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racking, cleaning, copper microetching, and hole and surface catalyzing with palladium and electroless copper. Typical steps are as follows: 1. Cleaner-conditioner. Alkaline cleaning is used to remove soils and condition holes. 2. Microetch. This slow acid etching is used for removal of copper surface pretreatments, oxidation, and presentation of uniformly active copper. Persulfates and sulfuric acid hydrogen peroxide solutions are commonly used. 3. Sulfuric acid. This acid removes persulfate residues. 4. Predip. This process maintains the balance of the next step. 5. Catalyst (activator). Neutral or acid solutions of palladium and tin are used to deposit a thin layer of the catalytic metal on the nonconductive surfaces. Some palladium is unintentionally absorbed onto the foil surface and innerlayers. 6. Accelerator (postactivator). This process removes colloidal tin on board surfaces and holes or change the charge of the palladium tin colloid. 7. Electroless copper. This alkaline-chelated copper-reducing solution deposits thin copper in the holes (20 to 100 min) and surfaces. 8. Antitarnish. This neutral solution prevents oxidation of active copper surfaces by forming a copper conversion coating. 28.5.2 Mechanism Equations 28.1 and 28.2 illustrate the process. Pd+2 + Sn+2 Pd + Sn+4 Pd CuSO4 + 2HCHO + 4NaOH Pd Cu + 2HCO2Na + H2 + 2 H2O + Na2SO4 (28.1) (28.2)

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However, Eq. 28.2 is an old two-step catalyzation sequence that is no longer in use in the industry.

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Electroless Copper Processes New materials and increased reliability criteria have precipitated a newer generation of electroless copper baths. Lead-free assembly forces the PWB to undergo higher thermal excursions, thus increasing the stress on the plated through holes. Proprietary additives (which are not listed in Table 28.3) affect the integrity of the electroless copper-plated deposit. Selection from the several types available depends on the type of image transfer desired. Operation and control of three bath types and the function of constituents are given in Tables 28.3 and 28.4. The problems encountered with this system are as follows: 1. Uncoppered holes or voids. Voided holes appear as black or dark color in the holes. Corrective actions : Ensure that the process is functioning correctly by verifying the times, temperatures and concentrations of all preceding process tanks, including the desmear process as specified. The electroless copper bath components should be verified as well as the dwell time. Low loading factor, low temperature, or high air agitation lead to low bath activity and poor plating characteristics. Voids may also be caused by an overaggressive electrolytic preclean line. 2. Hole wall pull-away. This is the separation of the copper pulling away from the dielectric. The defect is usually detected during the cross-sectioning inspection. If the hole wall pull-away is severe, large blisters can be seen in the hole with the naked eye. Hole wall

TABLE 28.3 Electroless Copper Processes Operation and control Low deposition Copper HCHO NaOH Temperature Air agitation Filtration Tank design Heater Panel loading Replenish mode Idle time, control Deposition time Thickness 3 g/l 6 9 g/l 6 9 g/l 65 85 F Mild Periodic Static Teflon 0.25 1.5 ft2/gal Manual 70 85% 20 min 20 min Medium deposition 2.8 g/l 3.5 g/l 10 11 g/l 115 5 F Mild/moderate Continuous Overflow, separate sump Teflon 0.1 2.0 ft2/gal Manual or continuous Turn off heat 20 min 40 60 min Heavy deposition 2.0 g/l 3.3 g/l 8 g/l 115 5 F Moderate Continuous Overflow, separate sump Teflon 0.1 2.0 ft2/gal Automatic Turn off heat 20 30 min 60 100 min

Using (5.28), we can obtain the components of the Riemann tensor. First, using the symmetries of the Riemann tensor together with a b = diag( 1, 1, 1, 1), note that R r r = R r r = R r r = R r r = R r r = R r r

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