Electrolytic Copper

Plating Additives
and Contaminants

Wayne Jones
 Electrolytic Copper Plating Chemistry

Typical DC Acid Copper Electroplating Solution contains:

> Inorganic
• Sulfuric Acid (180 - 250 g/l)
• Copper Sulfate (40 - 100 g/l)
• Hydrochloric Acid (25 - 100 mg/l)

> Organic
• Brightener (2 - 10 mls/l)
• Leveler (5 - 15 mls/l)
• Carrier (25 - 100 mls/l)

> Water (Balance)

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 Electrolyte Control
Sulfuric Acid – Virtually unconsumed…Dragout
¾ Titration or Specific Gravity

Copper Sulfate – Maintained by Anode Erosion

¾ Titration, UV/Vis

Chloride – Maintained by chemical analysis

¾ Titration, Ion Specific Electrode, UV/Vis

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 Additives – Mostly Proprietary
Brighteners – are plating accelerators, which act as a micro-leveler and impact grain
refinement. They tend to be attracted to cathode induction zone points of higher electro-
potential, temporarily packing the area and forcing copper to deposit elsewhere. As the
copper deposit levels, the local point of high potential disappears and the brightener drifts
away, as well as depleting (hydrolysis) to a higher level of activity.
Chemical Family - Organic Sulfides, Disulfides, Thioethers, Thiocarbamates.

Levelers – are strong secondary plating inhibitors, which typically co-function with
Brighteners to reduce copper growth at protrusions and edges. They improve mass
transfer to localized sites of lesser electro-potential or feature height.
Chemical Family – Quaternary Nitrogen Cmpd.

Carriers – are plating inhibitors or suppressors, they create and maintain a defined
diffusion layer at the Anode (which regulate the flow of Cu+2 ions into the electrolyte and
ultimately to the cathode (board surface). Carrier depletion occurs as the PEG cleaves.
Chemical Family – Polyethylene Glycol (PEG), Polyalkylene Glycol (PAG)

Chlorides – mild plating inhibitors, which stabilizes the Cu+1 ion that serves as an
intermediate in the electro-deposition process during reduction to Cu +2. Additionally they
modify adsorption properties of carrier to influence thickness distribution.
Chemical Family – Hydrochloric Acid
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 Hull Cell – Additive Control
ASF 75, Needs Brightener

Carbon Treated Copper Bath ASF 90, Proper Operating Range

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 CVS/CPVS – Cyclic (Pulse) Voltammetery Stripping

CVS/CPVS is an indirect bath

measurement which measures
the “combined” effect of the
additives and by-products
on the plating quality

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 CVS and CPVS Instrumentation

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 Copper Anodes

Phosphorized: 150 – 650 ppm P

Oxygen Free Casting
Typical Chemical Analysis
Grain structure grows from surface Contam inant Concentration, Wt %
to the center, resulting in uniform Lead 0.0002
corrosion of the anode. Zinc 0.0001
Nickel 0.0002
Iron 0.0004
Anodes are “conditioned” when new Sulfur <0.0010
by developing a necessary black Antimony 0.0001
CuO film – Dummying. Arsenic 0.0002
Silver <0.0010
Tin 0.0002
Balls, Nuggets, Bars.

Anode surface area and continuous bath agitation is critical.

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 Pattern Plating

1) Full panel Electroless Copper deposition.

2) Photoresist apply, expose with positive image artwork -
majority of copper surface shielded, develop.
a) Reduced electroplated surface.
b) Lower current capacity required.
c) Less copper anode bank consumption.
d) Less copper in etchant.
3) Plate Copper, Plate Tin (Etch Resist)
a) Adds several additional wet process baths.
4) Strip Photoresist – Potassium Carbonate
5) Etch Copper – Ammoniacal
6) Strip Tin Resist – Nitric Acid
7) Antioxidant - BTA

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 Panel Plating

1) Full panel Electroless Copper deposition.

2) Full panel Electrolytic Copper plated.
a) Higher current capacity required.
b) Significant copper anode bank erosion.
c) Smooth, even, bright finish on panel and hole walls.
d) Easily cleaned/prep’d for downstream processing.
3) Photoresist apply – Negative Image
4) Develop - Carbonate
5) Etch – Ammoniacal or Cupric Chloride
a) Significant copper buildup in etch, more maintenance.
6) Strip – Potassium Hydroxide
7) Antioxidant - BTA

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 Contaminants – Drag in / Leach Out

Inorganics – ICP / GFAA analysis Trace Metals

¾ Iron (Fe)
¾ Calcium (Ca)
¾ Tin (Sn)
¾ Lead (Pb)
¾ Nickel (Ni)
¾ Antimony (Sb)
Organics – Hull Cell / CVS / TOC
¾ Cleaner/Predip surfactants (inactive)
¾ Resist Photo-initiators (inactive)
¾ Anode Bag Sizing (inactive)
¾ Additive breakdown products / fragmentation (active)

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 Chemistry Impact / FMEA
Inorganic Organic
Defect / Failure Mode
CuS04 H2SO4 Cl- Brightener Leveler Carrier

Burned Copper Deposit Low Low / High Low Low

Poor Throwing Power High Low
Poor Leveling Low Low / High
Roughness Low
Pitting
Streaking High
Poor response to additives High High
Step Plating Low
Grain Structure Poor High Low Low Low
Anode Color Green High
Anode Color Dark Low
Anode Color Bright High
Soft Copper Deposit Low
Brittle Copper Deposit High
Low Tensile Strength
Dull/Matte finish
Copper Nodules High
Spiked Copper Deposit Low / High
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 Contaminant & Process Impact / FMEA
Contaminant / Impurities Mechanical / Electrical
Defect / Failure Mode
TOC Particulates Trace ASF Anodes Circulation Agitation Temp

Burned Copper Deposit High High High Low Low

Poor Throwing Power High High
Poor Leveling High Low
Roughness High High High / Low Filtration
Pitting High High Low
Streaking High High
Poor response to additives High High High / Low High
Step Plating
Grain Structure Poor
Anode Color Green
Anode Color Dark
Anode Color Bright
Soft Copper Deposit High
Brittle Copper Deposit High High
Low Tensile Strength High High
Dull/Matte finish
Copper Nodules High Low / High
Spiked Copper Deposit Low / High

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 Burnt Plating – Unbalanced CD / ASF

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 Even After Microetch

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 Plating Characteristics Impact Etch Differential

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 Topography Differential – SEM/BSE

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 Copper Topography Variations (80x)

Burnt Copper Plating Transitional

Detectable Bright / Leveled

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 Spiked Copper – Surface / Knee

Courtesy Sanmina-SCI, Owego

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 Spiked Copper – Hole Wall

Courtesy Sanmina-SCI, Owego

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 Grain Structure Failure – Blind Via

Courtesy Sanmina-SCI, Owego

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 Copper Chicklets – Grain Structure

Courtesy Sanmina-SCI, Owego

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 Cobblestones – Hole Wall

Courtesy Sanmina-SCI, Owego

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 Cobblestones – Hole Wall

Courtesy Sanmina-SCI, Owego

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 Surface Nodule – Process Debris

Courtesy Sanmina-SCI, Owego

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 Surface Nodule - Debris

Courtesy Sanmina-SCI, Owego

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 Barrel Crack / Lam Voids – 6x TS

Courtesy Sanmina-SCI, Owego

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 Summary: Surface Contaminant Evaluation

Macro Level: PCB fabricator - SPC, IPC TM’s and spec’s, customer
requirements, cleanliness, water quality, post process residues,
solderability, visual inspection.

Micro Level: Post fab evaluations employing FTIR, Raman

Spectroscopy, HPLC, SEM - EDS/Auger, IC, ICP/GFAA.

What to look for:

¾Process residues (MOP, Resist Remnants, HW Salts, OSP)?
¾Co-plated contaminants (inorganic / organic)?
¾Hydrides, Oxides, Sulfides, Carbides, Halides?
¾Gas entrapment?

What’s changed the most:

¾Etch Resists (Sn vs Sn/Pb) and strip chemistry?
¾High Temp OSP’s?
¾DC or Pulse (Reverse and Duplex) Plating and chemistry – High aspect ratio?

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