PC-600-脉冲酸铜、填通孔

PC-600 ACID COPPER PLATING PROCESS

PC-600 ACID COPPER PULSE PLATING PROCESS

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DESCRIPTION

PC-600 is an acid copper plating additive system that has been specifically optimized for use with pulse periodic reverse rectification on a continual production basis.

READ ENTIRE TECHNICAL DATA SHEET BEFORE USING THIS PRODUCT

FEATURES & BENEFITS

The process produces a fine-grained, ductile deposit with excellent distribution characteristics, and is maintained with two components. The combination of PC-600 and a periodic reverse pulse plating rectifier can significantly shorten plating times while maintaining excellent distribution ratios.

PHYSICAL PROPERTIES

PROCESS COMPONENTS REQUIRED

Product Name Product     Code

PC-600 Carrier PC-600 Replenisher

EQUIPMENT

Tanks, pipes, fittings and valves should be acid resistant. All plastic parts should be of Teflon®, PVC, PVDF, polypropylene or high-density polyethylene construction. Soft PVC (e.g. Tygon®) is not recommended for constant contact with the bath.

Anode bars, cathode bars and bus bars should be made of copper. Bolts, fixtures, etc. that are not immersed in the plating solution may be made of copper, bronze, 316 stainless steel or titanium. Metal parts that will be immersed in the plating bath should be constructed of titanium.

Acid copper sulfate solutions are corrosive. It is important to protect the floors, plumbing and any other equipment, which may come in contact with the plating solution. Vinyl coatings, asphalt or several coats of rubber-based paint will usually provide adequate protection.

Rectifier output (amperage) should be calibrated to 土5% or less across the working range. Also the pulse wave form (especially the % overshoot and rise time) should be checked with an oscilloscope by a qualified technician.

The preferred rack materials are copper and copper alloys. The rack area, if immersed in plating solution, should be coated with a non-conductive material (e.g. Plastisol®, Koroseal®).

MAKE UP PROCEDURE

Note: COPPER SULFATE CONCENTRATE from MacDermid Enthone typically contains about 270 g/L (36 oz/gal) of copper sulfate pentahydrate, or 68.7 g/l (17.5 oz/gal) of copper metal.

Mixing Instructions:

Fill to half of final working volume with deionized water.

With mixing, add the required amount of copper sulfate and dissolve.

With heavy mixing, slowly add the required amount of sulfuric acid. The addition of sulfuric acid produces a considerable amount of heat. If PVC structures are present, monitor the temperature of the solution and do not allow it to exceed 49 °C (120 °F).

Cool, with mixing, to 29 °C (85 °F).

Add 0.41 g/L of Manganese Sulfate monohydrate pre-dissolved in DI water (CAS #10034­96-5, tech grade or better).

With mixing, add the required amounts of PC-600 Carrier and PC-600 Replenisher.

Fill to final volume with deionized water and mix.

Check the chloride content of the bath and add sufficient hydrochloric acid to raise the chloride to approximately 80 ppm.

Note:

(ppm chloride add desired) (bath volume in liters) = mLs of 37% (concentrated HCI to add

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Electrolyze (dummy plate) the bath for 3 hours at 20 ASF (2 ASD) while maintaining the brightener concentration by CVS, CPVS or dilution Hull cell (the feed rate of PC-600 Replenisher should be about 0.2 to 0.5 mL/amp. hr, however, the initial feed rate for the first day may be higher). The PC-600 Carrier feed rate should be about 0.2 to 0.5 mL/amp. hr. The pulse waveform should be set at 40 msec forward; 2.3 msec reverse and a 2 to 1 reverse current ratio. Plate a test panel and obtain cross-section results to be sure the optimum performance is obtained before starting production. Some plating tank or board designs may require special waveforms or brightener concentrations in order to obtain optimum results.

OPERATING CONDITIONS

The operating conditions for the PC-600 Acid Copper process are as follows:

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MAINTENANCE AND REPLENISHMENT

The copper, sulfuric acid, and chloride content of the acid copper plating solution are analyzed using the analytical procedures that are included in this data sheet. The PC-600 Carrier and

PC-600 Replenisher concentrations are controlled by proprietary CPVS and or CVS procedures (as well as specially prepared Hull cell methods). Please refer to the separate control procedure bulletins for these methods or consult your technical service representative.

All new anode bags and filters should be leached before use in an acid copper plating bath.

The materials should be leached in hot water (43 to 71 °C, 110 to 160 °F) with changes of water until fresh leach water no longer foams. The initial leach can be augmented by the addition of 3% sulfuric acid.

The anode current density should be maintained between 10 and 30 ASF (0.93 to 2.8 ASD) in general operation. Excessive anode current density can lead to anode polarization and poor deposit distribution and structure.

Anode to cathode distance spacing is also important in the general operation of an acid copper-plating bath. An anode to cathode distance of 20 to 30 cm (8 to 12 inches) is recommended to insure a more uniform distribution of the deposit.

It should be noted that anode and cathode placement, agitation, copper concentration, temperature, electrical connection and circuit configurations could affect distribution and usable current density range. More details of these effects can be found in the attached troubleshooting guide.

The optimum temperature for most situations is 24 °C (75 °F) with a range of 21 to 27 °C (70 to 80 °F). Low temperatures may cause burning.

FUNCTION OF BATH COMPONENTS

Copper Sulfate Content

Copper sulfate provides copper ions for the deposition process. It should be maintained within the specified limits of 55 to 75 g/L. Higher levels give no advantage at 30 ASF but may help increase leveling at higher current densities. Lower concentrations will reduce maximum operating current density but can give improved metal distribution.

Sulfuric Acid

Sulfuric acid provides solution conductivity. It should be maintained between 12 to 13.5% by volume. Higher concentrations may lead to anode polarization. Low concentrations may degrade deposit distribution.

Chloride Content

Chloride supports the action of the PC-600 Replenisher and ensures an even dissolution of the anodes. A low concentration will lead to a streaky or nodular deposit. A high concentration will cause anode polarization with a characteristic white anode film. Tanks using anode bags and anode screens may require a chloride range <75 ppm.

The consumption of chloride will be higher during the filming of new anodes and it may be necessary to maintain the concentration by additions of hydrochloric acid.

PC-600 Replenisher

PC-600 Replenisher is responsible for the grain refining and superior throwing power of the deposit and is usually replenished at approximately 0.2 to 0.5 mL/amp. hr. A low concentration will cause rough matte deposits. High concentrations may cause loss of throwing power and leveling.

PC-600 Carrier

PC-600 Carrier is responsible for the wetting action and throwing power of the solution and it is necessary for a minimum quantity to be present to ensure that the PC-600 Replenisher works optimally. Under normal conditions a replenishment rate of 0.2 to 0.5 mL/amp hr is sufficient.

CARBON TREATMENT

After a period of time, acid copper plating baths will require a carbon treatment. The plating bath may become contaminated with organics from rack coatings, additive or resist breakdown, drag-in chemicals, and even the water supply. Under most conditions about 350 to 600 amp hr per L (1300 to 2300 A hr per gal) is recommended for a PC-600 bath. When the carbon treatment is needed, one of the following procedures should be followed.

If the carbon treatment is for conversion from another brightener system, the tank and anodes should be cleaned and all bags and filters must be replaced with new bags and filters.

Method #1:        BATCH

B1. Transfer entire plating solution into a properly cleaned and leached treatment tank.

B2. Follow steps “a，，through “d，，or “e，，through “g，，depending on the availability or applicability of heat. The total time that any one charge of carbon is exposed to the bath should not exceed 8 hours.

With Heat

Raise temperature to approximately 43 °C (110 °F).

Add with stirring, 250 mL of technical grade 30% hydrogen peroxide per 100 L of solution (1 quart per one hundred gallons). Agitate solution well for at least two hours at 43 °C (110 °F).

Raise temperature to about 60 °C (140 °F) and continue agitation for at least two more hours.

Cool the solution to a temperature below 38 °C (100 °F), and add to the bath at least 750 g of finely powdered activated carbon per 100 Liters of solution (6 pounds per 100 gal). Continue to mix well for two hours. At the end of two hours, turn off agitation and allow solution to settle.

Without Heat

Add with stirring, 250 mL of technical grade 30% hydrogen peroxide per 100 L of solution (1 quart per 100 gallons). Air agitate the solution vigorously for 10 or more hours.

Add to the bath at least 750 g of finely powdered activated carbon per 100 Liters of solution (6 pounds per 100 gal). Continue to mix well for two hours. At the end of two hours, turn off agitation and allow solution to settle.

B3. Filter the carbon out of a small sample of the plating solution for hull cell testing. The resultant hull cell should be matte across the entire range of current densities. No brightness should be seen, except at very low current densities and a 0.5% PC-600 Carrier add should not greatly increase the brightness seen on the panels. If a matte hull cell is obtained, proceed to step 4. If not, filter the carbon out of the bath and repeat steps B1 and B2).

B4. Pump the treated plating solution through filters packed with diatomaceous earth and into the regular plating tank (filters rated at 3 microns or less are recommended). Be careful that the carbon does not pass from the treatment tank into the plating tank.

B5. Once the solution has been properly carbon treated, remake the bath according to the make-up section of this data sheet.

Method #2:        CARBOLATION

C1.   Remove anodes, store in water or dilute sulfuric acid (3 - 5%).

C2. Follow steps “a，，through “d，，or “e，，through “f，，depending on the availability or applicability of heat.

With Heat

Raise temperature to approximately 43 °C (110 °F) and add 250 mL of technical grade 30% hydrogen peroxide per 100 L of solution (1 quart per 100 gallons).

Agitate the solution well for at least two hours at 43 °C (110 °F).

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Raise temperature to about 60 °C (140 °F) and continue to agitate for at least two   hours.

Allow solution to cool below 43 °C (110 °F).

Without Heat

Add 250 mL of technical grade 30% hydrogen peroxide per 100 L of solution (1 quart per 100 gallons).

Air agitate the solution vigorously for 10 or more hours.

C3. Filter through activated carbon. At least 950 g of granular carbon per 100 Liters of solution (8 pounds per 100 gallons) should be used. Since most carbolators will not hold that much carbon, several charges of carbon will be necessary. The solution should be turned over 2 or more times for each charge. The total time that   any   one

charge of carbon is exposed to the bath should not exceed 8 hours.

C4. Verify complete carbon treatment by full matte Hull cell. The resultant hull cell should be matte across almost the entire range of current densities. No brightness should be seen, except at very low current densities. If a matte hull cell is obtained, proceed to step C5. If not, repeat steps C1 and C3.

C5. Once the solution has been properly carbon treated, remake the bath according to the make-up section of this data sheet.

In most cases, it is simpler and cheaper to regularly decant a portion of the solution rather than carbon treating to keep contaminants and by-products at a low level. It is suggested that enough solution be decanted, daily or weekly, to turn a bath over every 6 to 9 months.

ANALYTICAL PROCEDURES

PROCEDURE NUMBER: AP.0528.02

PROCEDURE DESCRIPTION: Titrimetric procedure to determine the concentration of copper in an acid copper plating solution.

EQUIPMENT & SETTINGS:

250 mL Erlenmeyer flask

2 mL adjustable pipette

50 mL burette

10 mL graduated cylinder

REAGENTS:

0.05 M EDTA - Weigh 18.162 g of disodium EDTA dihydrate. Dissolve in 1 liter volumetric flask with DI water.

NAS Indicator - Dissolve 0.5 g of napthyl azoxine S in 100 mL DI water.

pH 5 Buffer - To 245 grams of sodium acetate trihydrate, add 58 mL of Glacial Acetic Acid. Dilute to 1 liter with DI water.

PROCEDURE:

Pipette 2 mL of bath sample into a 250 mL flask.

Add 50 mL of DI water.

Add 10 mL of pH 5 buffer.

Add 10 drops of NAS indicator.

Titrate with 0.05 M EDTA to a red endpoint.

Record the volume used.

CALCULATIONS:

g/L Copper metal = mL EDTA x M     EDTA        x       31.8

g/L Copper Sulfate = mL EDTA x M EDTA          x 125

oz/gal Copper metal = mL EDTA x M EDTA x 4.24

oz/gal Copper Sulfate = mL EDTA x M EDTA x 16.6

PROCEDURE NUMBER: AP.0348.02

PROCEDURE DESCRIPTION: Titrimetric procedure to determine the concentration of sulfuric acid in an acid copper plating solution.

EQUIPMENT & SETTINGS

250 mL Erlenmeyer flask.

5 mL pipette

50 mL burette

REAGENTS

1 N Sodium Hydroxide solution (NaOH) - Dissolve 40 grams of sodium hydroxide C.P. into 500 mL of DI water and dilute to 1 liter.

Methyl Orange indicator - Dissolve 0.1 g of methyl orange in DI water and dilute to 100 mL.

PROCEDURE

Pipette 5 mL of plating solution into a 250 mL Erlenmeyer flask.

Add about 100 mL of DI water.

Add 2 to 3 drops of methyl orange indicator.

Titrate with 1 N sodium hydroxide solution until color changes from pink to yellow.

Record the results.

CALCULATIONS

g/L sulfuric acid = mL NaOH x N NaOH x 9.88

% by volume sulfuric acid = mL NaOH x N NaOH x 0.56

oz/gal sulfuric acid = mL NaOH x N NaOH x 1.32

PROCEDURE NUMBER: AP.3605.06

PROCEDURE DESCRIPTION: Potentiometric procedure to determine chloride concentration in a solution.

EQUIPMENT & SETTINGS

Millivoltmeter

Silver Billet Electrode (Fisher 13-620-122 or equivalent)

Reference Electrode (Fisher 13-641-900 or equivalent)

Magnetic Stirrer

50 mL pipette

150 mL beaker

50 mL burette

REAGENTS

A. 0.02 M Silver Nitrate - Dissolve 3.38 g of solid silver nitrate in DI water, then dilute to 1 liter.

PROCEDURE

Pipette 100.0 mL of solution into a 150 mL       beaker.

Add about 50 mL of DI water.

Place beaker onto magnetic stirrer, insert electrodes, switch on millivoltmeter and note the potential difference.

Add 0.02 M silver nitrate in 0.5 mL increments, noting the potential difference after each addition.

Continue for 2 mL beyond the point where       the largest         change in potential difference occurs.

The titration figure is taken as the average        of the two values       between which the    largest

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change in potential difference occurs.

Largest change occurred between 5.5 and 6.

Therefore, titration figure = (5.5 + 6)/2 - 5.75

CALCULATIONS

ppm chloride = mL silver nitrate x M silver nitrate x 355 PROCEDURE NUMBER: AP.4208.02

PROCEDURE DESCRIPTION: Measure Carrier in a PC 600 acid copper plating bath by CVS.

EQUIPMENT & SETTINGS

Appropriate CVS analyzer capable of performing a Dilution Titration (DT)

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Instrument settings:

The use of different Outer Junction Fill Solutions require a modification of the electrochemical parameters.

** Volumes may vary depending on the equipment available.

REAGENTS

VS blank solution (1 liter):

Add 75 g of copper sulfate pentahydrate to 1 L volumetric flask.

Add about 600 mL of DI water.

With heavy mixing, slowly add 100 mL of concentrated sulfuric acid.

Add 0.13 mL of concentrated hydrochloric acid.

Cool to room temperature.

Add deionized water to a total volume of 1 L.

3% Carrier Standard:

Add 3 mL of PC 600 Carrier to a 100 mL volumetric flask.

Fill to line with CVS blank solution.

PROCEDURE

Note: All procedures consistent with proper operation of the CVS instrument (e.g. pump priming, electrode maintenance, etc.) must be followed.

Initial set up: Create a memory/method file labeled “PC 600 Carrier，, setting the parameters for the analysis as outlined above in Equipment & Settings.

Call up the “PC 600 Carrier” memory file.

Using 100 mL of CVS blank solution under the electrode, run conditioning      cycles as

needed, then run the calibration using the 3% Carrier Standard for addition.

Run 3% Carrier Standard as sample by using 100 mL of fresh CVS blank        solution under

the electrode and 3% Carrier Standard for addition. The result should be         between 2.8%-

3.2%, otherwise repeat conditioning and calibration.

Run the sample by using 100 mL of fresh CVS blank solution under the electrode and additions of the undiluted sample bath per normal Dilution Titration operating procedures.

CALCULATIONS

% Carrier = CVS Reading (mL/L)

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PROCEDURE DESCRIPTION: Measure PC 600 Replenisher in acid copper plating bath by CVS.

II. EQUIPMENT & SETTINGS

Appropriate CVS analyzer capable of performing a Modified Linear Approximation Technique (MLAT).

Instrument settings:

* Some instruments may require the use of the Linear Approximation Technique (LAT). ** The use of different Outer Junction Fill Solutions require a modification of the electrochemical parameters.

*** Volumes may vary depending on the equipment available.

REAGENTS

CVS blank solution (1 liter)

Add 75 g of copper sulfate pentahydrate to a graduated container.

Add about 600 mL of DI water.

With heavy mixing, slowly add 100   mL   of concentrated         sulfuric acid.

Add 0.13 mL of concentrated hydrochloric acid.

Cool to room temperature.

Add deionized water to a total volume of 1 L.

CVS Intercept solution.

Add 5 mL of PC 600 Carrier to a 100 mL volumetric flask.

Fill to line with CVS blank solution.

PC 600 Replenisher.

PROCEDURE

Note: All procedures consistent with proper operation of the CVS instrument (e.g. pump priming, electrode maintenance, etc.) must be followed.

Initial set up: Create a method/memory file labeled “PC 600 Replenisher”，setting the parameters for the analysis as outlined above in Equipment & Settings.

Before each batch of samples: Using a 100 mL of CVS blank solution under the electrode, run 20 to 30 conditioning cycles.

For each sample:

Using 100 mL of CVS blank solution under the electrode, run 10 conditioning cycles.

Using 100 mL of CVS Intercept solution under the electrodes, click on “get new intercept” and run for new intercept.

Place 95 mL of sample bath and 5 mL of PC 600 Carrier into 150 mL plastic beaker under the electrode, mix well.

Run the sample per the normal MLAT procedures using undiluted PC 600 Replenisher for the additions.

After each batch of samples:

Using 100 mL of CVS blank solution under the electrode, run 10 to 15 conditioning cycles.

Using 100 mL of clean CVS blank solution under the electrode, run 10 to 15 conditioning cycles.

CALCULATIONS

mL/L PC 600 Replenisher = CPVS reading x 1.05

% PC 600 Replenisher = mL/L PC 600 Replenisher

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PROCEDURE NUMBER: AP.3428.01

PROCEDURE DESCRIPTION: The method to control the PC-600 Replenisher in PC- 600 Acid Copper Plating bath by Hull cell.

This procedure characterizes the concentration of the PC-600 Replenisher in the plating bath by diluting the bath to produce a characteristic appearance on the Hull cell panel.

Contaminants are generally not a factor with dilution Hull cells because the contaminants are also diluted.

Because several factors influence the appearance of the plated cathode plate, care must be taken to insure reliable and repeatable results. For this reason the following guidelines have been established.

EQUIPMENT & SETTINGS

Air agitated Hull cell. Suggested suppliers include McGean-Rohco in Cleveland, OH and Kocour Company - Chicago, IL

Air pump. Suggested suppliers include: Rolf C. Hagen Corp - Mansfield, MA: Bite 801& 803

Phosphorized copper anode

Rectifier capable of providing 2 amps.

Brass Hull cell panels. Suggested suppliers include McGean-Rohco in Cleveland, OH and Kocour Company 一 Chicago, IL

REAGENTS

Copper Blank Solution: In 1.0 L volumetric flask, add the following: