Indium Corporation
From One Engineer to Another®

Tin Wiskers, Solder Alloy Density, Safety: Sharing a Few Comments

Monday, April 16, 2012 by Dr. Ron Lasky [Dr. Ron Lasky]

Folks,

Some time ago I wrote a post, “In Search of Tin Whiskers,”  Michael responds below.  He makes some good points.

Dr. Ron, I'm responding to your  blog regarding tin whiskers. I actually have a failure analysis report I did a couple of years ago in which failure of our product was due to this issue and occurred on a part that came into RoHS compliance only 3 months prior.
 

I'm not sure that your question of identifying whisker issues in product that proper steps have been taken to mitigate the problem is a constructive one. The fact is that many of the component manufacturers from overseas jumped into compliance without any thought or regard to this issue thereby flooding the industry with components such as plagued my company. We have not had this issue since we've specified an alternate finish.

These whiskers are so delicate that most problems disappear when the technician starts to work on the failed unit and the problem never re-appears so it is written off as an anomaly, loose/bad connection and not investigated any further. It was only my own curiosity as to the number of "no problem found" failures of our keypads we had suddenly encountered that caused me to dig deeper and when I looked into the connector I was amazed at the crystal city staring back at me. I couldn't believe what I was seeing after all of these years.

After seeing this problem first hand I became, and am, quite convinced that there were and are people who will be losing life, limb, and property because this forced compliance with its risk was not given proper worldwide attention.

Michael.

A popular topic Re my blog is solder density calculations. Rhonda writes……

Hi Dr. Lasky,
I am a precious metals recycler and would very much appreciate your verifying the validity of an equation that approximates the Karat Value of various alloys of gold based on S.G. which I will call density or "D," and the Karat Value is "K." The equation is seems to hold relatively true even when the exact composition of the alloy is unknown, although the percent of error obviously will increase as density decreases. I would also appreciate not only verification but also more specific information on percent of error for densities below about 14 or 15 g/cc. Here is the equation:

K = 0.0089D^3 - 0.550D^2 + 12.5299D - 77.06

Thank you so much for whatever assistance you can provide.

Rhonda

These types of equations can only work for one alloying metal with the gold.  This one is only for copper.  It is also calibrated in Rhonda’s favor as it reads the karat level about 10% low.   I was able to determine this by using the Excel Solder Density worksheet that I developed. If the alloy was gold and lead, a 50% by weight gold (12 karat) would show as 15.7 karat with this equation and Rhonda would lose her shirt.

 

 

In response to my blog post on copper as the precursor to civilization, Harvey writes about pollution from early mining operations…..

Also interesting, early copper mining and processing led to the first examples of human induced environmental damage. There are documented sites in the Alps where copper processing by prehistoric peoples has left areas treeless to this day, due to heavy metal contamination.

Harvey

Mining and smelting were very tough businesses in ancient days.  In addition to pollution, many workers died from toxic fumes.

Dr. Ron

Indium-Lead (In/Pb) Solder Alloys for Reliable Gold Interconnects in Semiconductor Assembly

Wednesday, April 4, 2012 by Dr. Andy Mackie [Dr. Andy Mackie]

Maria Durham, Indium’s new Technical Specialist in Semiconductor and Advanced Assembly Materials, has been doing some research on indium lead (In/Pb) solder alloys. We chatted about her findings this week. 

 [Andy C. Mackie: ACM] Which indium/lead solder alloys are most common, and what are their properties?

Maria Durham indium corporation semiconductor solder flux[Maria Durham: MD] Firstly, the use of lead-(Pb-)containing solders in some soldering applications is restricted due to local environmental and RoHS compliance, but there are still many applications where they are  allowed. Many military, aerospace, and industrial equipment uses, as well as many applications related to vehicles, are exempt. The table below shows the most common indium/lead (In/Pb) alloys (pink) and their properties, sorted by liquidus temperature; the higher of the two melting points (solidus and liquidus) seen for non-eutectic alloys. In blue are three comparison materials.

 

Indalloy 205 is the most commonly used, probably because it has the closest liquidus temperature to the tin/lead eutectic (183°C), 63Sn/37Pb (Indalloy 106). This means it can be reflowed using a standard Sn/Pb eutectic profile. The next most common alloys that are used are Indalloy7, 204, and 206.  Besides the melting range, indium has comparable thermal and electrical conductivity to standard materials.

 

Table 1 InPb copyright Indium Corporation 2012(C)[ACM] What makes indium-lead (In/Pb) solders so attractive, and why have we seen a recent resurgence in their usage?

 [MD] One main attraction to using indium/lead (In/Pb) solder alloys in soldering to precious metal surfaces is that, unlike tin-containing solders, they do not leach gold. That is, gold does not dissolve in them to any appreciable extent. During discussions at Semicon West in 2011, one of our California customers reported going through 8 simulated reflows with Indalloy 205 in contact with a gold surface with no loss of joint strength and no joint embrittlement. That is pretty impressive. Note that embrittlement is often caused by gold-intermetallic formation. It has been noted that even at 250°C, 50In/50Pb dissolves Au at a rate 13 times slower than it does into 63Sn/37Pb, although this, of course, is a kinetic, not a solubility limit, study.

 

The higher melting Indalloy 164 (92.5Pb/5In/2.5Ag) has the lowest coefficient of thermal expansion (CTE) of all of the In/Pb solders and is able to withstand the higher temperature excursions that can be seen in step-soldering type applications (where a very high melting solder is used to form the first joint, followed by a next lowest melting alloy, and so on). This is seen in applications such as power electronics assembly, where the first step solder is often used for die-attach either as a solder paste, wire, or preform. The high melting point helps the solder withstand the operational temperatures associated with under-the-hood electronics, in applications such as engine control modules, where Indalloy 151 (92.5Pb/5Sn/2.5Ag) or Indalloy 163 (95.5Pb/2Sn/2.5Ag) are most commonly used. In/Pb solder is excellent on very rigid structures such as ceramic-to-metal or ceramic-to-ceramic. The desired solidus / liquidus temperature range can be adjusted by changing the indium:lead ratio, making it very easy to “dial in” the alloy to a specific reflow process.

Another attraction to using In/Pb solders is that they exhibit good fatigue resistance in thermal cycling from -55°C to 125°C.  In testing, the 50In50Pb solder joint fatigue life is about 100 times greater than that for 63Sn/37Pb.

 [ACM] What fluxes are used in these applications, and how are they formulated differently?

 [MD] The fluxes most compatible with the lower melting point (<200°C) indium-containing solders are NC-SMQ-80 (solder paste) or the lower-tack TacFlux® 012 (suitable for use with wire, preforms, and spheres). These are no-clean fluxes, specifically formulated for lower temperature reflow.  Under appropriate low temperature reflow these fluxes leave behind benign residues that do not need to be cleaned off (“no-clean” flux), although they are often cleaned off in most practical applications, usually to ensure reliable wirebonds absent of flux spatter.

===== 

 [ACM]  Maria, thank you very much!

 To learn more, please contact us.

 Cheers!  Andy

Switching from High Lead Solders to Eutectic AuSn

Friday, January 20, 2012 by Amanda Hartnett [Amanda Hartnett]

Two categories of solder are available to choose from when the in-service environment for a device reaches above 125°C either in continuous operation or thermal cycling accelerated life testing. These categories are those comprised primarily of lead, and those of gold. From the electronics industry’s drive to eliminate lead, many manufacturers who have traditionally used lead solders are treading cautiously, looking now at the gold solders, primarily at Indalloy 182 (80Au20Sn).

Intermetallics are more brittle than solder.  This is the typical location for solder joint failure.The most common concern regarding this switch relates to the strength of AuSn, which is much higher than the lead solders. The degree that this should be of concern however, should be realized within the scope of the application.

For instance, review this case scenario:

Indalloy 159 (90Pb10Sn) was used in a device for years to adhere high temperature sensors to a calibration probe that is slowly cycled in operation from 350K (~75°C) to 500K (~225°C). The solder joins a nickel and gold plated Kovar™, or platinum or platinum coated, nickel lead to a tinned copper lead. The solder joint is not placed under tension or shocked.

Considering the high temperature solder options in this scenario, the AuSn would be mechanically preferred.

Why?

Well, tin-bearing soft solders will leach gold from gold metallizations during soldering, creating a brittle Au-Sn intermetallic layer within the solder joint. The more gold available, the more consumed, and the greater the thickness of the resultant intermetallic layer. The brittle nature of this layer, situated intimately next to the relatively soft PbSn solder layer, creates differential stresses that promote crack propagation upon thermal cycling.

AuSn was not considered previously because the engineers were familiar with its hardness and, given the cracking failure described using a softer solder, they did not anticipate improvement. It was a pleasant surprise to them to find that switching to a lead-free solder would not sacrifice the quality of their device. AuSn is a brittle alloy but, unlike the description above, no differential stresses are involved. 

Note: Eutectic gold solders have been used for many years to solder nickel plated Kovar™ lids to high reliability ceramic packages and have a good history of fatigue performance.

Military/Aerospace Lead-Free Solder Reliability Still Unproven

Monday, December 12, 2011 by Dr. Ron Lasky [Dr. Ron Lasky]
Manhatan Chart

Folks,

I’m taking a few moments from Wassail Weekend , held annually in my village, Woodstock VT, “The prettiest small town in America”, to write a post about last week’s workshops at ACI.

Indium colleague Ed Briggs and I gave a 3 hour presentation on “Lead-Free Assembly for High Yields and Reliability.” I think Ed’s analysis of “graping” and the “head-in-pillow” defect is the best around. 

There was quite a bit of discussion on the challenges faced by solder paste flux in the new world of lead-free solder paste and miniaturized components (i.e. very small solder paste deposits.) One of the hottest topics was nitrogen and lead-free SMT assembly. There seemed to be uniform agreement that solder paste users should be able to demand that their lead-free solder paste perform well with any PWB pad finish (e.g. OSP Immersion silver, electroless nickel gold, etc.) without the use of nitrogen. Not only does using nitrogen cost money, but it will usually make tombstoning worse. However, in the opinion of most people, nitrogen is a must for wave soldering and, since it minimizes dross development, it likely pays for itself.

After Ed and I finished, Fred Dimock, of BTU, gave one of the best talks I have ever experienced on reflow soldering. He discussed thermal profiling in detail, including the importance of assuring that thermocouples are not oxidized (when oxidized they lose accuracy). He also discussed a reflow oven design that minimizes temperature overshoot during heating, and undershoot when the heater is off. Understanding these topics is critical with the tight temperature control that many lead-free assemblers face.

Fred Verdi of ACI finished the meeting with an excellent presentation on “Pb-free Electronics for Aerospace and Defense.” Fred’s talk discussed the work that went into the “Manhattan Project.” A free download of the entire project report is available.

There appears to be agreement that acceptable lead-free reliability has been established for consumer products with lifetimes of 5 years or so, but not for military/aerospace electronics where lifetimes can be up to 40 years in harsh service conditions. These vast product lifetime and consequences of failure differences are depicted in the Fred's chart (above). Commercial products are in quadrant A and military/aerospace products in quadrant D.

One of the greatest risks faced by quadrant D products is tin whiskers. Fred spent quite a bit of time discussing this interesting phenomenon. One of the challenges of this risk is that there is no way to accelerate it, so you can’t do an equivalent test to accelerated thermal cycling or drop shock. Fred mentioned that there have now been verified tin whisker fails, the Toyota accelerator mechanism being a confirmed one.

In addition to tin whiskers, lead-free reliability for quadrant D products (with a service life of up to 40 years) in thermal cycle and other areas remains a concern.  I mention that tin pest was not on the list of issues for this quadrant.

Fred and the Manhattan Project Team have identified many "gaps" that need to be addressed to determine and mitigate the risk of lead-free assembly for quadrant D products.  They plan to start this approximately $100M program in 2013.

For those that missed this free workshop, ACI host Mike Prestoy is planning another one in 6 months.

Cheers,

Dr. Ron


Intermetallics In Soldering

Friday, November 11, 2011 by Eric Bastow [Eric Bastow]
Intermetallics are a necessary evil in the metal-to-metal bonding world, which definitely includes soldering. There are two basic ways that metal will "chemically" bond to another metal: 1) solid solution 2) intermetallic. We will focus just on intermetallics for the moment as that is the most pertinent to the soldering world.

Many people confuse or interchange "wetting" for intermetallic formation (bonding). Wetting is just wetting. Just because a solder "wets" to a surface does not mean that an intermetallic "bond" has been formed. For example, and I have done this myself, 55.5Bi 44.5Pb can be melted onto a piece of copper. The molten BiPb will flow and "wet" to the surface of the copper. However, upon solidification (cooling) of the alloy, the BiPb can be peeled off. Why?... because no intermetallic was formed between the BiPb and the copper surface.

Intermetallic LayerIn order for an intermetallic to form, some amount of the surface metallization must dissolve into the molten solder. For this reason, Sn (tin) has long been a critical component of solder alloys. Molten Sn (tin) is an excellent solvent of many other metals. And, conveniently for us, those "many other metals" include elements like copper, gold, silver and, to a lesser degree, nickel. The rates at which these other metals dissolve into molten tin (solder) will differ. Gold dissolves readily into solder; whereas nickel does so slowly. So, because the rate of dissolution is different for each metal, the rate of intermetallic formation is also different. I have dealt with companies that have a long history of soldering to copper, and, for whatever reason, they are forced to switch to an ENIG (Electroless Nickel / Immersion Gold ) surface. (It is important to note that the gold layer is very thin and only applied to protect the nickel from oxidation. This gold layer readily dissolves completely into the molten solder and the "bond" is actually made to the nickel surface). When they make the change they sometimes encounter a number of issues such as incomplete wetting, poor bond strength, etc. and do not know why. They are not aware that the same reflow profile (time and temperature) that yielded a good (intermetallic) bond to copper is not sufficient to get the same intermetallic bond to nickel. Once they adjust their profile (more time and/or higher temperature) to allow for sufficient intermetallic formation , they are able to achieve acceptable solder joints. Keep in mind that dissolution, the phenomenon of a solid dissolving into a liquid, is effected by both time and temperature. Generally speaking, more time and more temperature allows for more dissolution and, hence, more intermetallic formation.

As mentioned in my opening line, intermetallics are a necessary evil. Why "evil"? Because they tend to be the most brittle part of the solder joint. Some intermetallics are more brittle than others. (This should be taken into consideration when choosing a solder alloy for a particular metallization).  For example, intermetallics that form between Sn and Au are often extremely brittle.  Being brittle, they can be subject to fracture, etc. This is a case where more is not always better. Yes, you need an intermetallic to get a "bond". Too thin of an intermetallic layer can be bad; but too thick of an intermetallic layer can be just as bad, if not worse. Believe it or not, the solder may not adhere well to its own intermetallic layer. Intermetallics are generally crystalline and chemically-stable structures....they do not really react with anything else once they have formed. If you have ever looked at a fractured solder joint, you may have noticed that the fracture likely took place right at the interface between the intermetallic layer and the bulk solder.

One other possible outcome of an excessively thick intermetallic layer is "voiding" at the interface. Why? Well, we first need to look at the reaction products. There are two basic types of reaction products that form the intermetallic layer between Sn and Cu. They are Cu3Sn and Cu6Sn5. In the fKirkendall Voidingirst case there are 3 Cu atoms to every Sn atom and in the second case 6 Cu atoms to every 5 Sn atoms. In both cases the Cu is being consumed faster than the Sn atoms. Because of this disparity in the reaction, in an exaggerated scenario, little holes or vacancies ("voids") can form in the copper surface.

Intermetallic formation is not only limited to the solder process. Metal atoms can diffuse even in the solid state. And that movement can cause the metal atoms to interact, react, and form intermetallics or cause the existing intermetallic layer to thicken. "Ageing" experiments are often performed to measure how much the intermetallic layer will change and what effect it will have on the mechanical nature of the joint.

It is well beyond the scope or purpose of this blog post to provide an exhaustive discussion of intermetallics. Whole books could be written on the topic. So, I am far from doing justice to the topic of intermetallics. I can only hope to shed a little light on the subject.

Comments or questions are very welcome.

SMTAI 2011: My Review

Thursday, October 27, 2011 by Dr. Ron Lasky [Dr. Ron Lasky]
Dr. Lasky participating in a CONFLICT MINERALS panel discussion at SMTAI 2011.Folks,

I was at SMTAI 2011 last week and, as usual, JoAnn Stromberg and team did an amazing job.

I think SMTAI's technical program is the best around, offering scores of topics and world class speakers.  I chaired a session (MFX4) Alternate Lead-Free Alloys, with papers by Dr. Ning-Cheng Lee, Srinivas Chada, and Jasbir Bath.

I also co-authored three papers:
 
1. Choosing a Low Cost Alternative to SAC Alloys for PCB Assembly, with Brook Sandy-Smith

2.  Correlation of SIR, Halide/Halogen and Copper Mirror Tests, with Nicole Palma

3. Minimizing Voiding in QFN Packages Using Solder Preforms,  with Seth Homer

The technical sessions were extremely well attended, with 30-60 people in each.  An emerging trend is that the tech sessions are  swamped and the show floor not so much.  I think the Internet allows people to get a sense of products online, while the technical talks enable one-on-one discussions with experts in the Q&A after the papers.  It is tough to beat this interaction, even in an Internet world.

The new hot topic, to me, is the interest in "Conflict Minerals."  I participated in a panel discussion on this topic (see image).  It appears that the Dowd-Frank act will require publicly held companies to show "due diligence" in investigating their supply chain to determine if their tin, tantalum, gold, and tungsten come from "conflict" mines.  This requirement will likely ripple up and down the supply chain.  So we all need to become knowledgeable in this topic. Indium Corporation is very involved in this.

As for the venue, Forth Worth was nicer than I expected (not that a business traveler ever gets to see much). There was a nice restaurant area near the conference center. It reminded me of the Gaslamp Quarter in San Diego.  But for me, I longed for Disney World a little. Next year!

Cheers

Dr. Ron

Why doesn't my 80Au 20Sn solder look any thing like gold?

Wednesday, August 24, 2011 by Eric Bastow [Eric Bastow]
80Au 20Sn solder frames compared to the appearance of stainless steel tweezersIf you have ever handled a piece of 80Au 20Sn solder alloy, one of the things that you might have noticed is that it does not look anything like gold (yellow lustrous metal). In fact, it does not look all that different than tin or any other tin based alloy.

And, yes, before we continue....it is the same gold (Au) used in jewelry, etc.

To the AuSn newbie, the first shipment of 80Au 20Sn solder may cause a little bit of alarm. "Did they send me the wrong alloy? This doesn't look like it has any gold in it!!!"

To the human mind, when one thinks of something that is comprised of 80% of a material, one naturally assumes that material will dominate the properties of the composite material. And, normally, that would be a valid assumption. However, in the case of a solder alloy, the composition is almost always reported in terms of percent by weight. So, in the case of 80Au 20Sn, the alloy is 80% by weight gold and 20% by weight tin. The "issue" lies in the fact that gold is more than twice as dense as tin; 19.3 g/cc versus 7.3 g/cc. 

So, let's think about this.............

If we have 100 grams of 80Au 20Sn alloy, you have an alloy comprised of 80 grams of gold and 20 grams of tin. But, it terms of volume of gold and tin, you have 4.15 cc of gold and 2.74 cc of tin. So, by volume, the alloy is 60% gold and 40% tin. The 40% (by volume) of tin in the alloy is enough to "dilute" the gold and greatly diminish any "yellowing" that one would expect the gold to impart to the appearance of the alloy. 


If anyone has ever attempted to accurately photograph a shiny metallic surface, one can appreciate the difficulty in so doing. So, the photo shows some 80Au 20Sn solder preform in comparison to a pair of stainless steel tweezers. Visually there is very little, if any difference in appearance.

 

High Melting Pb-free Solder Paste

Wednesday, August 3, 2011 by Dr. Andy Mackie [Dr. Andy Mackie]
Dr Ning-Cheng Lee (Indium Corporation's Vice-President of Technology) just let me review his team's excellent upcoming paper on solder technology for high temperature Pb-free (lead-free) [HTLF] applications, such as Power Semiconductor die-attach. Dr Lee will be giving this paper at the ICEPT-HDP Conference in Shanghai (August 2011).

The basis of his work is that solders that do not melt at 260C ( that is, solidus > 260C), and thus are theoretically able to allow components to pass MSL level 1 testing per JEDEC/IPC J-STD-020D-.01, usually have a variety of drawbacks. These include cost, sensitivity to oxidation, poor wetting, and excessively high required reflow temperatures. For some engineers, gold/tin (the eutectic 80Au/20Sn alloy or 79Au/21Sn) with its high melting point (eutectic m.p = 280C) and excellent thermal conductivity remains the only possible solution, but the rising cost of gold is driving many to seek viable alternatives.

BiAg versus BiAgX - solder technology high temperature Pb-free lead-free HTLF  Power Semiconductor die-attachDr Lee's team's innovation is a mixed-solder approach called BiAgX, which uses one of the solder components to melt and form an intermetallic with the substrate surface, which is then itself wetted by the majority alloy component of the paste.

The most dramatic evidence of BiAgX's improvement in wetting/solderability over the standard 89%Bi/11%Ag alloy is seen in photographs (right) of reflow onto oxidized bare copper and alloy 42.

There are also dramatic improvements in thermal cycling over the standard Indalloy 151 (92.5Pb/5Sn/2.5Ag) and 171 (95Pb/5Sn), too, and I look forward to discussing this further with the team. I recommend you watch Dr Lee's presentation or read his paper to learn more.

Please note, as always, that the metal percentages reported in the above are all based on weight (%w/w), not on molar units.

Cheers!  Andy

Solder Wire

Tuesday, August 2, 2011 by Carol Gowans [Carol Gowans]
Indium wire: solder, cryogenic hermetic sealing, die attach, thermal interface managementSolder wire is generally used for manual soldering operations, including rework.  But, it can also be used in automated applications such as die-attach soldering.  Solder wire can be flux-cored, or solid with a separate flux used.

Each application can have different requirements for the wire.  For example, wire used in die-attach applications needs tight dimensional tolerances to insure an exact, repeatable amount of solder is deposited each time.  Reduced oxides are also critical to eliminate any "splattering" of the molten solder during the deposition process.

Wire can also be used for non-soldering applications. For example, indium (and indium alloys) wire are often used as a sealing material (particularly in cryogenic sealing applications) - more here) and as a thermal interface / management material.
Sn Ag Die Attach Wire
Decades ago, 0.030" (0.76mm) diameter was the standard size, but today we are able to produce diameters as small as 0.001" (0.025mm) in tin silver (Sn Ag), tin silver copper (SAC) and gold tin (Au Sn) alloys.  Considering that a human hair is about 4X that size, that is a very small diameter!  Pure indium wire is limited to 0.010" (0.254mm), but alloys containing indium can be produced smaller than that.

The wide variety of diameters available in Au Sn make this alloy ideal for the complex applications in medical, aerospace, and other high reliability applications.  However, the Sn Ag and the Sn Ag Cu are used across a variety of standard applications that require lead-free materials.  Sn Ag is particularly good in soldering to Nitinol.

At first look, wire seems like a pretty simple product.  But specifying the right alloy, diameter, tolerances, and packaging can make all the difference.  It can help you achieve a repeatable process that gives you high yields, strong solder joints, and enhanced profitability.  For further information - contact me.

Carol Gowans

Indium Corporation at Semicon West 2011

Friday, July 15, 2011 by Dr. Andy Mackie [Dr. Andy Mackie]
Many, many thanks to the hundreds of you who came by the Indium Corporation booth at Semicon West this year. Some of you came to hear about our recent global Semiconductor Assembly Materials Roadmap presentations, and all of you wanted to talk about your specific materials needs. Special thanks to those of you who shared the many successes you are having with our growing portfolio of applications-specific materials.


Based on these discussions, just a few of the topics that you will be hearing about in this blog in the coming months are:

- Lead/indium paste for multiple reflow applications onto gold pads
- Tin antimony solder paste
- Fluxes for 2.5D and 3D flip-chip applications
- Waferbumping fluxes for microbumps
- Jetting epoxy fluxes
- Tombstoning in semiconductor applications

PoP paste 9.88-HFAlso: a final big THANK YOU to our friends at Nordson/Asymtek for showcasing the Indium halogen-free PoP paste Indium9.88-HF which was still dispensing after over 3 days of continuous usage at room temperature: proving its hard-earned reputation as the Energizer bunny of Pb-free (lead-free) dispense pastes. Here is a picture from the final day.

We look forward to seeing you all in 2012 (Exhibits: July 10-12th, 2012).


Cheers!  Andy

Solder Alloy Densities: Comparing Calculated to Actual

Sunday, June 19, 2011 by Dr. Ron Lasky [Dr. Ron Lasky]

Folks,

I have
occasionally written on calculating solder alloy density, as there is surprisingly more interest than I thought there would be in this topic. Recently, it occurred to me that it might be beneficial to compare the calculated densities to actual densities of a few alloys to see how accurate the correct formula is (for the derivation of the correct formula see below). The formula assumes “perfect mixing” (i.e. no interactions between the alloy elements). The alloys we investigated were tin-bismuth-silver, tin-silver, tin and tin-bismuth.

To measure the density, I obtained a few alloys from Indium Corporation. My student, Evan Zeitchik, determined that a good technique to measure density is to machine the alloy into a rectangular parallelepiped (see photo), weigh it, and calculate its volume from its dimensions.  The results agree with the correct formula to about 1 to 2 %. Some people would ask why there is any difference. The reason is that all alloys form different phases, and some form intermetallics. These phases and intermetallics would typically have different densities than that calculated for the alloy. I will have more detail on this work in a future post. 

Here is a derivation of the correct density formula:

Many people incorrectly assume that if you have an alloy of x % tin and y % silver, that the density of this alloy would be 0.x*Density tin +0.y*Density silver. This intuitive linear formula is incorrect however, as density has two units (mass and volume).  An easy way to understand the derivation of the correct formula (proposed by Indium Corporation engineer Bob Jarrett) is to consider a 96% tin, 4 % silver example.

Lets assume I have 1 g of this alloy, 0.96 g is tin and 0.04 g is silver.

The volume of the tin is 0.96 g/7.31g/cc = 0.131327cc

The volume of the silver is 0.04g/10.5g/cc = 0.00381cc

So 1 g of the alloy has a volume of 0.131327 + 0.00381 cc = 0.135137 cc

Hence it's density is 1g/0.135137cc = 7.39989g/cc

Hence, the general formula is:

1/Da = x/D1 + y/D2 + z/D3

Da = density of final alloy

D1 = density of metal 1, x = mass fraction of metal 1

same for metals 2, 3

The formula continues for more than 3 metals.

I have developed an Excel spreadsheet that calculates density automatically. If anyone wants a copy, send me an email at rlasky@indium.com

Cheers,
Dr. Ron

PS:  Interesting thought: About 165,000 tonnes of gold have been mined throughout history. If all of this gold was gathered into a cube it would only be about 21 meters on a side. At $1550/oz, its value would be $8.5 trillion, quite a bit less than the almost $15 trillion debt of the US government.  Yikes!

Bismuth Solder Alloy Follow On

Wednesday, May 18, 2011 by Dr. Ron Lasky [Dr. Ron Lasky]

Folks,

 A few people asked some questions after my last post on bismuth solders. Here they are:

Bismuth1.      The low melting point of these solders is encouraging. What are realistic field use conditions?


Bismuth solders tend to be brittle, so drop shock environments such as mobile phones would not be recommended. However, thermal cycle performance from 0 to 100C is good, so stationary office equipment, televisions, desktop computers, etc may be good candidates.

 

2.     I am working with your colleagues on an automotive application and I am curious whether you have any idea how this alloy will perform between -40 and 0°C? We have not been reviewing bismuth-containing alloys due to their lower sheer strength, but may need to look at them in the future.

We can find no information on thermal cycle performance at these low temperatures.

3.     I hear that bismuth is rarer than silver, if we start using bismuth in solders couldn’t that make it very expensive.


An old number from Prismark puts the world solder use at about 50,000 metric tons (MT) per year.  Assume bismuth solders took a 5% market share (I think this would be the highest) that is 2,500 MT of bismuth solder (Bi57Sn42Ag1) or 1,425 MT of bismuth.

 

Although bismuth's occurrence in the earth's crust is 0.009 ppm (silver is 0.075 and gold 0.004 ppm), about 22,000 MT are produced each year.  In comparison, about 2,000 MT of gold, 20,000 MT of silver, 400 MT of indium and 5 MT of rhodium are produced each year.  In comparison to more common metals, total lead production is 8,000,000 MT/year and tin a little less than 700,000 MT.

 

 Realistically, it would seem to me to be unlikely that use of bismuth in solder, at 1,425MT/year out of 22,000 MTs,  would affect the price much, especially if the adaptation rate is more like 1-3%, instead of 5%. 

For those interested in how bismuth is produced, this Wikipedia quote may be of interest:

 

"According to the United States Geological Survey, world 2009 mine production of bismuth was 7,300 tonnes, with the major contributions from China (4,500 tonnes), Mexico (1,200 tonnes) and Peru (960 tonnes).[11] World 2008 bismuth refinery production was 15,000 tonnes, of which China produced 78%, Mexico 8% and Belgium 5%.[9]

The difference between world bismuth mine production and refinery production reflects bismuth's status as a byproduct metal. Bismuth travels in crude lead bullion (which can contain up to 10% bismuth) through several stages of refining, until it is removed by the Kroll-Betterton process or the Betts process. The Kroll-Betterton process uses a pyrometallurgical separation from molten lead of calcium-magnesium-bismuth drosses containing associated metals (silver, gold, zinc, some lead, copper, tellurium, and arsenic), which are removed by various fluxes and treatments to give high-purity bismuth metal (over 99% Bi). The Betts process takes cast anodes of lead bullion and electrolyzes them in a lead fluorosilicate-hydrofluorosilicic acid electrolyte to yield a pure lead cathode and an anode slime containing bismuth. Bismuth will behave similarly with another of its major metals, copper. Thus world bismuth production from refineries is a more complete and reliable statistic."

So I don't think bismuth supply and price would be affected by its use in solders.

Cheers,

Dr. Ron

image source

Solder Metal Prices Skyrocket, Especially Silver

Saturday, April 16, 2011 by Dr. Ron Lasky [Dr. Ron Lasky]
LMW Silver Price

Folks,

Many people have been infatuated by the price of gold in recent months, but the price of silver has also skyrocketed. In 2000 silver was about $3.00 per troy oz. In the eight years that followed, its price grew to $15/oz. Today it is trading at over $41/oz! This price is almost an all time high, except for the time when the Hunt brothers tried to corner the silver market in 1980. The aberration of their efforts jolted the silver price to just short of $50/oz, but it settled down to $11 or so after the Hunts came under margin call and other pressures.

Unfortunately, the dramatic price increase today, does not appear to be an aberration. Although we may hope that it will soon drop to more historic levels, we may not have reason to expect that it will.

Although not as dramatic, tin and copper have experienced significant prices increases as well. The price of tin has doubled in the last year to $15/pound and copper has increased from about $3/lb to $4.50.  These metals are obviously key ingredients in critical electronic materials such as solder pastes, solder bar, and solder preforms.

In addition, oil, which is used for most organic electronic materials such as PWB resins, flip chip underfill, and epoxy fluxes, has increased to $110/bbl - approaching its all time high of $145/bbl.

All of these price increases have a significant impact on the electronic materials supply chain. Although we are used to price decreases in the cost of our mobile phones and PCs, at this point in time, the price of the materials that go into these devices will be increasing.

As one materials supply chain executive commented at APEX, “It’s not like we can be clever and somehow work around the price increase of silver and these other materials, we have to pass it on to our customer, or go out of business.”

Cheers,

Dr. Ron

ITO (Indium-Tin Oxide) Sputtering Target Reclaim/Recycling

Thursday, February 3, 2011 by Eric Bastow [Eric Bastow]

ITO is one of the materials that makes the magic of flat panel displays (monitors, TVs, etc.) possible. When sputtered on in a thin layer, it acts as a transparent conductive film. However, the process of sputtering is very inefficient in its use of ITO. And, with the explosion of flat panel display sales, large amounts of ITO end up as "waste".

It is important to understand the economics of ITO. The main precursor of ITO is indium (metal). Indium is a semiprecious metal and trades on the open market like gold and silver. It is subject to price fluctuations just like the other precious metals. So, there is an economic impetus to reclaim as much of the unused ITO as possible.

Indium (Metal)
As mentioned earlier, flat panel displays employ a sputtered ITO coating. The indium metal must first be converted to indium oxide and then blended with the appropriate amount of tin oxide. The result is a pale green powder.
ITO (Indium-Tin Oxide) Powder
In order for the ITO to be usable, it must first be compressed in to a sputtering target. Planar sputtering targets are the dominant form of sputtering target used for sputtering of ITO. The geometry of the ITO sputtering target is often a rectangle or disc. Compressing the powder causes it to take on a darker color.
ITO (Indium-Tin Oxide) Sputtering Target (Disc)
Inherent to the sputtering process is the uneven erosion of the sputtering target. The target material erodes in a "race track" pattern. These images of a spent nickel-vanadium sputtering target show the classic "race track" erosion pattern (valley).
Used Sputttering Target

Sputtering Target "Race Track" Erosion (Valley)
The remaining material is unusable in the sputtering process. In the case of an ITO sputtering target, the unused portion can represent a significant amount of indium. It makes sense to reclaim or recycle as much of the target as possible.

The target user will break up the remaining target in to chunks.
ITO (Indium-Tin Oxide) Sputtering Target Chunks
The chunk ITO is sent to a recycling/reclaim center where the chunk ITO is converted back in to indium metal. And the cycle starts all over again.
Indium (Metal)

祝大家新年快乐,幸福吉祥!+ 金锡共晶合金 AuSn

Wednesday, February 2, 2011 by Anny Zhang [Anny Zhang]

在这里给大家拜年了:祝愿大家身体健康,万事如意,财源滚滚,阖家幸福!

Happy Chinese New Year!

有人告诉我2011年是金兔年(Golden Rabbit Year)。我上网查了一下,还是得不到考证。但是却让我想到了,Indium公司和金gold (Au) 这种金属,还是有一定相关性的。

金gold (Au)自身的熔点是0C,但是如果和锡tin(Sn)在一起,做成80%Au20%Sn的共晶合金,熔点就只有280 0C了。金锡共晶金属有很高的焊点强度(joint strength),抗腐蚀能力,导热性能好(thermal conductivity),能够与各种贵金属兼容,还符合无铅的要求;可靠性很高。

Properties of Eutectic AuSn

金锡共晶金属在SMT里或是电子焊接中的用途很广泛。在SMT中,如果需要分温度层焊接(step soldering),金锡的280度正好作为第一梯度的焊接;第二梯度的焊接合金可以选择锡银铜SAC或是锡铅SnPb;如果有第三梯度,可以选择锡铋SnBi。 在IGBT,automotive, 和 Radio Frequency (Power Amplifier) 的第一层焊接中,金锡常常是首选。 在电子焊接中,金锡的用途就更广泛了,特别是在医疗器械、仪器中。比如说在catheter导管的应用中,就可以用金锡做成微细的像小弹簧形状的物体,放入心导管中,帮助心肌梗塞的病人…随着全球人群的老龄化,在医疗器械、仪器方面的金锡应用,应该会越来越广泛。(当然,我可不希望有一天自己要靠它来救命哦。)  

当然,金的价格不菲,特别是这几年的疯长。所以选用这种合金,出于经济的考虑因素,也是要很谨慎的。 如果几年前我也买了金存着,现在也是一笔增值可观的小财富了:-)

Cheers!

PS: 我们家的张“小兔”宝宝五月底就要出生了,他现在已经在我肚子了老是练功夫了,踢来滚去的,肯定是我怀孕以来突然多看了功夫片和武侠小说的缘故。如果今年真的是金兔年(Golden Rabbit Year),只希望小兔以后能够健康和财运亨通(lots of gold!),并且有一颗金子般的心(a golden heart).

Pic:
1. Baidu image
2. www.indium.com Indium Corporation

 

Metallurgy as Modern Alchemy: Bismuth

Wednesday, November 17, 2010 by Brook Sandy [Brook Sandy]

Although most scientists today feel that alchemy has been widely discredited, and I have been taught to agree, the idea of it is whimsical and exhilarating.  Of course, I don’t have a hope of changing the makeup of bismuth or transforming it into another metal, but in a modern way, it’s very interesting how bismuth can be used to change the properties of other metals significantly - through alloying. In my last post on bismuth, I outlined its physical properties, some of which I find rather unusual. The main reason I originally researched bismuth was because of its viability for use as a low temperature Pb-free alloy.

BACKGROUND:
I'm not an alchemist like Newton, I can't transmute bismuth to gold like Seaborg, but I can use bismuth and metallurgy to transform an alloy.

I just read a fascinating article about Sir Isaac Newton titled, “Moonlighting as a Conjurer of Chemicals”. Newton is widely regarded as one of the most important people in the history of science, and he was very devoted to his work. The revelation in this article about the depth of his interest in alchemy left me somewhat awestruck. In my previous reading about Newton, I remember perhaps a mention of his interest in alchemy, but I guess I figured it was because science and alchemy, at that time, were fairly closely related. As scholars are starting to translate more of his diaries, they are discovering that his passion was alchemy and he saw it as the path to complete control over the natural world.  

I suppose if it was still socially acceptable to be an alchemist that is what I would have wanted to be; it just never seemed to be a viable option. What I have chosen to do now kind of makes sense considering chemistry/metallurgy is about as close as you can get nowadays. 

Reading this article reminded me of some interesting information I had come across while researching bismuth a couple months ago; namely that, although bismuth wasn’t one of the seven central metals in alchemy, it has an "alchemical" symbol (#52 in the image to the left) and was frequently used, although it’s not known for what purpose. I also came across this bit of information:

“In 1980, a scientist named Glenn T. Seaborg was able to transmute a minute quantity of bismuth into gold at the Lawrence Berkeley Laboratory, via nuclear collisions.” 

Seaborg is a fascinating scientist in his own right and discussion about him could fill quite a number of blog posts. Is it possible that alchemists underestimated bismuth and should have focused more on turning it into gold?

BACK TO MODERN TECHNOLOGY:
The eutectic alloy of 58Bi/42Sn has been used since the Pb-free transition as a low temperature (138°C liquidus) option for soldering products used at ambient temperatures - such as consumer electronics.  Note the low melting temperature of this alloy, despite the individual melting temperatures of bismuth and tin, 271°C and 232°C, respectively. Although bismuth is typically known to be quite brittle, this alloy has been shown to perform similarly to the SnPb eutectic solder (in response to a comment on my last post, for further data-based information, please feel free to contact me directly). In cases where more ductility is desirable, 1% silver can be added, further improving thermal shock and fatigue resistance. Perhaps the similarity in performance makes sense because of bismuth’s proximity (right next to) lead on the periodic table, although they differ in several other qualities such as toxicity.

The more I learn about bismuth, the more interested I become. Now if only I could find some in-depth alchemical information about it from Sir Isaac Newton.

Unique Solderspheres

Wednesday, April 21, 2010 by Dr. Andy Mackie [Dr. Andy Mackie]

Solderspheres or solder spheres, or even solder balls: whatever you call them, Indium Corporation has been making them for years and has rightly acquired the reputation for doing whatever it takes to meet our customers' unique needs.

Unique Alloys:

Hard to find alloys (like multipart alloys; low-melting alloys and even gold/tin (80Au/20Sn)) are our bread and butter. As "Indium Corporation" it should be no surprise that we lead the world in our ability to supply low-melting indium-alloy solder spheres, as well as other forms of these alloys, such as engineered solders or solder pastes.

Unique Quantities:

We don't want you to buy more than you absolutely need. If you just want 100 spheres, we can easily do that: if you want more - we can do that, too. But remember that, because each customer's need is unique, our prices may be higher than our competitors, especially for more standard alloys. Some customers also have unique inventory-control needs, so we work with many customers to ship on-demand by retaining a buffer stock of spheres here at Indium.

Unique Sizes:

Our current dimensional capabilities as of this writing are from 80microns to 0.062inches, or even bigger. Generally, the bigger the sphere - the less spherical it is (within the limits of surface tension and viscosity), and we can't control the laws of physics, so instances where a very large amount of solder is needed, a preform may have better dimensional control. Also, notice that we won't ask that you order in a specific unit of diameter measurement, like the mil or the micron or the millimeter: we're a global company - just tell us what you need.

Unique Packaging:

Often needed for more delicate alloy spheres, we can offer specialty overpacking that eliminates oxides from the atmosphere around the solder spheres, essentially stopping oxidation in its tracks. It's the same technique we use to package our soft solder die-attach (SSDA) wire: a technique that showed that the very reactive wire was still "as new" 3 years later. We also offer spheres in tape & reel packaging (see image) for 24mil, 35mil and 62mil diameter spheres.

Unique Tolerances:

Just as a case in point, a MEMS customer of ours had a need for a low-melting indium-alloy solder sphere with a tolerance of +/-5microns (+/-0.005mm) for a sphere with a 350micron diameter. That demands a tolerance of just over 1% - pretty demanding, but we did it.

Our standard tolerance is +/-1mil (1 thousandth of an inch, or 25.4microns), but as you can see, we have the capability to go to much tighter tolerances using three proprietary manufacturing techniques.

Other Needs:

We are also seeing people asking for doped-alloy spheres; low-alpha emission solder spheres and other things that we could never have dreamed of...

So please just let us know what you need. We'd be happy to help out, and if we can not do what you ask - we'll let you know why.

Cheers!  Andy


Eutectic Gold Tin (AuSn)

Tuesday, September 22, 2009 by Amanda Hartnett [Amanda Hartnett]

Eutectic Gold Tin (AuSn) with a composition of 80Au20Sn is a unique material.  This particular alloy of gold tin (AuSn) is considered a solder because it has a melting temperature of 280ºC, which is lower than the 350ºC transition temperature into braze materials.  Still, there are some similarities between this solder alloy and braze alloys. The most obvious is the hardness of the gold tin (AuSn) alloy. With a tensile strength of 40,000PSI, this solder is much more rigid than the tin solders most are familiar with. The strength is more closely compared to the silver brazes which melt above 500ºC. 

 

With that strength has come some unique manufacturing difficulties. For many years, one obstacle for implementation of gold tin (AuSn) as a solder preform or wire, was its availability in thin forms or fine diameters. The gold tin (AuSn) is extremely hard and it became brittle as it was handled through manufacturing and would crack if it was pressed too thin or fine.  

 

Luckily, in the 40+ years since eutectic gold tin (AuSn) was first used in electronics manufacturing, processing techniques have come a long way.  Today, gold tin (AuSn) solder can be made into dimensions much smaller than the soft solders, allowing it to be used in applications which require the highest level of precision.

 

Typical dimensions and tolerances of gold tin (AuSn) can be found in the below chart.



 

This chart as well as more detail on gold tin (AuSn) applications are available in the paper titled, “Process and Reliability Advantages of AuSn Eutectic Die-Attach,” presented at IMAPS 2009.    


Pb-Free Solders are Not the Cause of Tin Whiskers

Monday, July 6, 2009 by Amanda Hartnett [Amanda Hartnett]
Tin Whiskers growing between pure tin-plated hook terminals of an electromagnetic relay.  Image courtesy of nepp.nasa.gov

Tin Whiskers growing between pure tin-plated hook terminals of an electromagnetic relay. Image courtesy of nepp.nasa.gov

 

A recent blog posting on Metroblogs titled, "Tin Whiskers sound harmless, don't they?" left me shaking my head regarding the association which is often made between Pb-Free Solder and tin whiskers. It has been proven time and again that in cases where tin whiskers have formed, it is almost never a result of the Pb-free solder, but rather the pure tin-plated surface finish.  Still, Pb-free solder gets the bad rap.
 
Shortly after I began my current position, the Pb-free solder initiative titled RoHS was enacted. This new legislation restricted the use of leaded solders and a wave of new alloys, all tin-based and Pb-free, were their replacement. These new solder alloys were scrutinized and discussed in every electronics assembly meeting and forum, and one major point of interest were Tin Whiskers, believed by some to be the result of Pb-Free solders. 
 
Fortunately, years of testing have disproved this theory. Tin Whiskers are formed out of pure tin under high stress, such as applications which experience sub-zero temperatures. My understanding is that the tin whiskers problem should be nearly abated since the tin plating companies now dope their tin plating with enough lead to prevent whisker formation. 
 
Pb-free solders are almost always alloys of tin, silver, copper and/or antimony; never pure tin.  During the initial Pb-free transisiton, the number of cited tin whisker cases grew because the Pb-free solder alloys stress a tin plating more than leaded solder, so whiskers were more likely to occur.  Now that the tin platers are using doped tin, the issue should be mitigated.  Other alternatives would be to use another solderable surface finish such as copper, nickel, or gold.  
 
Based on these details, I feel the need to defend Pb-free solder alloys. I do not believe that they are the mass murderers they are accused of. It is possible that tin whiskers are the cause of the crash on the Red Line between the Takoma and Fort Totten stations, or even the airbus crash, however, if that is true, I doubt that Pb-free solder alone caused these whiskers.      

 

Soldering to Gold with Au/Sn or Tin Solder

Tuesday, May 19, 2009 by Amanda Hartnett [Amanda Hartnett]

 

Various assemblies utilize solders, including Au/Sn and tin solder, for thermal attachments. These solders perform multiple functions:
1)      As a metal interface, they are thermally conductive and will spread heat quickly away from a heat source.
2)      As a soldered attachment, they will form intermetallics with base metals. This bond is strong and will remain mechanically reliable for the lifetime of the device.
3)      This solder bond will be electrically conductive.
 
If the primary reason for implementing a solder bond is purpose 1 (thermal attachment), a void-free solder bond is highly desirable. This will maximize the thermal dissipation through the high K solder. 
 
Void-free soldering is typically achieved on gold-plated substrates. There are particular tactics for soldering to gold. Some of these involve the solder choice. Popular solder alloys include Au/Sn, tin alloys, or indium solders. Details regarding these material choices are outlined in our application note on soldering to gold
 
For more information on assembly techniques when soldering to gold, check out my previous posting on soldering to gold.