Industrial-level Quality PCB Through Hole Plating

About: My main hobby is electronics - from circuit design to making PCB's at home.

WARNING for US Readers: For some meaningless reasons the hypophosphorous acid and its salts (including calcium hypophosphite) is included into DEA List I of chemicals, so its distributions is controlled and availability is limited. I'm really sorry, that this method is unavailable for US readers.

Described method does not use expensive,  hazardous or hard to obtain chemicals, provides good adhesion of plated copper and has very good productivity, because all holes are processed at once. Sounds like miracle? But it is not.

Basically the method is very simple to use: just put board into activator solution, then into oven for about a half of hour, then wash it and put into galvanic bath to perform electroplating of the copper layer of necessary thickness. That't it. Of course the key is the activator solution. You need to prepare it once and then you can process several boards with it. While not in use solution can be stored for a long time without degradation of its properties.

Note, that description below does not include the electroplating step. There are several guides, recipes and detailed descriptions of the process, so I see no need to repeat them again. Especially taking into account, that most convenient one heavily depends on various conditions, availability of chemicals/materials and other things.

Lets begin with a little bit of history. This method uses ability of the some copper compounds to decompose under high temperature with the release of nano-particles of metallic copper. This allows to form a conductive layer on the processed surface and then deposit solid copper layer using regular electroplating. It was developed several years ago at the former USSR as a replacement for expensive palladium based method. After death of the USSR development of this method continued and at the beginning of the 90x group of the chemists leaded by Oleg Lomovsky obtained patent for the industrial version of the PCB through hole plating method (page is in Russian). This method was almost unknown to wide hobbyist audience until about year ago, when at VRTP.RU forum user JIN  published his article (page is in Russian) about through hole plating. The article described early version of the method, which has some issues which prevented its use in industry, but most of these issues are irrelevant for home use. What is more important, the article described recipe of base activator solution suitable for repeating in home environment. In fact method described below heavily based on the same recipe. Since then method started quickly gaining popularity in Russian-speaking hobbyist communities.

As mentioned above, to use this method, we need an activator solution. Next step describes preparation of the activator solution in details.

Step 1: Preparing Activator Solution

WARNING! DO NOT WORK WITH CHEMICALS WITHOUT GLOVES!
Although all ingredients are not hazardous in general, they still present danger to your skin.
Also, it is suggested to perform final steps of the solution preparation at the open air or with very good ventilation (keeping window open might be not enough). See below why.

To prepare an activator solution we will need following things:
1. Distilled water
2. Copper sulfate 
3. Calcium hypophosphite (Ca(H2PO2)2)
4. Ammonium hydroxide (25%)
5. Liquid soap

All ingredients are required in small quantities (see below) and most of them are widely available. The only less accessible component is calcium hypophosphite, but in fact it is not rare nor expensive, just can't be purchased in nearest drugstore or Home Depot. Probably simplest way to obtain it is just buy online as an analytic reagent. Minimal quantities usually about 1kg, this will be enough to open your own small PCB shop :)

The activator solution is prepared as follows.
1. Take 140ml of water and dissolve 30g of copper sulfate in it. Stir until all copper sulfate is dissolved. At this point solution will get light blue color.
2. Pour into solution 22g of calcium hypophosphite and carefully stir it for 3-4 minutes. Once you pour calcium hypophosphite into solution, there will appear sediment which change solution color to white-blue. The sediment consists mostly of gypsum (calcium phosphate). Note that there is quite high amounts of sediment, so use at least 0.5 liter cans for preparing solution.
3. Filter the solution through funnel with filter paper placed into it. Again, use large funnel. Also, at the end speed of the filtering might be quite slow, so be patient. The solution should have light blue (perhaps a little dull) color.
4. Pour through the sediment another 100ml of water.
5. Remove funnel and add 40ml of 25% ammonium hydroxide. WARNING! This reagent stink! So, while you'll be doing this, try to keep nose as far from the solution as possible. Once ammonium hydroxide is dissolved in the solution, it stinks much less, so activation solution is usable indoor, although it still stink so the container with the solution should not be left open for long time. The solution quickly thicken for some time and you'll see white flakes, but they quite quickly disappear and solution obtains deep blue color. You may speedup this process by stirring the solution.
6. Add about 5-6ml of liquid soap and stir for few seconds.
7. Add about 8-10g of calcium hypophosphite. Part of it will dissolve, but part of it will remain as a sediment in the solution. Stir solution for few seconds to speedup process.
Solution is ready. It is quite stable and can be stored for a long time without loosing its properties. Use tightly closed container and store it in dry place, away from direct sunlight and out of reach of children and pets. Since solution contains copper compounds, it might be toxic if you'll drink it, so it is not recommended to do so :)
Solution requires maintenance, especially if used intensively. Maintenance is quite simple - just check from time to time if there is still calcium hypophosphite sediment at the bottom of the container where solution is stored and if necessary add few grams of calcium hypophosphite.

Once you prepared the solution you're ready for the next step.

Images provided below show activator solution at different stages of preparation.

Step 2: Preparing Copper Laminate

Preparation of the laminate is very important step, it actually defines quality of holes after plating, so take special attention to this step.

1. Cut laminate to size slightly larger than board size. One edge usually is used for the fixing board during electroplating, so at one side make larger margin. 
2. Drill the board. All drills must be of exact necessary size, there will be no chance to drill hole of larger diameter without destroying copper in hole once hole is plated. Use tungsten carbide drill bits to get clean holes suitable for the plating.
3. Carefully inspect all holes against the light source and make sure there are no copper chips left in the holes.
4. Carefully sand copper surface with the flint paper of largest available number (i.e. with the smallest size of abrasive particles) and make sure that there are no copper borders around holes, especially at the opposite side.
5. Carefully wash the board using dishwashing detergent with soft abrasive, for example Cif or something like that. 
6. Finally carefully rinse the board in water.
7. Inspect holes again and make sure they are clean.

The board is ready for the next step.

Image shows prepared board right before activation.

Step 3: Activating the Board Surface

This process is quite simple:

WARNING! DO NOT TOUCH BOARD DURING THIS STEP, EVEN IN GLOVES! This may cause problems with the plating.

1. Open the container with the activator and slowly put horizontally oriented board into the solution for 2-3 seconds (do not touch the bottom of the container!) and then lift it slightly above the surface of the liquid to let the activator flow down. You'll see that liquid at the board changes its color around the holes. This does mean that activator freely flows through the holes and wets them properly. Check if color is changed around all holes and if not, slowly put board back into solution and immediately lift above the surface. Usually this step need not to be repeated more than twice. If this is not so, then you have problem with the holes, so rinse the board in large amount of water, fix the problem and repeat entire step again. It is not recommended to keep board in the activator more than few seconds because this may result to problems at the further steps.
2. Once holes are wet, put board off the solution, rotate it vertically and let excessive activator flow down back to container.
3. Once most of the excessive activator flew down, close the container and distribute remaining activator as uniformly as possible by rotating board.

Once activator is distributed, board is ready for the next step.

Image shows activated board. Notice that all holes hold the activator. There is no need to remove it specially, but also no need to do anything if some hole lacks the activator film inside.

Step 4: Thermal Treating

To perform this operation you'll need some kind of electric oven. The monitoring and controlling of temperature is necessary.

1. Put board into the oven and start heating. When temperature reaches 125 degrees (Celsius) hold it at this level for at least 10 minutes (12-15 minutes highly recommended). 
2. Resume heating until it reaches 175 degrees and hold it at this level for at least 5 minutes (7-8 minutes highly recommended).
3. Stop heating and open oven but keep board inside until it's temperature crosses point 100 degrees.

At this point board has thin copper layer at most surfaces (including holes) covered with thick layer of remaining products of pyrolysis of the activator. All we need to do is just gently remove these products from the board as the next step. 

Images shown below show the board after first and after second stage of thermal treating.

Step 5: Cleaning Up the Board

This step is quite simple: just gently rinse the board in the water using soft sponge and some liquid soap. WARNING: Do not use washing liquids with soft abrasives at this step! The copper layer is very thin and can be damaged. Unlikely that you'll be able to remove it completely (adhesion is quite good), but you may break electrical connection between deposited layer inside holes and laminated copper. During electroplating lack of connection results to lack of copper deposition. So, be careful at this step.

Once board is cleaned up it is ready for the electroplating.

Image shows the board seen at previous steps after about 5 minutes (out of required ~60) of electroplating (i.e. it's almost the very beginning of the process). All holes are already plated with smooth shiny copper layer. 

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171 Discussions

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jhont13

Question 15 days ago

Where can I buy the calcium hypophosphite online?

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BogdanM47

9 months ago

I don't understand why should use some kind of alcohol or glycerol for mixing sodium hypophosphite with calcium chloride. My basic understanding is that resulting NaCl has the best solubility in water, it's easier to separate by filtering, so the remain powder is a good calcium hypophosphite.

here is a good pdf about synthesis of calcium hypophosphite:

https://www.atlantis-press.com/proceedings/ifeesd-...

5 replies
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BrunoB66BogdanM47

Reply 21 days ago

I also don't understand the use of Metanol or Glycerol to make the Calcium Hypophostphite. I would appreciate if someone could explain that. Sorry for my lack of understand of the chemistry involved.

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BrunoB66BrunoB66

Reply 21 days ago

I have put together a "plan" that I plan on trying tomorrow. The following information is not validated cause, like I said, I don't have any chemical knowledge other than some googling around and my high school chemistry classes. This article doesn't look very active, but if anyone more knowledgeable can give some pointers, that would be awesome:

Molar Masses
Na2PO2H2 88 g/mol
Na2PO2H2.H2O 106 g/mol
CaCl2 111 g/mol
NaCl 58.4 g/mol
Ca(H₂PO₂)₂ 170 g/mol
H2O 18 g/mol

Balanced Equation
2NaPO₂H₂.H₂O + CaCl₂ = 2NaCl + Ca(H₂PO₂)₂ + 2H₂O
(amounts) 126,7g 65,28g 68,9g 100g 21,0g

Solubility of reagents
NaPO₂H₂.H₂O (Monohidrate)
In Water 1000g / L
In Glycerol "Soluble"
NaPO₂H₂ (Anydrous)
?
CaCl₂ (Anydrous)
In Water 745g / L
In Glycerol "Readily soluble"

Solubility of products
NaCl
In Water 360g / L
In Glycerol 61g / L
Ca(H₂PO₂)₂
In Water 117g - 154g / L
In Glycerol "Slightly soluble"

Instructions (The Plan)
1. Dissolve 126,7g of NaPO₂H₂.H₂O in 130ml of distilled water. Add a little heat if it gets hard to dissolve it all.

2. Dissolve 65,28g of CaCl₂ in 90ml of distilled water.

3. Mix both solution and stir for 5 minutes. Add a little heat to help the reacton to happen.

At this point, you should have a solution with 68,9g of NaCl mostly dissolved and 100g of Ca(H₂PO₂)₂ of which 33,88g will be dissolved and the rest 66,12g should have precipitated.

Now, pass the solution through a coffee filter, extract the paste and let it dry in an oven for an hour (or until it look dry).

That should be it. You should have your Calcium Hypophosphite. This method doesn't seem very efficient because it makes you lose about 34% of the Calcium Hypophosphite to the solution. But it's easy enough that anyone can do and you don't have to mess with flamable chemicals like methanol.

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syevtushenkoBogdanM47

Reply 23 days ago

I guess use of particular solvent depends on solubility of different instances in different solvents.

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BogdanM47BogdanM47

Reply 9 months ago

I follow the instructions for synthesis of calcium hypophosphite, then made the solution according with above instructions, but at the end, instead of adding 8-10g of calcium hypophosphite, i used sodium hypophospithe 15-20g. Worked much better for me.

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BrunoB66BogdanM47

Reply 24 days ago

So you just mixed sodium hypophospithe with Calcium Cloride with water and it worked? Were you able to get plated through holes?

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DominickP4

2 months ago

Does anyone still have the PDF file from this post as it is no longer active

1 reply
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syevtushenkoDominickP4

Reply 23 days ago

As far as I remember there are no PDF files inside article.

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ericmitc

2 years ago

If still interested: there is a way using Sodium Hypophosphite. to make an activator-solution like this one.

After some testing and reading through the literatur our Lib, I figured out an easy way that works with stuff that can be freely bought. In germany, like in many other countries its hard to get calcium hyp. when you dont want to order from china for actually at least 100€ (for 1 kg - gets less when order big quantities) with shipping-costs.

Well this is no receipe because Im still trying to normalize the procedure with best working parameters, but its at least one possible way to go.

You need:

sodium hypophosphite,

Ammonium Hydroxide

Copper-Sulfate

and HCL acid,

At first we need to get Hypophosphorous acid (the stuff your government won't like because its used to make crystal meth) from the sodium-hypophosphite and the HCL-acid.

Therefore you heat the sodium-hyp. to about 80C and put you HCL to it.

As a result you'll get Hypophosphorous acid and salt.

Cool down the solution to just over 0C for less soluability of salt and filter out the salt. Now you got a good acid with the clou that it can react with copper-salts to copper-hypophosphite, the main part of the reaction that syevtushenko described!

But there will be the problem that the Hyp.Acid directly wants to reduce a solution of copper-salts to copper in front of your eyes. That is why you need to make the sulfate-solution not with water but with the ammonium-hydroxid-solution. It builds complexes that cant be reduced this way. So put some of the Copper Sulfate (doesnt matter with hydrated or not) with the ammonium hydroxid together till all the CuSo4 got dissolved. Try to make a nearly saturated solution.

Then you put a little hypophosphorous acid to it and stirr.

When you go on as described by syevtushenko with putting your clean pcb into it and heating up the stuff, the ammonium hydroxid fastly evaporates and you'll get your nano-copper on the surface.

Of course you should use some soap, ethanol or tensides to make a solution that flews easily through the holes like described.

If there is still a need for informations, feel free to ask. I hope that someone is helped by these informations that took much time for me to get

Kind regards,

Eric Pidun

2 replies
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BrunoB66ericmitc

Reply 24 days ago

First of all, thank you for the information!
I was wondering if using Ascorbic Acid instead of the Hypophosphorous Acid would work. I've seen people extracting copper nanoparticles mixing Ascorbic Acid (vitamin C) and Copper Sulfate.

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LeeW65ericmitc

Reply 2 years ago

Hi Eric.

Thanks for the above. I'm keen to follow your instructions and wondering if you could share what quantities of the chemicals you are uesing?

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AliG89

1 year ago

Hello, calcium hypophosphite is not available in Turkey. What can I use alternative chemistry. thank you

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Muhammad NourE

2 years ago

HI,

Very nice

I have some questions regarding the chemicals used in the method, first of all can you in simple words :D explain the need of every component

For copper sulfate it is easy and obvious but for the other 2 components, I have no idea!

Also is there any alternatives for the Calcium hypophosphite ?

I am not expert in chemistry nor even beginner, my knowledge is extremely primitive and I barely know that heating accelerate reactions, nothing more :lol

Thanks

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SachinS84

2 years ago

Hi

Appreciate this great article !!

having read the article and all the comments , i have manged to plate my vias and holes. I am to apply the dry film photo resist film over the copper clad now and would later expose and develop it. My problem is :-

How would i protect the PTH from etching away

1 reply
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mientos4SachinS84

Reply 2 years ago

If you're using dry film, there is no problem - it can be used for tenting holes. But you must take care with lamination - too high temperature or pressure will damage the dry film around holes (I turn the laminator on for ~20-30s, then wait 20s and then insert the pcb, the temperature of rolls is something like 60C). Recommended temperature is 100C, but it depends of the pressure which cannot be adjusted in my case, and 100C damage my dry film.

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messina.david.7

2 years ago

Hello, I realized the solution,
I ask myself the following questions.

What is the chemical composition of the solution?
What is the reaction to 125 ° C?
What is the reaction to 175 ° C?
is there a safety sheet?

1 reply
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syevtushenkomessina.david.7

Reply 2 years ago

Chemical composition of the solution, at the best of my (limited) knowledge is the ammonia complex of copper hypophosphite. Both reactions (at 125 and at 175 degrees) are thermolysis of this complex with the release of copper nanoparticles. During first phase most of the copper is released while second phase is reflow during which copper nanoparticles are joined together. I believe that operational window for both reactions +- 10-15 degrees. Note that I'm not a chemist and here I just repeating what (and how) I did get from papers and from discussions with chemists. So, take this information with care.

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sean01

2 years ago

Hi ericmitc

Do I understand that I
can replace the Calcium Hypophosphite with Sodium Hypophosphite and do
the rest as per the recipe and it will work? What do you mean with 4/3
of amount of Copper Sulfate of you Sodium Hyp? I don't understand?

I
really hope this would work I can not get hold of the Calcium
Hypophosphite at all here in South Africa? I am also struggeling to get
hold of Ammonium Hydroxide normal Ammonia I can get that they use in
cleaning products.

Kind Regards

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ericmitc

2 years ago

For still interested people trying to do this with Sodium hypophosphite : it works fine! You need to take about 4/3 of the amount of CuSO4 of you Sodium Hyp. :)

Greetz,
Eric