With the study of zinc electroplating process by Electrochemical Noise (EN), it was found that the EN generated during the electroplating of large conglomerate zinc deposit has large potential oscillation amplitude and positive potential drift. However, small noise amplitude and little potential drift was seen in the case of compact zinc deposit. Any metal can be plated through zinc electroplating process, but the most common are steel and iron, on which the process offers sacrificial protection.

Steps of Commercial Zinc Electroplating Process
On the commercial scale, zinc electroplating is done by the following steps.
1. Surface of the metal is cleaned in alkaline detergent type solutions, and it is treated with acid, in order to remove any rust or surface scales. Cleanliness is essential for successful zinc electroplating, as the molecular layers of oil or rust can prevent adhesion of the coating.
2. Next, the zinc is deposited on the metal by immersing it in a chemical bath containing dissolved zinc. A DC current is applied, which results in zinc being deposited on the cathode. Alkaline zinc baths are used by the finished products, to produce a more consistent zinc thickness, especially in recesses.
3. Hence an increased protection from corrosion is provided, as the corrosion of the deposited zinc is reduced. The zinc coating can increase the time required for the formation of white rust, by ten times. Finished Products also apply sealers, which are now commonly being specified by the automotive industry, further increasing corrosion protection.

It is very difficult to obtain a uniform thickness of coating, with electroplating technique. The thickness of the coating is very much dependent on the geometry of the object being plated, and it is preferentially on the external corners and protrusions of the metal body, hence not much of it is deposited on internal corners and recesses. Zinc electroplating process is used to make a clean, smooth and corrosion resistant surface. It also makes an excellent undercoat for powder coating or paint and can leave recesses on complex shaped components without sufficient zinc coating, in order to provide corrosion protection.

This article describes a number of key factors affecting copper electroplating for microvia filling and the levels of performance that are currently available to meet the needs of this important market.

Bath Chemistry Parameters Affecting Via Fill
The vast majority of via fill electroplating baths are based on electrolytes consisting of copper sulfate and sulfuric acid. Combining low cost and convenient operation, these sulfate based systems are a well established technology, having now been used in the PCB industry for over 50 years and for via fill applications for over 10 years.

A typical acid sulfate system contains copper sulfate (the primary source of cupric ions), sulfuric acid (for solution conductivity) and chloride ion (as a co-suppressor). Of these components, copper sulfate, typically at concentrations above 200 g/L, has the most significant affect on via filling ability.

Acid copper sulfate system operated without additives typically yield deposits of poor physical properties. Organic additives, typically consisting of materials described as brighteners, suppressors and levelers, are therefore used to further refine deposit characteristics.
Carriers are typically large molecular weight polymers that work in conjunction with small amounts of chloride to form a surface film on the plating surface, which retards the plating reaction. This limits the lifetime of individual growing grains, causing the deposit grain size to become smaller than that obtained without carrier. Carriers are present in relatively high concentration (500 to 3,000 g/L) and show relatively low sensitivity to variations in the rate of mass transfer to the surface. However, in the absence of additional additives, deposits from such formulations do not have smooth, bright surfaces.

Brighteners are typically small, molecular weight sulfur-containing compounds that locally increase the plating reaction by displacing adsorbed carrier. The impacts of brightener additions occur preferentially at points of lower field density, typically in surface recesses or at the bottoms of vias or trenches. The function of the brightener is to locally accelerate the rate of the copper plating reaction and further refine the grain size of the deposit.

Levelers, a further class of additives, act as selective suppressors and typically operate at low concentration (< 10 ppm). At these low concentrations, the activity of levelers is much more mass transfer dependent then that of carriers, with the consequence that less isolated locations (such as the panel surface) are more suppressed than more isolated locations, such as the interior surfaces of vias and recesses within via hole walls.

Bottom-Up Fill Mechanism
For blind vias to be filled with a high quality continuous copper deposit, the plating rate within an individual via must vary. The plating rate at the base of the via must be substantially faster than that that of the remaining areas to avoid premature closure of the mouth of the via opening and the consequent formation of voids or seams.

Accelerated bottom-up filling has been attributed to the mode of action of the organic additive system (1). The suppressor or carrier forms a current inhibiting film on the Cu surface. This film forms uniformly at all locations, assisted by the high solution concentration of suppressor. The accelerated bottom-up filling (i.e. “superfilling”) is believed to be driven by brightener concentration enhancement at the base of the feature (via or trench) during the plating process. Progressive reductions in surface area of via bottoms during deposition “squeeze” the brightener into ever decreasing areas. This localized concentration of brightener further accelerates the plating rate relative to the surface. The leveler acts to suppress the plating at the corners of vias, and aid in reducing the formation of a void. To maintain bottom-up filling behavior, brightener concentration must be controlled within specified limits.

Process Parameters Affecting Via Fill
In addition to process chemistry formulation and bath composition, the key process factors affecting via filling are substrate condition, solution flow, current density and the pretreatment process.
Via profile, thickness and uniformity of the initial conductive layer, degree of surface oxidation and type of dielectric material have a significant impact on via filling ability. A ‘V’-shaped via, with uniform sidewalls free of overhang or protruding glass fibers, promotes consistent seed layer formation and enhances subsequent via fill. Accordingly, non-reinforced dielectric materials are generally easier to fill. A thin or discontinuous seed layer will significantly degrade via fill performance.

While lower levels of solution flow will generally improve via filling performance, particularly of large (100 µm or above) vias, this improvement comes at the price of increased risk of improperly filled small (75 µm or less) diameter vias. Improper fill may manifest itself as defects ranging from seams within the plated deposit, to completely voided vias. The consequence of this behavior is that equipment parameters must be optimized to achieve acceptable levels of fill and plating quality for the specific applications being run.
The effects of current density are somewhat less confounded, as lower current density will both enhance via filling performance and also produce product with lower levels of improperly filled vias. However, the impact of current density is strongest at the very early stages of via filling. Once vias have partially filled, higher current densities can be applied without adverse effects.

At the beginning of the line, the end of one coil is welded to the start of the next coil. Then there are two basic methods for continuously galvanizing sheet which differ in the way that the strip is cleaned before galvanizing-chemically or by thermal treatments. Coils of annealed cold reduced sheet may be fed directly to the galvanizing line, or alternatively, coiled sheet is continuously heat treated in the pretreatment line. After leaving the galvanizing bath, in which strip only stays for a few seconds, the surface is wiped to remove excess zinc and may be further treated to after the surface appearance, composition, smoothness or mechanical properties.

The steel sheet electroplating process utilizes the same basic principle as that for conventional decorative finish electroplating. However, the steel sheet process differs in that the electroplated coating is applied by passing the strip at high speeds through a series of plating cells, building the coating thickness by a small amount each time the strip passes through an individual cell. This continuous process for electroplating steel strip requires necessary equipment to transport the strip at high speeds (150 to 200 meters per minute and higher) through a series of individual plating cells, and is not as simple as it sounds.

An Electroplating Cell

The simplest electroplating cell is shown in the sketch where the plating solution bath is zinc sulfate.

The common schema of the electroplating cell.
This simple plating cell illustrates the actions during the plating process. At cathode (steel, for example), zinc ions dissolved in the zinc sulfate solution combine with two electrons and form elemental zinc, which deposits onto the cathode surface. At anode, water is converted to oxygen and hydrogen ions to maintain electrical balance. The oxygen forms a gas and nothing is deposited on the anode surface. The plating solution carries the current between the cathode and anode.

Plating of Steel Sheet in a Continuous Process

There are many types of anode arrangements. Some are horizontal, others are vertical, and one process utilizes a radial cell wherein the strip passes around large diameter rolls inside each plating cell, and the anodes have a radial design to match the diameter of the large rolls submerged into the plating solution. Each type of anode arrangement and design has advantages and disadvantages; thus, it is easy to see why different manufacturers use different methods. Each requires very close control of the anode-to-strip spacing to achieve efficient plating, avoiding arc spots and other defects in the coating.
Modern Continuous Electroplating Line.
Maintenance of the large volume of plating solution that is contained in all the cells is a science unto itself. Whether the plating solution for electrogalvanizing is based on zinc sulfate or zinc chloride chemistry, maintenance of the proper ranges of zinc ion concentration and solution pH are important control features. Besides plating zinc, some manufacturers have the ability to deposit alloy coatings. This requires, at a minimum, at least one more level of control of the plating solution. For example, producing a zinc/nickel alloy coating requires close control of the concentrations of both the dissolved zinc and nickel in the solution. Solution control has to be accomplished on a dynamic basis since these lines operate continuously.

Power Requirements

The electroplating process requires a large amount of electric power to deposit a metallic coating. The total power requirement is a direct function of the coating thickness that is needed to meet the customer’s specification. For example, the power required to deposit a zinc coating mass of 80 g/m2 is approximately twice that required to deposit a coating of 40 g/m2. A typical line that has the capability to process 70 to 120 tons/hour with a coating mass of 50 g/m2 will consume hundreds of thousands of amperes during this one hour of processing time. It is easy to see why power costs are major cost component for a facility that processes large quantities of electroplated sheet product.

Product Types

The most common electroplated coating for steel sheet products is zinc. Electrogalvanized zinc coatings are used by a number of automotive companies for exposed car-body panels, where the typical coating mass ranges from about 50 to 80 g/m2 per side. These coatings are considerably thicker than the electrogalvanized coatings typically used for non-automotive applications, so the lines built to make products for automotive applications usually have a large number of plating cells. Also, each automotive customer has their own specific coated-product specification.

Another attribute associated with the use of electrogalvanized coatings for automotive applications is excellent surface finish that is attainable with the electroplating process. Twenty-five years ago, when automotive companies began using large amounts of galvanized sheet for exposed body panels to improve corrosion protection, one of the few coated sheet products that could meet the demanding surface quality requirements was electrogalvanized. Hot-dip galvanized was, and still is, used for unexposed body parts. As the surface of hot-dip products improves, they continue to replace electrogalvanized sheet for exposed automotive body panels.

Other zinc electroplating lines have been built through the years to make thinner coatings. Typically, the sheet that is made on these lines has a coating mass of less than 25 g/m2. The applications for this product are often indoors; applications where the environment is not very corrosive. Many applications involve painted products. These coating lines often have the ability to apply paint pre-treatment so that the customer can paint directly without additional in-house treating.

A second type of electroplated coated-steel sheet being manufactured today has a coating composed of a zinc/nickel alloy. Typically, the nickel content is 10 to 16 percent with the balance being zinc. The unique feature of this process is that the zinc and nickel ions are co-deposited to make a true alloy coating. It is not composed of alternating layers.

The application for this product has been limited primarily to a few automotive companies. These companies have developed in-house product design and manufacturing processes to take advantage of the unique characteristics of the zinc/nickel coating. For these automotive applications, the metallic coating is often coated with a special corrosion-resistant thin organic coating on top of the zinc/nickel. The zinc/nickel alloy coating is covered by ASTM Specification A 918.

A third type of electroplated coating is zinc/iron alloy coating. The attributes of this specialized coating are somewhat like those of hot-dip galvannealed product. Like zinc/nickel alloy, zinc/iron coating is co-deposited as an alloy coating. Iron is uniformly deposited throughout the coating thickness. Also, like zinc/nickel coating, zinc/iron coating is used predominantly by the automotive industry. The attributes of electroplated zinc/iron is that it is relatively easy to weld and paint if the proper electro-priming equipment is available to the automotive manufacturer. Also, the coating is very hard, making it is less susceptible to scratching during stamping and handling. This is the important feature since the zinc/iron alloy coated-sheet product is being used almost exclusively for exposed car-body panels.

Corrosion Resistance of Electroplated Coatings

Concerning the corrosion behavior of electrogalvanized versus hot-dip galvanized coating, it is important to note that it is essentially equivalent for identical coating masses. A coating mass of 100 g/m2 will provide essentially the same amount of corrosion protection whether it is a hot-dip galvanized or electrogalvanized coating.

The reason that the automotive companies can successfully use a coating mass in the 50 to 80 g/m2 range is because they apply additional treatments on top of the metallic coating, including a zinc phosphate coating, an electro-deposited organic-based coating, a primer, and multiple-layer finishing paint coatings. Clearly, the corrosion resistance needed to protect a car body panel for over 10 years is more than that afforded by the metallic coating alone. Application of the above coatings over the electroplated metallic layer results in a synergistic system, whose corrosion resistance is more than the sum of its individual components.