Ltd.     

Interwoven nickel(II)-dimethylglyoxime nanowires in 3D nickel foam for dendrite-free lithium deposition

Metal skeletons, such as Nickel Foam (NF) has attracted worldwide interests as stable host for lithium metal anode because of its high stability, large specific surface area and high conductivity. However, most metal skeletons have lithophobic surface and uneven current distribution that result in sporadic lithium nucleation and uncontrolled dendrites growth. Herein, we describe a sequential immersing strategy to generate interwoven Nickel(II)-dimethylglyoxime (Ni-DMG) nanowires at NF to obtain composite skeleton (NDNF), which can be used as an stable host for Li metal storage. The Ni-DMG has proved effective to realize uniform lithium nucleation and dendrite-free lithium deposition. Combing with the three dimensional (3D) hierarchical porous structure, the composite host shows a significantly improved coulombic efficiency (CE) than pristine commercial nickel foam. Moreover, the corresponding Li||Li symmetrical cells can run more than 700 h with low voltage hysteresis 22 mV at 1.0 mA/cm², and Li@NDNF||LiFePO₄ full-cell exhibits a high capacity retention of 82.03% at 1.0 C during 630 cycles. These results proved the effectiveness of metal-organic complexes in governing Li metal growth and can be employed as a new strategy for dendrite-free Li metal anode and safe Li metal batteries (LMBs).     

Synthesis of Ag/Pd nanoparticles via reactive micelles as templates and its application to electroless copper deposition

Ag/Pd nanoparticles have been synthesized with a reactive alcohol-type surfactant, sodium dodecyl sulfate (SDS), without the presence of an external reducing agent. Both UV-vis absorption spectra and X-ray diffraction patterns for the bimetallic and physical mixtures of individual nanoparticles revealed the formation of a bimetallic structure. Based on this method, an ordered 3D grapelike nanostructure was formed, possibly due to transformation of the liquid crystal phase of the micelles. Data from the energy-dispersive X-ray analysis show that the composition of bimetallic nanoparticle is approximately equal to the feeing solution. Furthermore, the Ag/Pd nanoparticles exhibit distinct catalyst for electroless copper deposition and may be a substitute for the conventional palladium system, which is expensive and unstable in operation.     

Metallic single-crystal CoSi nanowires via chemical vapor deposition of single-source precursor

We report the synthesis, structural characterization, and electrical transport properties of free-standing single-crystal CoSi nanowires synthesized via a single-source precursor route. Nanowires with diameters of 10-150 nm and lengths of greater than 10 mum were synthesized through the chemical vapor deposition of Co(SiCl(3))(CO)(4) onto silicon substrates that were covered with 1-2 nm thick SiO(2). Transmission electron microscopy confirms the single-crystal structure of the cubic CoSi. X-ray absorption and emission spectroscopy confirm the chemical identity and show the expected metallic nature of CoSi, which is further verified by room-temperature and low-temperature electrical transport measurements of nanowire devices. The average resistivity of CoSi nanowires is found to be about 510 muOmega cm. Our general and rational nanowire synthesis approach will lead to a broad class of silicide nanowires, including those metallic materials that serve as high-quality building blocks for nanoelectronics and magnetic semiconducting Fe(1-x)Co(x)Si suitable for silicon-based spintronics.     

Synthesis of high-purity GaP nanowires using a vapor deposition method

High-purity gallium phosphide (GaP) nanowires were successfully synthesized on the nickel monoxide (NiO) or the cobalt monoxide (CoO) catalyzed alumina substrate by a simple vapor deposition method. To synthesize the high-purity GaP nanowires, the mixture source of gallium (Ga) and GaP powder was directly vaporized in the range of 850–1000 °C for 60 min under argon ambient. The diameter of GaP nanowires was about 38–105 nm and the length was up to several hundreds of micrometers. The GaP nanowires have a single-crystalline zinc blend structure and reveal the core-shell structure, which consists of the GaP core and the GaPO₄/Ga₂O₃ outer layers. We demonstrate that the mixture of Ga/GaP is an ideal source for the high-yield GaP nanowires.     

Synthesis of hybrid solar cells using CdS nanowire array grown on conductive glass substrates

High-density CdS nanowire (NW) arrays were successfully grown on fluorine-doped tin oxide (FTO)-coated glass substrates by vapor–liquid–solid (VLS) mechanism at a remarkably reduced temperature of ～450 °C. Bi catalyst layer and polyvinyl alcohol (PVA) played a major role in the low-temperature synthesis of high-quality CdS NW arrays. CdS NWs were defect free single crystalline Wurtzite crystals and they were 50–100 nm and 2–5 μm in diameter and length, respectively. CdS NWs were combined with poly[2-methoxy-5-(2′-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV), a conjugated polymer to form organic–inorganic hybrid structures. The UV–visible light absorption and emission behavior of MEH-PPV/CdS hybrids was investigated and their potential to be used as photovoltaic cells was demonstrated.     

Synthesis of nickel nanoparticles supported on metal oxides using electroless plating: Controlling the dispersion and size of nickel nanoparticles

Nickel nanoparticles supported on metal oxides were prepared by a modified electroless nickel-plating method. The process and mechanism of electroless plating were studied by changing the active metal (Ag) loading, acidity, and surface area of metal oxides and were characterized by UV–vis spectroscopy, transmission electron microscopy, scanning electron microscopy, and H₂ chemisorption. The results showed that the dispersion of nickel nanoparticles was dependent on the interface reaction between the metal oxide and the plating solution or the active metal and the plating solution. The Ag loading and acidity of the metal oxide mainly affected the interface reaction to change the dispersion of nickel nanoparticles. The use of ultrasonic waves and microwaves and the change of solvents from water to ethylene glycol in the electroless plating could affect the dispersion and size of nickel nanoparticles.     

Preparation of free-standing nanowire arrays on conductive substrates

By combining supercritical drying technique with AAO template-assisted electrodeposition, noncollapsed, vertically aligned, and free-standing nanowire arrays on a conductive Au film have been fabricated. We also demonstrate that these free-standing nanowire arrays can be feasibly used for fabricating nanowire-based electrically driven devices.