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34.4.1.5 Special Problems Encountered During Etching13 1. Low etch rate with low pH, <8.0. This is caused by excessive ventilation, heating, downtime, and spraying when the solution is hot, under conditions of adequate replenishment or low ammonia. The pH must be raised with anhydrous ammonia. Automatic replenishment equipment must be checked.

2. Low etch rate with high pH, >8.8. This is caused by high copper content, water in etchant, or underventilation. 3. Low etch rate with optimum pH. This is due to error of copper thickness, oxygen starvation in the etcher, or contamination of the etchant. 4. Solder attack. This is caused by excess chloride in the etchant, improper tin/lead deposits, or insufficient phosphate content. 5. Residue on solder plate, holes, and traces. These may be caused by etchant solution imbalance or by spent finisher. 6. Under- or overetching. This may be due to improper pH or equipment adjustments. 7. Sludging of etch chamber with low pH, <8.0. See special problem 1. Sludge will be gritty and dark blue. This may be corrected by the addition of anhydrous ammonia. 8. Sludging of etch chamber with high pH, >8.8. See special problem 2. Sludge will be light blue and fluffy. This may be due to the copper concentration exceeding the capacity of the chloride concentration. It may be corrected by adding ammonium chloride. It may also be due to water added to the etchant. 9. Presence of ammonia fumes. The cause of this is leaks in the etcher. Ventilate for operator safety. 10. Pollution. This results when water coming from the etchers contains dissolved copper. If so, it must be chemically treated and separated from ammonia-bearing rinses. Thin-clad copper laminates present a further problem because their faster movement through the etcher increases the transport of etchant into the rinses. Evaluate isolation roller placement and cleanliness, internal etcher overspray, and proper chemical and water rinsing.

Cupric Chloride Cupric chloride is the second mainstream etchant of choice. (See Table 34.1 for characteristic cupric chloride solutions.) It is more compatible with photopolymer resists and is the etchant of choice for precision etching of small features. Because the cuprous ion buildup renders the etchant impractically slow, this etchant must always be used as a regenerative system with continuous oxidizer management and control. These systems have been the subject of many innovations to achieve continuous regeneration, lower costs, and a constant, predictable etch rate. Steady-state etching with acidic cupric chloride permits high throughput, material recovery, and reduced pollution. Regeneration in this case is somewhat complex but is readily maintained. Dissolved copper capacity is high compared with that of batch operation. Cupric chloride solutions are used mainly for fine-line multilayer inner details, print-and-etch boards, and panel-plate/tent-and-etch boards.14 In addition to photoresists, screened inks, gold, and tin-nickel have been used. Solder and tin resists are not compatible with cupric chloride etchant.

TABLE 34.1 Characteristic Cupric Chloride Etching Solutions Component CuCl2 2H2O HCl (20 Be) NaCl NH4Cl H2O Solution 115 1.42 lb 0.6 gal Solution 216 2.2 M 30 mL/gal 4M * Solution 317 2.2 M 0.5 N 3M * Solution 418 0.5 2.5 M 0.2 0.6 M 2.4 0.5 M *

The etching reaction is as follows: Cu + CuCl2 Cu2Cl2 (34.3)

Chloride ions, when added in excess as hydrochloric acid, sodium chloride, or ammonium chloride, act to solubilize the relatively insoluble cuprous chloride and thereby maintain stable etch rates. The complex ion formation can be shown as

(34.4)

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The formation and diffusion of this chloro-complex form of the Cu(I) ion determine the etching rate for cupric chloride Thus, the rate is affected by chloride ion concentration as well as the typical diffusion concentration and film thickness variables The etchant is regenerated by reoxidizing the cuprous chloride to cupric chloride by several chemical choices as illustrated by the following equations: Air 2Cu2Cl2 + 4HCl + O2 4CuCl2 + 2H2O (345) This method of regeneration is not used because the oxygen reaction rate in acids is slow and the solubility of oxygen in hot solution is low (4 to 8 ppm) Spray etching induces air oxidation, but is not sufficiently reactive to support practical etching rates An additional option of using ozone can accelerate the rate of this process, but ozone concentrations in an oxygen stream are difficult to maintain at above 3 percent, thus limiting utility.