Copper electrodeposition onto the dendrimer-modified native oxide of silicon substrates

Adherent copper films were electrochemically grown onto the native oxide surfaces of Si wafers modified by the adsorption of polyamidoamine (PAMAM) dendrimers. Metallic nuclei of copper grow at isolated nucleation sites, associated with adsorbed dendrimers, and film coalescence can be observed above a metal thickness of about 10,000 monolayers (∼2.5 μm). Film microstructure depends on the deposition mode; higher coverage and better adhesion were obtained by galvanostatic control of the deposition process. It is hypothesized that reduction of Cu²⁺ ions complexed with functional groups of the chemisorbed dendrimer leads to the formation of metallic copper nuclei, and that metal films grow from these nuclei. Further improvement of this process may open the way to the direct integration of metal electrodeposition with silicon microfabrication processes and selective deposition by dendrimer patterning.     

Nanostructures formed by displacement of porous silicon with copper: from nanoparticles to porous membranes

ABSTRACT: The application of porous silicon as a template for the fabrication of nanosized copper objects is reported. Three different types of nanostructures were formed by displacement deposition of copper on porous silicon from hydrofluoric acid-based solutions of copper sulphate: (1) copper nanoparticles, (2) quasi-continuous copper films, and (3) free porous copper membranes. Managing the parameters of porous silicon (pore sizes, porosity), deposition time, and wettability of the copper sulphate solution has allowed to achieve such variety of the copper structures. Elemental and structural analyses of the obtained structures are presented. Young modulus measurements of the porous copper membrane have been carried out and its modest activity in surface enhanced Raman spectroscopy is declared.     

Filling of microvia with an aspect ratio of 5 by copper electrodeposition

The filling of microvias with a diameter of 5 μm and a depth of 25 μm (aspect ratio of 5) by copper electroplating was investigated. Filling experiments were evaluated by analyzing cross-sections of filled vias with scanning electron microscopy and focused ion beam. The fill-up evolution shows a bottom-up mechanism, also known as superfilling mechanism. The evolution of potential with time (chronopotentiometric measurements) was recorded during the fill-up process of vias and is interpreted based on potentiodynamic polarization measurements.The bottom-up fill mode is affected by the concentration of leveler inside the vias. A differential plating rate that is responsible for bottom-up plating, develops along the profile of the via on depletion of the leveler inside the vias. Since the depleted via is less inhibited, the local electrodeposition rate increases in the via. At the top part and outside the via, the electrodeposition rate is strongly inhibited due to a higher leveler concentration comparable to the one in the bulk electrolyte, what results in a low local electrodeposition rate.In this paper, the contribution of levelers to the bottom-up mechanism during the electrodeposition of copper in microvias is investigated. The observed microstructure supports the superfilling mechanism.     

Effect of chloride ions on immersion plating of copper onto porous silicon from a methanol solution

The effect of chloride ions (Cl⁻) during the immersion plating of copper onto porous silicon (PS) from a methanol (MeOH) solution has been studied. The presence of Cl⁻ in the Cu²⁺ solution was found to slow down the rate of copper deposition, as confirmed by inductively coupled argon plasma emission spectroscopy and X-ray photoelectron spectroscopy measurements. The threshold concentration of Cl⁻ at which the deposition of copper is very severely diminished was found to be 0.1 M. The inhibition effect is discussed on the basis of the rest potential values of PS and polarization curve measurements. They revealed that the rest potential of PS upon dipping in these solutions appears to direct the metal deposition. Current density-potential curves show that at Cl⁻ concentrations higher than 0.1 M, the reduction of Cu ions proceeds in two steps; the reduction of Cu(II) to Cu(I) followed by the reduction of Cu(I) to Cu(0). This suggests that Cu(I) species in MeOH solution can be stable over a certain potential range and this stability of Cu(I) is responsible for the inhibition of metal deposition. Fourier transform infrared spectroscopy and scanning electron microscopy (SEM) were also performed to investigate the structural changes and characterizations of PS samples after the plating process.     

Immersion plating of copper onto porous silicon with different thickness

This work aims to detail the mass change of a porous silicon sample during copper immersion plating. Gravimetric measurements and quantification of the deposited copper by induced coupled plasma spectroscopy (ICP) permit to separate the contributions to the mass change. The results indicate that immersion plating proceeds independently of the porous layer thickness at short immersion time. However, after long immersion duration, the deposition stops and thick porous layers are not fully oxidised. The oxidation of the porous layer is homogeneous and proceeds in depth with time, down to several micrometers.     

Exploratory study of copper particles electrodeposition on nickel by induction heating

Copper and the oxides which are spontaneously formed on its surface have numerous interesting properties that can be exploited in fields such as catalysis, gas sensing, antimicrobial activity, etc. Furthermore, metallic nanoparticles (NPs) have many size-dependent properties such as a large surface area to volume ratio that can enhance these copper/copper oxides properties. This work aims to highlight the beneficial effect of induction heating versus conventional heating on the electrodeposition of copper particles on nickel substrates. We showed that in temperature-equivalent conditions, conventional heating leads to a low coverage of the Ni electrode with weakly adherent copper microparticles (these particles having a very large size distribution and uncontrolled morphology) while induction heating leads to a high coverage of the surface with copper nanoparticles (these particles having a sharp unimodal size repartition and a truncated octahedron/octahedron shape exposing mainly (1 1 1) facets). Furthermore, while no crystalline copper oxide could be highlighted for copper nanoparticles electrodeposited at room temperature, induction heating leads to the formation of a crystalline Cu₂O shell that could have interesting catalytic properties, among others.     

Luminescence of mesoporous silicon powders treated by high-pressure water vapor annealing

We have studied the photoluminescence of nanocrystalline silicon microparticle powders fabricated by fragmentation of PSi membranes. Several porosities were studied. Some powders have been subjected to further chemical etching in HF in order to reduce the size of the silicon skeleton and reach quantum sizes. High-pressure water vapor annealing was then used to enhance both the luminescence efficiency and stability. Two visible emission bands were observed. A red band characteristic of the emission of Si nanocrystals and a blue band related to localized centers in oxidized powders. The blue band included a long-lived component, with a lifetime exceeding 1 sec. Both emission bands depended strongly on the PSi initial porosity. The colors of the processed powders were tunable from brown to off-white, depending on the level of oxidation. The surface area and pore volume of some powders were also measured and discussed. The targeted applications are in cosmetics and medicine.     

Nanostructured copper/porous silicon hybrid systems as efficient sound-emitting devices

In the present work, the photo-acoustic emission from nanostructured copper/porous silicon hybrid systems was studied. Copper nanoparticles were grown by photo-assisted electroless deposition on crystalline silicon and nanostructured porous silicon (nanoPS). Both the optical and photo-acoustic responses from these systems were determined. The experimental results show a remarkable increase in the photo-acoustic intensity when copper nanoparticles are incorporated to the porous structure. The results thus suggest that the Cu/nanoPS hybrid systems are suitable candidates for several applications in the field of thermoplasmonics, including the development of sound-emitting devices of great efficiency.     

Transient surface photovoltage studies of bare and Ni-filled porous silicon performed in different ambients

Mesoporous silicon and porous silicon/Ni nanocomposites have been investigated in this work employing light-dark surface photovoltage (SPV) transients to monitor the response of surface charge dynamics to illumination changes. The samples were prepared by anodization of a highly n-doped silicon wafer and a subsequent electrodepositing of Ni into the pores. The resulting pores were oriented towards the surface with an average pore diameter of 60 nm and the thickness of the porous layer of approximately 40 μm. SPV was performed on a bare porous silicon as well as on a Ni-filled porous silicon in vacuum and in different gaseous environments (O₂, N₂, Ar). A significant difference was observed between the ‘light-on’ and ‘light-off’ SPV transients obtained in vacuum and those observed in gaseous ambiences. Such behavior could be explained by the contribution to the charge exchange in gas environments from chemisorbed and physisorbed species at the semiconductor surface.

PACS

81.05.Rm; 73.20.-r; 75.50.-y; 82.45.Yz     

Comparative study of initial stages of copper immersion deposition on bulk and porous silicon

Initial stages of Cu immersion deposition in the presence of hydrofluoric acid on bulk and porous silicon were studied. Cu was found to deposit both on bulk and porous silicon as a layer of nanoparticles which grew according to the Volmer-Weber mechanism. It was revealed that at the initial stages of immersion deposition, Cu nanoparticles consisted of crystals with a maximum size of 10 nm and inherited the orientation of the original silicon substrate. Deposited Cu nanoparticles were found to be partially oxidized to Cu₂O while CuO was not detected for all samples. In contrast to porous silicon, the crystal orientation of the original silicon substrate significantly affected the sizes, density, and oxidation level of Cu nanoparticles deposited on bulk silicon.     

Stability of iodine on ruthenium during copper electrodeposition and its effects on the nucleation behavior of electrodeposited copper

Cyclic voltammetry, current-time-transient measurements, and X-ray photoelectron spectroscopy (XPS) have been used to study the nucleation behavior of electrochemically deposited Cu films on Ru substrates as a function of Ru pre-treatment. Pre-treatment consisted of cathodic polarization in either 1 M H₂SO₄ or in 1 M H₂SO₄ + 1 mM KI, followed by sample emersion and placement in a 1 M H₂SO₄ + 50 mM CuSO₄ plating bath. XPS measurements confirmed the presence of adsorbed I on the Ru surface following pre-treatment in the KI/H₂SO₄ solution. Cyclic voltammogram (CV) data for electrodes either as-received or pre-reduced in H₂SO₄ and then immersed in the plating solution exhibited a broad peak in the overpotential region consistent with oxide reduction followed by Cu deposition. No underpotential deposition (UPD) feature was observed for these electrodes. In contrast, the sample pre-reduced in I-containing electrolyte exhibited a narrow Cu deposition peak in the overpotential region and a UPD Cu feature centered at 80 mV vs. Ag/AgCl. Current-time-transient (CTT) measurements of Cu deposition on as-received electrodes or electrodes pre-reduced in I-free solution exhibited potential-independent kinetics that are not well described by either progressive or instantaneous nucleation models and which at long times indicate a combination of diffusion and kinetic control. In contrast, CTT measurements of deposition kinetics for samples reduced in I-containing electrolyte exhibited complex, potential-dependent behavior and that at long times indicates diffusion control. XPS results also indicated that the iodine adlayer on Ru reduced in I-containing electrolyte is stable upon polarization to at least −200 mV vs. Ag/AgCl. These data indicate that a protective I adlayer may be deposited on an air-exposed Ru electrode as the oxide surface is electrochemically reduced, and that this layer will inhibit reformation of an oxide during the Cu electroplating process. Therefore, electrochemical pre-treatment in I-containing electrolyte may be of practical utility under industrial conditions for Cu electroplating.     

Effects of (NH4)2SO4 and BTA on the nanostructure of copper foam prepared by electrodeposition

Copper foam with dendritic copper nanostructure was synthesized by an electrodeposition process using hydrogen bubbles as dynamic templates. To modify the morphology of the copper nanostructure in the foam walls, (NH₄)₂SO₄ and BTA (benzotriazole) were introduced into the electrolytic bath as chemical additives, and their influences on the morphologies and the structural characteristics of copper deposits were examined by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The mechanical strength and stiffness of the copper foam were evaluated by the compression test. The corncob-like deposits of the copper foam were changed to needle-like nanodendrites by the addition of (NH₄)₂SO₄, which significantly improved the mechanical strength and stiffness due to the self-supporting effects of the tightly interlocked needle-like nanodendrites. In contrast, the copper foam prepared from the solution with (NH₄)₂SO₄ and BTA shows high ductility but low mechanical strength due to the formation to grape-like copper deposits. Both the copper foams exhibited higher mechanical properties than the one with corncob-like deposits formed in the additive-free solution. The reaction mechanism of (NH₄)₂SO₄ and BTA on the nanostructure of the copper foam at high cathodic current density was clarified by analyzing the effects of the additives on the copper deposition reaction and hydrogen gas evolution reaction, respectively.     

Copper electrodeposition on pyrolytic graphite electrodes: Effect of the copper salt on the electrodeposition process

The electrodeposition of copper on pyrolytic graphite from CuSO₄ or Cu(NO₃)₂ in a 1.8 M H₂SO₄ aqueous solution was investigated. The Cu deposits were formed potentiostatically and characterized by electrochemical methods, scanning electron microscopy, energy dispersive X-ray and X-ray photoelectron spectroscopy. It was found that the deposition of copper in the presence of CuSO₄ induced the codeposition of sulfate anions. In addition, electrochemical quartz crystal microbalance revealed that the increase of the Cu mass was higher than expected from Faraday's law with the CuSO₄/H₂SO₄ solution. These results confirmed the specific adsorption of anions during the Cu deposition. On the other hand, the use of Cu(NO₃)₂ resulted in a non-contaminated surface with different surface morphologies. The Cu nuclei size, the population density and the surface coverage were monitored as a function of the deposition potential. From the analysis of the chronoamperometric curves, the nucleation kinetics was studied by using various theoretical models. Independently of the Cu source, the nucleation mechanism follows a three-dimensional (3D) process. Copper nucleates according to an instantaneous mode when the deposition potential is more negative than −300 mV versus Ag/AgCl, while the nucleation was interpreted in terms of a progressive mode at −150 mV. The nuclei population densities were also determined by using two common fitting models for 3D nucleation and growth (Scharifker-Mostany and Mirkin-Nilov-Heerman-Tarallo). Their values are reported here as a function of the deposition potential.     

Electroluminescence from porous silicon formed by photoetching in an HF/I<Subscript>2</Subscript> solution

We demonstrate the formation of a light-emitting porous silicon (PSi) layer by photoetching in an HF/I₂ solution. The use of a Xe lamp makes possible a large and homogeneous PSi layer on an n-type Si(100) wafer. An insulating layer has been formed on the PSi layer by chemical oxidation in an acidic solution. These techniques are used to fabricate electroluminescent (EL) devices of metal/insulator/semiconductor (MIS) type. It is shown that the present device is superior with respect to emission efficiency to the conventional Schottky- or metal/semiconductor-type device.     

Magnetic interactions between metal nanostructures within porous silicon

Electrochemically deposited magnetic nanostructures arranged in a three-dimensional system are investigated with respect to their cross-talk between each other. The nanostructures are embedded in porous silicon templates with different morphologies which means pores offering dendritic growth of different strengths. An increase of the uniformity of the pores is concomitant with an increase of the smoothness of the metal deposits which strongly influences the magnetic behavior of the system. Less dendritic structures lead to an increase of the coercivity of the nanocomposite which reveals less cross-talk between the metal deposits due to a modification of the stray fields. The system allows in a cheap and simple way to tune the magnetic interactions of magnetic nanostructures in a three-dimensional arrangement.

PACS

81.05.Rm; 81.07.Gf; 75.75.-c     

Ruthenium electrodeposition on silicon from a room-temperature ionic liquid

Electrochemical deposition of ruthenium on n-type silicon from an ionic liquid is reported for the first time. The study was performed by dissolving ruthenium(III) chloride in a 1-butyl-3-methyl imidazolium hexafluorophosphate (BMIPF₆) room-temperature ionic liquid (RTIL). Cyclic voltammetry (CV) studies demonstrate reduction and stripping peaks at −2.1 and 0.2 V vs. Pt quasi-reference, corresponding to the deposition and dissolution of ruthenium, respectively. Metallic Ru films of ∼100 nm thickness have been deposited and were analyzed using scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS).     

Porous silicon carbide structures with anisotropic open porosity for high- temperature cycling applications

We have prepared porous silicon carbide by a novel two-step template method. Graphite/SiC composites of required size and shape are first fabricated by hot pressing at 2125 °C, followed by the removal of the graphite template by controlled heat treatment. The anisotropy in the composite structure is restored after the removal of the template and porous SiC with anisotropic properties is obtained. The composite can be easily machined by electrical discharge machining because of the presence of graphite, and porous SiC can be obtained by heat treatment, solving the inherent difficulty in the machining of SiC. The mechanical properties, thermal conductivity, and thermal shock resistance of porous SiC have been studied in both directions. The material shows good thermal shock resistance in the perpendicular to pressing direction even at 1400 °C. Hence porous SiC suitably machined preserving the proper direction can be a potential candidate for thermal cycling applications.     

Silver–copper electrodeposition from ammonium hydroxide solution: influence of EDTA and HEDTA

The influence of EDTA (ethylenediaminetetraacetic acid, disodium salt) or HEDTA (N-(2-hydroxyethyl)ethylenediaminetriacetic acid, trisodium salt) on silver–copper electrodeposition from ammonium hydroxide solution was investigated. Voltammetric studies showed that silver was deposited at potentials more negative than +0.100 V, while the copper(II) ion was reduced to copper(I) ion and metallic copper at potentials more negative than +0.100 and −0.375 V, respectively. Chronoamperometry, scanning electron microscopy and energy-dispersive X-ray spectroscopy (EDS) indicated that, for deposits obtained at −0.450 V, increasing either the silver content in the silver–copper deposit or the charge density of deposition led to dendritic growth. Moreover, dendritic growth decreased when either the EDTA or HEDTA concentration increased. EDS analysis of the deposits obtained at −0.200 V showed codeposition of copper with silver, which was attributed to Cu(I) ion disproportionation to Cu(0) and Cu(II). Moreover, the silver–copper deposits obtained at −0.200 V, from a solution containing EDTA or HEDTA, were non-dendritic in spite of the high silver content. The presence of EDTA and HEDTA improved the silver–copper morphology. X-ray diffraction analysis indicated that the silver–copper electrodeposit was a supersaturated solid solution.     

Soybean hull functionalized by phosphoric acid for sorption of copper from aqueous solution

One kind of potentially biodegradable cationic sorbent, which bears hydroxyl groups of phosphoric acid as its functional groups, with high sorption capacity of copper was prepared by thermochemically esterifying phosphoric acid (PA) onto soybean hull. Sorption of Cu(II) from aqueous solution onto modified soybean hull (MSH) was investigated in a batch system. The sorption experiments were performed under various conditions such as different initial pH, copper concentration, MSH dosage, and contact time. The maximum copper sorption was obtained when initial solution pH≥3.5. The isothermal data of copper sorption fitted the Langmuir model and the sorption process could be described by the pseudo-first-order kinetic model. The maximum sorption capacity (Q _m ) of MSH for Cu(II) was 31.55 mg/g. For 100 mg/l of Cu(II) solution, a sorption ratio above 91% could be achieved by 5.0 g/l of MSH. The equilibrium of Cu(II) sorption was reached within 50 min. The foreign cation and chelator in Cu(II) solution caused decline of Cu(II) sorption.     

SERS active silver nanoparticles synthesized by inkjet printing on mesoporous silicon

Inkjet printing technique is exploited for the synthesis of Ag nanoparticles (NPs) patterned on electrochemically etched silicon-based substrates. The nanostructure morphology, here analyzed by scanning electron microscopy, is dictated by the ink composition and the printing parameters. Under suitable excitation conditions, resonant surface-enhanced Raman scattering (SERS) performed on such metal-dielectric nanostructures can approach single-molecule detection as recently demonstrated on silvered porous silicon synthesized by immersion plating.

PACS

78.67.Bf; 78.30.-j