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

225 g/L CuSO4 50 g/L H2SO4 100 ppm HCl 600 ppm PEGDA 10 ppm Janus Green B 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.