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5 Ferric Chloride Ferric chloride solutions are used as etchants for copper, copper alloys, Ni/Fe alloys, and steel in PC applications, electronics, photoengraving arts, and metal finishing Current use of ferric chloride etchant in printed wiring fabrication is extremely limited in the United States because of costly disposal of the copper-containing etchant, and the much better commercial support for ammoniacal and cupric chloride etchants There is still considerable use for alloy etching and photochemical machining applications Ferric chloride can be used with screen ink, photoresist, and gold patterns, but it cannot be used with tin or tin/lead resists However, ferric chloride is an attractive spray etchant because of its ease of use, holding capacity for copper, and ability to be used on an infrequent batch application basis The composition of the etchant is mainly ferric chloride in water, with concentrations ranging from 28 to 42 percent by weight.

In the previous chapter, the overall response of the control system was no higher than second-order. For these systems, the step response must resemble those of Fig. 5.6 or of Fig. 8.2. Hence, the system is inherently stable. In this chapter we shall consider the problem of stability in a control system (Fig. 14.1) only slightly more complicated than any studied previously. This system might represent proportional control of two stirred-tank heaters with measuring lag. In this discussion, only set-point changes are to be considered. From the methods developed in Chap. 12 for determining the overall transfer function, we have from Fig. 14.1.

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Free acid is present because of the hydrolysis reaction and the need to maintain an acid environment The natural acidity is usually supplemented by additional amounts of HCl (up to 5 percent) to prevent formation of insoluble precipitates of ferric hydroxide Commercial formulations for copper alloy etching are usually 36 Be, or approximately 40 lb/gal FeCl3, and may contain antifoam and wetting agents Customary acid operating HCl content is 15 to 20 percent The effects of ferric chloride concentration, dissolved copper content, temperature, and agitation on the rate and quality of etching have been reported in the literature28,29 3446 Chromic-Sulfuric Acids These etchants for solder- and tin-plated boards were preferred for many years More recently, their use has been completely eliminated due to Cr(VI) listing as a critical environmental hazard.

Other problems with chromic-sulfuric etchants are difficulty in regeneration, inconsistent etch rate, the low limit of dissolved copper (4 to 6 oz/gal), and dangerous degradation of PVC and polypropylene equipment Chromic acid etchant is suitable for use with solder, tin/nickel, gold, screened vinyl lacquer, and dry or liquid film photoresists Chromicsulfuric mixtures etch copper slowly, and additives are needed to increase the etch rate For example, sodium sulfate and iodine have been used for rate increase Alkaline etchants have become so well controlled that there is no justification for the risks and costs of chromic acid formulations The following listing demonstrates some of the operational difficulties with chromic-sulfuric etchants 1 Solder attack The protective value of solder depends on the formation of insoluble compounds on the surface Solder is attacked if the sulfate content of the bath becomes very low or contains chloride or nitrates.

The solder plate composition can also cause etchant attack When the lead content becomes low, the sulfate film protection is lowered, and protection is lost..

(14.1)

2. Slow or no etching of copper. This can be caused by low chromic content, low temperature, insufficient acid, or high copper content. The solution is maintained as close as possible to 30 Baum (pH about 0.1, temperature 80 to 90 F) and should be discarded when copper metal content exceeds 5.5 oz/gal. 3. Staining of board materials. The surfaces of dielectric substrates such as paper-based phenolics are attacked by chromic acid etchants. Removal is difficult, and the boards are generally rejected. 4. Disposal. Spent chromic acid etchants present a serious disposal problem. Disposal must comply with pollution standards and approved practice. 5. Safety hazards. Chromic acid is an extremely strong oxidizing agent. It will attack clothing, rubber, plastics, and many metals. Safety measures require adequate ventilation to keep fumes out of room air, synthetic rubber gloves, aprons, face and eye shields, and storage away from combustible materials. Dermatitis and nasal membrane damage are possible dangers.7

Nitric Acid Etchant systems based on nitric acid have not found extensive application in PC manufacture. Copper etching is very exothermic, which may lead to violent runaway reactions. Problems with this system include solution control, attack on resists and substrates, and toxic gas fuming. However, nitric acid has certain advantages. These include rapid etching, high dissolved copper capacity, high solubility of nonsludging products, availability, and low cost. 34.4.7.1 Chemistry. Reaction in strong acids is shown by the following equation: 3Cu + 2NO3 + 4H+ 3Cu2+ + 2NO2 + 2H2O

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