Electroplating of Copper

NCNC
Ethan Kenon
Solution Formula
The absolute minimum formula for a Copper plating bath is a Copper Sulfate solution with some
Sulfuric acid. In addition to this, one can add inhibitors and levelers such as Polyethylene Glycol
(PEG), Janus Green B, or a brightener. Each of these slows the rate of plating at peaks on the
surface of the Copper, leading to a smoother plated surface. The other type of additive is an
accelerant, which helps the throwing power of the solution and increases the rate of plating.
Hydrochloric acid is the only accelerant that has been tested.
Some sample plating baths:
225 g/L CuSO4
225 g/L CuSO4
50 g/L H2SO4
50 g/L H2SO4
50 ppm HCl
50 ppm HCl
8 ml/L Brightener
Note: This plating
bath is the easiest to Note: The brightener
work with but gives does not give an
rough results without exact composition
any inhibitors or
and this bath showed
levelers.
little difference from
the first bath.

225 g/L CuSO4

50 g/L H2SO4
50 ppm HCl
8 ml/L Brightener
3ml/L PEGDA

225 g/L CuSO4

50 g/L H2SO4
100 ppm HCl
600 ppm PEGDA
10 ppm Janus Green B

Note: Polyethylene
glycol diacrylate
should supposedly act
the same as PEG but
Copper plated in this
bath had a reddish tint.

Note: This bath had the

issue of Copper coming
out of the bath looking
oxidized with a
turquoise or black
color.

A given plating bath can last for a couple of months of light to moderate use before it becomes
unusably contaminated by particulates and other impurities from inserting samples. At that point
the bath can be disposed into a spent ordinary acids container.
A new bath can be made by starting to dissolve the CuSO4 in about 90 percent of the water that
will be used. Then the acids can be added to this water/solution. The solution then must be
stirred to dissolve all or most of the CuSO4. Finally the additives may be added and the solution
can be brought to its final volume with the addition of water.
Seed layer
The majority of the plating tested used about 400nm of sputtered Copper as a seed layer.
Chrome has issues with either high resistance or for some other reason not plating. The power

supplies used for plating have a maximum 5 Volt potential, which may be insufficient to
electroplate onto Chrome. Gold has no trouble plating Copper, but there is poor adhesion
between the Gold and the Silicon wafer. Often the seed layer and everything plated will come
off just by rinsing the sample after removing it from the bath.
Current densities
As a general guideline, the ratio of forward to reverse current should be from 1:2 to 1:5 and the
ratio of forward time to reverse time should be about 5:1 to 20:1. These are not absolute limits;
it is more important to make sure the total forward current exceeds the reverse current. Ex:

Average current should be positive and high enough to meet the desired current density. A
current density of 0.1mA/mm2-1mA/mm2 would be a good place to start, but can be increased or
decreased if sample is either not plating or plating too fast.
Time
From the desired current density and plating thickness:

Power supply-operation
Press the menu button to cycle between the status, setup, and saved profiles.
To set the power supply, from the setup screen turn the knob to switch between forward, reverse,
and high or low current alarms. Then press the select button on one of these parameters
to change an aspect of that parameter. The coarse/fine button alternates between large
and small increments per click of the knob. Press enter when finished to save the
parameters.
To start the power supply, from the setup screen press the run/stop button. The power supply
will switch to the status screen and display the average current and voltage.
To stop the power supply, press the run/stop button from any screen.
Sample setup
Take the lid off of the plating solution and turn on the stir plate to give the solution some slow
movement.

Place a copper plating ball onto the titanium spoon and set the apparatus so that the copper ball
goes into the solution and the second clamp is above the solution.
Clip the green wire onto the titanium spoon and the black wire onto the sample.
Submerge the sample into the solution to the proper depth, making sure not to set the clip touch
the plating solution. Maneuver the black wire into the second clamp and tighten it to
hold the sample in place.
To take a sample out, reverse these instructions, rinsing anything that has been in the plating
solution with water.
The Copper balls will darken, but they still function normally. If a white-greenish film forms on
the Copper, it will not electroplate well until the layer has been scrubbed or scraped off.
Sample Results
First sample:
Bath: 225 g/L CuSO4, 50 g/L H2SO4, 50 ppm HCl, 8 ml/L Brightener
Seed layer: 470nm Cu
Area: 180mm2
Forward current of 52mA for 20.0ms, reverse current of 108mA for 1.0ms
Average current density: 0.25mA/mm2
Distance between anode and cathode: 2-3cm
Time: 68 minutes
This sample had a 28 micron thick plating of Copper with a variance of about 10% from the edge
just submerged in the plating bath (26 microns) to the base nearest the electrolytic copper ball
(30 microns). The plating was rough on the surface, visible as being Copper colored but not
shiny. Also see note below regarding both samples.
Second sample:
Bath: 225 g/L CuSO4, 50 g/L H2SO4, 50 ppm HCl
Seed layer: 440nm Cu
Area: 28mm2
Forward current of 52mA for 20.0ms, reverse current of 108mA for 1.0ms
Average current density: 1.6mA/mm2
Distance between anode and cathode: 2-3cm
Time: 60 minutes
This sample had a 110 micron thick plating of Copper with a variance of about 50% from the
edge just submerged in the plating bath (83 microns) to the base nearest the electrolytic copper
ball (140 microns). The plating was rough on the surface, visible as being Copper colored but
not shiny. This sample had a buildup of Copper at the pointed ends of the pattern being plated.

Note: Both of these samples had less than optimal geometry, with the seed layer placed over a
pattern so that parts of the seed layer are removed with the photoresist. This gives no protection
against the Copper plating sideways as well as upwards and closing up gaps in the pattern as in
Figure 1. This also makes the Copper not plate as thickly since it grows outward as well as
upwards. With small features, the Copper may connect across gaps.

Even the alternative of putting the photoresist over the seed layer and leaving it on during plating
can still have problems with small features, if the Copper plates faster at the corners, it can close
up the well, leaving a gap in the center with no Copper.

Copper (dark) electroplated on Silicon substrate patterned with KMPR1005.