Recessed anodes

RoUs and other relatively simple shapes make use of inert shields and thieves to avoid edge buildup and produce a more even plate thickness. For more compUcated shapes having deeper recesses thicker deposits from cyanide copper baths have been used as an undercoat to the copper sulfate deposit. Acid copper baths operate near 100% efficient over a wide current density range. The cathode efficiency is usuaUy slightly less than the anode efficiency, bringing about a slow increase in copper unless drag-out losses are high. 

In general, a uniform distribution of potential over a regular-shaped passivated surface can be readily obtained by anodic protection. It is much more difficult to protect surface irregularities, such as the recessions around sharp slots, grooves or crevices since the required current density will not be... 

Different views exist as to the reasons for selective dissolution of the asperities. According to older concepts, convection of the liquid is hindered in the solution layers filling recesses hence, reaction products will accumulate there and raise the concentration and viscosity in these layers. Both factors tend to lower a metal s anodic dissolution rate relative to that at raised points. According to other concepts, a surface condition close to passive arises during electropolishing. In this case, the conditions for passivation of the metal at raised points differ from those in recesses. 

In electropolishing, the metal workpiece is made the anode rather than the cathode. Instead of deposition onto the surface of the workpiece, some of the metal dissolves, leaving a bright, polished surface. High points dissolve at a faster rate than recessed areas. Electropolishing is performed to improve adhesion of subsequent electroplates, to deburr and Finish parts, and for decorative purposes (Schaer 1971). 

Let us begin with two common observations involving separated anodes and cathodes. The cathodic protection level obtained on metallic surfaces is often noted to vary with position. The metal is usually less well protected as the distance of the metal surface from the sacrificial or impressed current anode increases. Alternatively, the structure may be overprotected at positions close to the anode, leading to potentially embrittling hydrogen production. Similarly, it is well known that it is more difficult to plate metals electrolytically or throw current into corners or recesses, while exposed edges may receive a thicker plating deposit. The main explanation for this behavior is that the aqueous solution... 

Ateya and Pickering have been concerned with the cathodic polarization of a crevice or recess (21,22). Note that while the term crack has been used, the crack half-angle is zero, which is not realistic for actual cracks. They focus on the situation where the external surface is either anodically or cathodically polarized for various metals. Active/passive electrodes and actively corroding metals have both been considered in these analyses. 

Galvanic corrosion tends to occur when two metals with different electrochemical potentials are electrically connected and exposed in an electrolyte. As a result, the less noble metal will suffer from accelerated corrosion [58]. When excess copper is polished away by copper CMP, copper and barrier metal are exposed to the CMP slurry simultaneously. Copper and barrier metal have different electrochemical potentials and thus trigger galvanic corrosion at the interface between copper and barrier metal at a certain kind of slurry composition. In this galvanic corrosion, electrons are transferred from titanium anode to copper cathode. During overpolishing of the patterned wafer, titanium near the copper structure is recessed owing to dissolution (Ti Ti -I- 2e ) and Cu " ions are preferentially deposited onto... 

Saunders and Brown (38) reported a method to prepare recessed tip silver/silver chloride microelectrodes. In the first step of this procedure they electrochemically sharpened the end of a silver wire (diameter 125 /xin) by dipping it into basic sodium cyanide solution and anodizing it under voltage control. This was followed by an electrochemical chloride-coating step in 100 mM HC1 solution. 

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