Electrodeposition of Co-Cu-Zn/Cu multilayers: influence of anomalous codeposition on the formation of ternary multilayers

Electrodeposited Co-Cu-Zn/Cu multilayers have been prepared with various control modes. It was found in all cases that the Zn content of the magnetic layer is higher than that in the corresponding dc-plated sample. The data of the composition analysis were elucidated by the assumption of anomalous codeposition of Zn and Co. When the less noble layer is deposited, a Zn-rich zone is produced first, then it is covered with a Co-rich layer. If exchange reaction was allowed during the pulse-plating, Co dissolved selectively while the Zn content of the Co-rich layer remained unchanged. The relative resistance of Zn against the exchange reaction is due to the limited accessibility of the Zn-rich zone of the sample rather than electrochemical reasons. The structure of the deposit was analyzed by X-ray diffraction (XRD). It was revealed that Zn incorporation leads to strongly textured deposits with (1 1 1) orientation. The Zn atoms also enlarge the lattice distances of all phases formed. The incorporation of Zn into the magnetic layer of the multilayers decreases the magnetoresistance of the samples.     

Characterisation of CoNi(Cu)/Cu multilayers deposited from a citrate electrolyte in a flow channel cell

CoNi(Cu)/Cu multilayers consisting of 50 and 200 bi-layers were deposited from a citrate electrolyte in a flow channel cell by a dual pulse plating technique. The dissolution of the ferromagnetic components during pulse plating was studied using an oscilloscope and cyclic voltammetry. It was found that the dissolution was suppressed due to the passivation of the ferromagnetic layers before the deposition of an atomic layer of nonmagnetic component on them. The passivation was a function of the nickel ion concentration in the electrolyte. X-ray studies showed that the deposit had a preferred crystal orientation of [1 1 1] and suggested the formation of a super-lattice. Atomic force microscopy studies showed a four-fold increase of the roughness of the ferromagnetic surface with increasing layer thickness from 6 to 10 nm, whereas the roughness of the nonmagnetic surface only changed slightly with increasing layer thickness. The multilayers exhibit giant magnetoresistance.     

Electrochemical behaviour and physical properties of Cu/Co multilayers

Cobalt/copper multilayer formation was analysed over different substrates in order to control the bilayer thickness and quality of coatings. Using a sulphate-citrate bath, at pH 4.7, electrodeposition conditions were optimised to prepare good alternate Cu/Co layers with high efficiency, by minimising the oxidation of cobalt layers during copper deposition. For multilayers with cobalt and copper layers of several nanometers, direct observation by scanning electron microscopy (SEM) or tapping mode-atomic force microscopy (TMAFM) gives layer thickness in agreement with the value calculated from deposition charges. Therefore, this calculation has been used to estimate the thickness of the thinner layers for which direct observation was difficult or impossible. A relation between the response of different characterisation methods was found. When the thickness of each layer in Cu/Co multilayers is >1.8-2 nm, potentiodynamic stripping experiments show separate peaks related to cobalt and copper oxidation. In these conditions, magnetoresistance of the coating is low. For thinner layers, the stripping response shows overlapping peaks or even a single oxidation peak. In these conditions the magnetoresistance begin to increase.     

Preparation and Characterisation of Electrodeposited Ni—Cu/Cu Multilayers

Ni–Cu/Cu multilayers have been, grown from a single electrolyte under potentiostatic conditions at different electrolyte pH values. The current-time transients recorded during deposition indicated different growth modes of the Ni–Cu layers. Structural characterisation by X-ray diffraction revealed that the multilayers have the same crystal structure and texture as their (1 0 0) textured polycrystalline Cu substrate. Scanning electron microscopy showed that the films grown at low pH (2.2) have smoother surfaces than those grown at high pH (3.0). Energy dispersive X-ray analysis revealed that the magnetic layers of the multilayers electrodeposited at high pH contain much more Cu compared to those deposited at low pH. Anisotropic magnetoresistance was found for nominal Cu layer thicknesses below 0.6 nm, and giant magnetoresistance (GMR) above 0.6 nm. The shape of the magnetoresistance curves for GMR multilayers indicated the predominance of a superparamagnetic contribution, possibly due to the discontinuous nature of the magnetic layer. For multilayers with the same bilayer and total thicknesses, the GMR magnitude decreased as the electrolyte pH increased. Besides possible structural differences, this may have come from a strong increase in the Cu content of the magnetic layers since this causes a nearly complete loss of ferromagnetism at room temperature.     

Electroless thin film CoNiFe-B alloys for integrated magnetics on Si

Electroless magnetic thin films have been deposited from borane-based baths suitable for use in integrated magnetics on Si applications. The baths were developed for compatibility with standard photoresist for microfabrication of integrated magnetics on Si. The specific formulations, which differ from those reported previously, yield uniform, high saturation magnetisation (up to 2.15 T) deposits with low coercivity (<2 Oe). The resistivity of the film can be increased to minimise eddy current losses by using higher dimethylamine borane (DMAB) content or the inclusion of a second reducing agent, hypophosphite, to facilitate phosphorus codeposition of up to 7 at.%. The Ni content in the plating bath has been shown to exert significant influence over the composition, deposition rate and coercivity. XRD analysis suggests that the deposits consist of nanocrystalline phase with grains <20 nm. Such small grains are consistent with the observed low coercivity of the deposits.     

Electrodeposition of Co-Ni and Co-Ni-Cu systems in sulphate-citrate medium

Electrodeposition of Co-Ni and Co-Ni-Cu alloys was performed in a sulphate-citrate medium. Experimental electrodeposition parameters (pH, cobalt(II), nickel(II) and citrate concentrations) were varied in order to analyse their influence on the deposition. Anomalous Co-Ni codeposition occured in the citrate medium. High [Ni(II)]/[Co(II)] ratios (above 5) were suitable for the preparation of homogeneous magnetic Co-rich Co-Ni deposits of hexagonal close-packed (hcp) structure or face centred cubic (fcc) structure as a function of the deposition potential.The presence of very low copper(II) concentrations (<10⁻² mol dm⁻³) in the nickel-cobalt bath makes it possible to incorporate copper in the deposits in amounts ranging from 5 to 60% Cu, although uniform deposits are obtained only for low copper percentages. These ternary deposits are solid solutions with fcc structure and magnetic behaviour both dependent on the deposition potential.     

电沉积Ni80Fe20/Cu纳米多层膜及其巨磁电阻效应

采用单槽控电位双脉冲技术在n-Si（111）晶面上制备了［Ni₈₀Fe₂₀/Cu］_n多层膜,用SEM观测了多层膜的断面形貌,利用X射线衍射（XRD）表征了多层膜的超晶格结构。采用四探针法研究了多层膜的巨磁电阻（GMR）性能,结果表明,多层膜的GMR值随着Cu层厚度的变化发生周期性振荡,随着NiFe层厚度的增加先增大后减小;当样品结构为［NiFe（1.6 nm）/Cu（2.6 nm）］₈₀时,GMR值可达6.4%;多层膜的最低饱和磁场仅为750Oe。磁滞回线测试结果表明,反铁磁耦合多层膜具有较小的矩形比,更适宜作为磁头材料。     

Electrochemical deposition of copper and ruthenium on titanium

Copper electrochemical deposition on titanium with a ruthenium seed layer was investigated. The chemicals for the acid-bath ruthenium electrochemical deposition were ruthenium(III) chloride hydrate (RuCl₃·3H₂O), hydrochloric acid (HCl), sulfamic acid (NH₂SO₃H), and polyethylene glycol. The chemicals for the acid-bath copper electrochemical depositions were copper(II) sulfate hydrate (CuSO₄·5H₂O), sulfuric acid (H₂SO₄), and polyethylene glycol. Results were analyzed by field-emission scanning electron microscopy (FESEM), atomic force microscopy (AFM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Rutherford backscattering spectrometry (RBS). Ruthenium thin film of ∼30 nm thickness, with equiaxial grains <10 nm, was deposited, on a blanket Ti with a root mean square roughness of 8.3 nm, at 2 V for 90 s. XPS and RBS analyses showed the presence of metallic Ru. The Ti substrate was found stable with respect to ECD of Ru but the Ru/Ti bilayer was not found stable in the Cu acid bath, resulting in the diffusion of Ti into Ru film. The depth profiling studies indicates that Ru film thickness ca. 1.4 nm and deposition time of 10 s can act as a good seed layer.     

Fabrication of magnetic nanodot array using electrochemical deposition processes

We investigated fabrication processes of magnetic nanodot arrays for the ultra-high density magnetic recording media by using an electrodeposition. A CoZrNb underlayer was sputter-deposited on a glass disk substrate as a soft magnetic underlayer (SUL). Nano-patterns were formed on the substrate by UV-nanoimprint lithography (UV-NIL) and CoPt was electrodeposited into the nano-patterns. For obtaining uniform CoPt nanodot arrays with high perpendicular coercivities, we applied thin Cu intermediate layer on CoZrNb SUL and minimized its thickness. As a result, we obtained CoPt nanodot arrays with 150-nm diameter, 300-nm pitches, and 20-nm heights, which have uniform structures, on the substrates with the construction of Cu (1-2 nm)/CoZrNb (100 nm)/Cr (5 nm)/glass disk. The perpendicular coercivity of the CoPt nanodot arrays was as high as 5.4 kOe. From these results, we showed that the Cu intermediate layer with even 1-2 nm thick considerably improved the deposition condition on the substrates with CoZrNb SUL to successfully fabricate CoPt nanodot arrays with the diameter and pitches of 80 nm and 160 nm with sufficient uniformity.     

Electrodeposition of Ni-Co-Cu/Cu multilayers: 2. Calculations of the element distribution and experimental depth profile analysis

It has long been known that a concentration gradient can develop in electrodeposits along the growth direction as a result of the combined impact of anomalous codeposition and mass trasnport limitation of the reactants. It is shown in the present paper that this composition change in electrodeposited Co-Ni-Cu/Cu multilayers can be verified by secondary neutral mass spectrometry (SNMS). Various electrodeposited samples have been analyzed and the resulting composition profiles have been compared to the calculation based on the non-destructive analysis of the overall composition. The change of the Co:Ni ratio in the magnetic layer along the growth direction has been verified. A calculation method has been proposed by which the local composition of the magnetic layer can be estimated from the thickness dependence of the overall multilayer composition. It has also been shown that the deviation of the experimental depth profile data from the estimation based on the variation of the total composition with the Co-Ni-Cu layer thickness can be ascribed to the roughness increase during the sputtering in the SNMS instrument.     

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.     

Electrochemical deposition of cylindrical Cu/Cu2O microstructures

Cylindrical microstructures of Cu/Cu₂O have been electrochemically produced from the self-oscillating Cu(II)-lactate system using etched ion track polycarbonate membranes as templates. After removal of the polymer, arrays of free-standing cylinders were obtained. The influence of the applied current density and the deposition temperature on the oscillation pattern and quality of the deposited wires were studied in detail for pores having a diameter of about 1000 nm. The widest current density range for oscillations was found at 25 °C. Under these conditions the deposited wires were of equal length and showed smooth contours, while a granular structure was observed at higher temperatures.     

Interface structure of photonic multilayers prepared by plasma enhanced chemical vapor deposition

The structures of substrate/layer, layer/layer, and layer/air interfaces in optical multilayers made using plasma enhanced chemical vapor deposition (PECVD) have been probed for the first time using X-ray reflectivity and neutron reflectivity. From the point of view of optical applications the interfaces are extremely sharp, sharper than is often achievable with the self-assembly of block copolymers or deposition techniques in which the polymer layers contact while in a fluid state. The average interface width, a_I, between layers made from different precursors is about 40 Å (16 Å rms). The layer/layer interfaces are generally 2-3 times broader than the layer/air interfaces. Polymeric fluorocarbon films deposited on a Si substrate using PECVD with octafluorocyclobutane (OFCB) monomer show uniform scattering length density with depth except for a region of molecular thickness immediately adjacent to the substrate. Films made from deuterated benzene show uniform density throughout the film thickness.     

Effect of sub-layer thickness on magnetic and giant magnetoresistance properties of Ni-Fe/Cu/Co/Cu multilayered nanowire arrays

Ni–Fe/Cu/Co/Cu multilayered nanowire arrays were electrodeposited into anodic aluminum oxide template by using dual-bath method at room temperature. Scanning electron microscopy and transmission electron micros-copy were used to characterize the morphology and structure of the multilayered nanowire arrays. Vibrating sample magnetometer and physical property measurement system were used to measure their magnetic and giant magnetoresistance (GMR) properties. The effect of sub-layer thickness on the magnetic and GMR proper-ties was investigated. The results indicate that magnetic properties of electrodeposited nanowires are not affect-ed obviously by Cu layer thickness, while magnetic layers (Ni–Fe and Co layers) have significant influence. In addition, GMR ratio presents an oscillatory behavior as Cu layer thickness changes. The magnetic and GMR properties of the multilayered nanowire arrays are optimum at room temperature for the material structure of Ni–Fe (25 nm)/Cu (15 nm)/Co (25 nm)/Cu (15 nm) with 30 deposition cycles.     

Electrodeposition of hard magnetic films and microstructures

Electrochemical deposition of materials with hard magnetic properties in the as-deposited state is essential for the efficient integration of micro-magnetic components into MEMS devices. Here we discuss the growth process and the microstructure-magnetic properties correlation for two Co-rich alloys, Co-Ni-P and Co-Pt. Under suitable synthesis conditions, these materials exhibit perpendicular anisotropy and hard magnetic properties in the as-deposited state; in addition, such properties are maintained up to several micrometer film thickness through close control of the film microstructure. In the case of Co-Ni-P films we achieved a saturation magnetization of 1.21 T (963 emu/cm³), perpendicular coercivity up to 188 kA/m (2.36 kOe) at a thickness of 10 μm, and energy products up to 4.2 kJ/m³. Co-rich Co-Pt films were grown on several substrates - Cr, Cu(0 0 1), Cu(1 1 1), and Ru(0 0 0 1) - in order to control magnetic anisotropy and achieve optimum hard magnetic properties. Cu(1 1 1) contributes to stabilize the hexagonal hcp phase at high current density yielding excellent hard magnetic properties, although only in films thicker than 100 nm; saturation magnetization in these films was about 1.04 T (828 emu/cm³). Perpendicular coercivities up to 485.6 kA/m (6.1 kOe) were obtained in 1 μm thick film deposited at 50 mA/cm². Ru(0 0 0 1) seed layers provide an appropriate interface structure to further facilitate the epitaxial growth of hcp films, yielding hard magnetic properties and perpendicular coercivity with a squareness ∼1 in films as thin as 10 nm. The hard magnetic properties were only marginally compromised at large film thickness. Deposition at higher current density (50 mA/cm²) favored markedly improved hard magnetic properties. The Co-Pt films on Ru exhibited perpendicular anisotropy with anisotropy constant up to 1.2 MJ/m³. The electrodeposition process was further extended to fill lithographically patterned hole arrays (850 nm diameter, center-to-center distance 2550 nm and about 700 nm thick resist), yielding arrays of micron-sized hard magnetic cylinders with perpendicular coercivity of 361 kA/m (4.54 kOe) and high squareness.     

Magnetic anisotropy in isotropic and nanopatterned strongly exchange-coupled nanolayers

In this study, the fabrication of magnetic multilayers with a controlled value of the in-plane uniaxial magnetic anisotropy field in the range of 12 to 72 kA/m was achieved. This fabrication was accomplished by the deposition of bilayers consisting of an obliquely deposited (54°) 8-nm-thick anisotropic Co layer and a second isotropic Co layer that was deposited at a normal incidence over the first layer. By changing the thickness value of this second Co layer (X) by modifying the deposition time, the value of the anisotropy field of the sample could be controlled. For each sample, the thickness of each bilayer did not exceed the value of the exchange correlation length calculated for these Co bilayers. To increase the volume of the magnetic films without further modification of their magnetic properties, a Ta spacer layer was deposited between successive Co bilayers at 54° to prevent direct exchange coupling between consecutive Co bilayers. This step was accomplished through the deposition of multilayered films consisting of several (Co_{8 nm-54°}/Co_{X nm-0°}/Ta_{6 nm-54°}) trilayers.     

Long-term stability of Cu/Pd nanoparticles and their feasibility for electroless copper deposition

Poly-vinylpyrrodione (PVP) protected Cu/Pd nanoparticles synthesized with citric complexing agent were developed as activator for electroless copper deposition in printed-circuit boards (PCBs) industry. Cu/Pd nanoparticles in different molar ratio were employed in electroless copper deposition and found that the catalytic activity was influenced not only by the amount of Pd content or particle size but also by the surface protected PVP layer. From the time-resolved electroless copper deposition, we suggested that the catalytic efficiency should be evaluated by both initial activity and the structure of deposited copper film. As a result, the Cu/Pd nanoparticles of molar ratio = 1/2 was found to have best catalytic activity which was comparable to traditional Pd/Sn or pure Pd activator. In regard to the most concerned stability issue of Cu-content system, a surprising slow galvanic corrosion of Cu was found when Cu/Pd nanoparticles were exposed to the open air. Besides, slightly oxidation of Pd was found after air-exposure. Surprisingly, these Cu/Pd colloids maintain part of activity and well suspension even after 6-month exposure, suggesting well long-term stability as activator. In short, Cu/Pd nanoparticles synthesized with citric complexing agent with high catalytic activity and long-term stability was a promising activator for electroless copper deposition.     

All-wet fabrication process for ULSI interconnect technologies

“All-wet process” for fabrication of Cu wiring on a silicon chip was proposed as a novel ultra-large scale integration (ULSI) interconnect technology for integrated circuits (ICs) applications. Electroless-NiB film was deposited on SiO₂/Si substrate modified by self-assembled-monolayer (SAM) activated with PdCl₂. The NiB film formed by this method has highly uniform, with good adhesion to the substrate and with good diffusion barrier characteristics against Cu diffusion. Cu was electrodeposited directly on the electroless NiB film that acted as a seed layer. This was done without any conventional conductive or adhesive layer that is conventionally formed by physical vapor deposition (PDV). The thermal stability of electroless NiB layer as a barrier preventing copper from diffusing into the SiO₂/Si substrate was evaluated by secondary ion mass spectroscopy (SIMS) and sheet resistance measurement at several annealing temperatures. It was confirmed that the electroless NiB film blocked Cu diffusion and kept the layer integrity under annealing temperatures of up to 400 °C for 30 min. The same process of electroless NiB was used for the capping layer that was also formed by “wet process”, as the electroless NiB film deposited selectively onto a surface of Cu wiring was also applicable to a capping layer. We conclude that the proposed process is very promising for sub-100 nm technologies as it offers a variety of desirable properties: it has good step coverage while showing good barrier and seed layer properties.     

Novel mixed method for the electrochemical deposition of thick layers of Bi2+xTe3−x with controlled stoichiometry

A new method for the electrochemical deposition of Bi_2+xTe_3−x is presented, which combines voltage-controlled deposition pulses with current-controlled resting pulses. This method is based on results of a comprehensive electrochemical investigation including cyclic voltammetry, chronoamperometry and chronopotentiometry, which has been performed on the system Bi and Te on Pt in 2 M HNO₃. The influence of electrolyte composition, deposition potential and deposition pulse duration on morphology and stoichiometry of the deposited material as well as the variation of the composition over the thickness of the layer has been investigated by means of SEM and EDX. The crystal structure was examined with XRD. Layers deposited with the new method show a constant and reproducible stoichiometry over their entire thickness. Layers of up to 800 μm thickness deposited with deposition rates of up to 50 μm/h have been achieved. The composition and hence the thermoelectric behavior may be adjusted via electrolyte composition or the deposition potential. Fabrication of n-type and, for the first time, p-type Bi_2+xTe_3−x is demonstrated and verified by measurements of the Seebeck coefficients. The suitability of the proposed method for low-cost fabrication of micro-thermoelectric devices is shown. The advantages of this method may also apply for electrochemical deposition of other binary or ternary compounds.     

Electroplating of a Co–Cu alloy from a citrate bath containing boric acid

The effects of bath composition, current density and temperature on cathodic polarization, cathodic current efficiency of codeposition, composition and structure of Co–Cu alloys electroplated on a steel substrate from citrate baths have been studied. Addition of boric acid to citrate electrolyte increases the percentage of Co in the deposits and improves the quality of these deposits. The cathodic current efficiency of the baths is relatively high and increases with increases in the metal content in the bath and the current density but decreases with temperature. The composition of the deposit is controlled by the applied current density. At low current densities, Cu‐rich alloys were obtained. At higher current densities, the composition of the alloys was controlled by the limiting current density of Cu codeposition. The Co content of the deposits increases with increases in the metal content in the bath and the temperature. The structure of the deposited alloys was characterized by anodic stripping and X‐ray diffraction techniques. The deposited alloys consisted of a single solid solution phase with a face‐centred cubic structure. © 2000 Society of Chemical Industry