Patent Grant
10174433
The present disclosure relates to tin electroplating. In particular, the present disclosure relates to a stannous methanesulfonate solution for tin electroplating applications and a method of forming the same.
With reference to
In tin electroplating applications, methanesulfonic acid (MSA) solutions are commonly used as the electrolyte. MSA has certain advantages over other types of electrolytes (e.g., fluoroborate, sulfate, halogen and phenolsulfonic acid (PSA) chemistries) in that it is: less corrosive than fluoroborate and sulfate chemistries; less likely to exhibit Sn(II) to Sn(IV) conversion; and less costly than fluoroborate, PSA, and halogen chemistries for effluent treatment and disposal (i.e., more environmentally friendly). Also, MSA is highly soluble in water. Further. MSA is a strong acid that provides high conductivity, high current densities, and high throwing power and covering power. Modern Electroplating, 4th Edition, eds. M. Schlesinger and M. Paunoic, Wiley-Interscience, New York, 2000.
Normally, the operating pH of MSA is less than 1 for tin electroplating applications. However, in certain applications, such as applications involving specialty membranes, this operating pH may be too low.
The present disclosure provides a stannous methanesulfonate solution for tin electroplating applications and a method of forming the same. The solution has an elevated pH. The solution also has a sufficient tin concentration for electroplating applications.
In one form thereof, the present disclosure provides a solution including at least one stannous methanesulfonate species, the solution having a tin concentration of about 15 g/L or more, and a pH of about 1.50 to about 2.20.
In certain embodiments, the tin concentration is about 15 g/L to about 100 g/L, or about 56 g/L to about 82 g/L, or about 58 g/L to about 62 g/L.
In certain embodiments, the pH is about 1.60 to about 2.00, such as about 1.80, or about 1.50 to about 1.70.
In certain embodiments, the solution has a density of about 1.1 g/mL.
In certain embodiments, the at least one stannous methanesulfonate species comprises Sn(CH3SO3)2.
In certain embodiments, the solution further includes a second stannous methanesulfonate species comprising at least one of Sn(OH)(CH3SO3) and Sn(O)(CH3SO3).
In another form thereof, the present disclosure provides a method for forming a stannous methanesulfonate solution including reacting tin with an aqueous methanesulfonic acid solution in the presence of an oxygen-containing gas to produce an aqueous stannous methanesulfonate solution having a pH; and adjusting the pH of the aqueous stannous methanesulfonate solution to an adjusted pH of about 1.50 to about 2.20 by adding a pH-adjusting agent to the aqueous stannous methanesulfonate solution.
In certain embodiments, the pH-adjusting agent is a base.
In certain embodiments, the pH-adjusting agent is one of a metal oxide, such as tin oxide, a carbonate, and a hydroxide, such as sodium hydroxide.
In certain embodiments, the adjusted pH is about 1.80.
In certain embodiments, the method further includes diluting the aqueous stannous methanesulfonate solution to a tin concentration of about 56 g/L to about 82 g/L.
In yet another form thereof, the present disclosure provides a stannous methanesulfonate species comprising SnxRz(CH3SO3)y, wherein x is 1, y is less than 2, and z is greater than 0.
In certain embodiments, the species comprises at least one of Sn(OH)(CH3SO3) and Sn(O)(CH3SO3).
In certain embodiments, R comprises at least one of a hydroxy group or and an oxo group.
In certain embodiments, the Sn has an alpha content less than about 0.002 alpha counts/hour/cm2.
The above-mentioned and other features and advantages of this disclosure, and the manner of attaining them, will become more apparent and the invention itself will be better understood by reference to the following description of embodiments of the invention taken in conjunction with the accompanying drawings, wherein:
The present disclosure provides a stannous methanesulfonate solution having an elevated pH and a method of forming the same.
1. First Reaction Stage for Preparation of Stannous Methanesulfonate
Solution
During a first reaction stage, tin (Sn) is reacted with an aqueous methanesulfonic acid (MSA or CH3SO3H) solution in the presence of an oxygen-containing gas (e.g., air) to produce an aqueous stannous methanesulfonate (Sn(MSA)2 or Sn(CH3SO3)2) solution, according to Reaction (1) below. In one embodiment, the reaction is performed in a normal atmospheric environment. In another embodiment, the reaction is performed in a modified environment having a higher oxygen content than the normal atmospheric environment.
Sn+2MSA+O2→Sn(MSA)2+H2O (1)
The temperature of the first reaction stage may vary. For example, the first reaction stage may be carried out at a temperature as low as about 20, 40, or 60° C. and as high as about 80, 100, or 120° C., or within any range delimited by any pair of the foregoing values.
The Sn reactant used in the first reaction stage may have a low alpha content. For example, the Sn reactant may have an alpha content less than about 0.002, 0.0015, or 0.001 alpha counts/hour/cm2. The alpha content may be measured using an alpha particle detector, such as the UltraLo-1800 Alpha Particle Counter available from XIA LLC of Hayward, Calif. In embodiments where the Sn in the solution is electroplated for electronic device packaging or other electronic manufacturing applications, the low alpha content of the Sn may reduce the risk of single-event upsets (“SEUs”), often referred to as soft errors or soft error upsets. The Sn reactant may be provided in the form of a powder or pellets, for example.
In certain embodiments, the MSA reactant used in the first reaction stage may be added in excess such that free MSA remains in the solution after the first reaction stage. The MSA content of the aqueous MSA solution used in the first reaction stage may vary. For example, the aqueous MSA solution may have a MSA content as low as about 50, 55, 60, or 65 weight % and as high as about 70, 75, or 80 weight %, or within any range delimited by any pair of the foregoing values.
The Sn(MSA)2 solution produced during the first reaction stage may have a Sn(II) concentration as low as about 18, 19, 20, or 21 weight % and as high as about 22, 23, 24, or 25 weight %, or within any range delimited by any pair of the foregoing values. In certain embodiments, the Sn(II) concentration may be less than 18 weight % or more than 25 weight %.
The Sn(MSA)2 solution produced during the first reaction stage may have a highly acidic pH. In certain embodiments, the pH of the solution may be about 1.0 or less, such as about 0.8, 0.9, or 1.0, for example.
An exemplary Sn(MSA)2 solution prepared according to Reaction (1) above includes Tin(II) Methanesulfonate Solution 300, Product No. 14557, CAS No. 53408-94-9, which is available from Honeywell Specialty Chemicals of Seelze, Germany.
Additional information regarding the preparation of Sn(MSA)2 is found in U.S. Pat. No. 5,162,555 to Remmers et al., the entire disclosure of which is expressly incorporated herein by reference.
2. Second Reaction Stage for pH Adjustment
During a second reaction stage, a pH-adjusting agent may be added to the highly acidic Sn(MSA)2 solution from the first reaction stage to increase the pH to a more neutral pH. When added to the highly acidic Sn(MSA)2 solution from the first reaction stage, the pH-adjusting agent may be basic in nature.
The pH-adjusting agent may be classified as a Brønsted base that accepts hydrogen ions (H+) in the solution and/or a Lewis base that donates a pair of electrons in the solution. Suitable pH-adjusting agents include metal oxides, such as tin oxide (SnO), and carbonates, such as sodium carbonate (Na2CO3), for example.
The pH-adjusting agent may also be classified more narrowly as an Arrhenius base that produces hydroxide ions (OH−) in the solution. Suitable pH-adjusting agents include sodium hydroxide (NaOH), potassium hydroxide (KOH), and other alkaline or alkali earth metal hydroxides, for example.
In embodiments where the pH-adjusting agent contributes additional Sn to the solution, such as when the pH-adjusting agent is SnO, free MSA may be present in the solution as excess from the first reaction stage to react with the additional Sn and to maintain the Sn in solution. By contrast, in embodiments where the pH-adjusting agent does not contribute additional Sn to the solution, such as when the pH-adjusting agent is NaOH, free MSA may be unnecessary in the solution.
The temperature of the second reaction stage may vary. For example, the second reaction stage may be carried out at a temperature as low as about 20, 40, or 60° C. and as high as about 80, 100, or 120° C., or within any range delimited by any pair of the foregoing values.
As discussed above, the first reaction stage may produce the SnxRz(MSA)y species of Sn(MSA)2, wherein x is 1, y is 2, and z is 0. Without wishing to be bound by theory, the present inventors believe that certain solutions of the present disclosure may contain soluble SnxRz(MSA)y species in addition to Sn(MSA)2. Adding the pH-adjusting agent during the second reaction stage may form hydroxide-anions (OH−) and/or oxo-anions (O2−) in the solution. In certain embodiments, such anions may cause SnxRz(MSA)y species other than Sn(MSA)2 to form in the solution. As a result, not all of the Sn ions in the solution may be present in the form of Sn(MSA)2, and at least some of the Sn ions in the solution may be present in the form of other SnxRz(MSA)y species.
The other SnxRz(MSA)y species produced during the second reaction stage may contain reduced levels of MSA compared to Sn(MSA)2, such that y is less than 2. Also, z may be greater than 0, so the SnxRz(MSA)y, species may contain one or more bridging R atoms or groups, including oxygen atoms (O), hydroxy groups (OH), or other bridging atoms or groups. One such species may include oxo-stannous methanesulfonate (Sn(O)MSA or Sn(O)(CH3SO3)), for example, wherein x is 1, y is 1, and z is 1 and the bridging R atom is O. Without wishing to be bound by theory, Sn(O)MSA may have the crystal structure shown in solid lines in
In embodiments where the pH-adjusting agent contributes additional Sn to the solution, such as when the pH-adjusting agent is SnO, the present inventors believe that the additional Sn ions from the second reaction stage may react with free MSA left over from the first reaction stage to produce Sn(OH)MSA according to Reaction (2) below (See also Example 1 below).
SnO+[Sn(MSA)2+MSA]→Sn(MSA)2+Sn(OH)MSA (2)
By contrast, in embodiments where the pH-adjusting agent does not contribute additional Sn to the solution, such as when the pH-adjusting agent is NaOH, the solution may lack additional Sn ions from the second reaction stage and excess MSA from the first reaction stage, so the present inventors believe that Sn(OH)MSA may not form in the solution (See also Example 2 below).
It is within the scope of the present disclosure that the above-described first and second reaction stages may be combined and performed simultaneously.
3. Clarification
The Sn(MSA)2 solution may be clarified to remove precipitates, undissolved residues, and other solid substances from the liquid Sn(MSA)2 solution. Such undissolved residues may include excess amounts of the pH-adjusting agent added to the Sn(MSA)2 solution during the second reaction stage, for example.
In certain embodiments, the clarification stage may involve adding activated charcoal to the solution and then filtering the solution through a paper filter or another suitable filter, for example. In other embodiments, the clarification stage may involve centrifugation or gravity settling, for example.
After clarification, the solution may appear substantially clear and free of visible precipitates, undissolved residues, and other solid substances. The solution may have a solids content less than about 0.10, 0.05, or 0.01 weight %, for example. The solution may be colored (e.g., yellow).
Although the clarification stage follows the first and second reaction stages in this description, the order of these steps may vary. It is also within the scope of the present disclosure that the solution may be subjected to more than one clarification stage. For example, the solution may be subjected to a first clarification stage after the first reaction stage and to a second clarification stage after the second reaction stage.
4. Dilution
The Sn(MSA)2 solution may be diluted with varying amounts of water (e.g., distilled water) to achieve a desired Sn(II) concentration and/or a desired pH.
The desired Sn(II) concentration in the solution may be about 15 g Sn(II)/L to about 100 g Sn(II)/L. For example, the desired Sn(II) concentration in the solution may be as low as about 15, 20, 25, 30, 35, 40, 45, 50, or 55 g Sn(II)/L and as high as about 60, 65, 70, 75, 80, 85, 90, 95, or 100 g Sn(II)/L, or within any range delimited by any pair of the foregoing values. In certain embodiments, the desired Sn(II) concentration in the solution may be about 56 g Sn(II)/L to about 82 g Sn(II)/L. For example, the desired Sn(II) concentration in the solution may be as low as about 56, 58, 60, 62, 64, 66, or 68 g Sn(II)/L and as high as about 70, 72, 74, 76, 78, 80, or 82 g Sn(11)/L, or within any range delimited by any pair of the foregoing values. The desired Sn(II) concentration in the solution may be about 58 to about 62 g Sn(II)/L, for example.
The desired Sn(II) concentration may also be expressed as a weight percentage. For a solution having a density of 1.1 g/mL and a Sn(II) concentration of about 56 g Sn(II)/L to about 82 g Sn(II)/L, for example, the Sn(II) concentration may be about 5.1 weight % (which corresponds to 56 g Sn(II)/L) to about 7.5 weight % Sn(II) (which corresponds to 82 g Sn(II)/L). The weight percentage range may vary as the density of the solution varies.
The desired pH may be about 1.50 to about 2.20. For example, the desired pH may be as low as about 1.50, 1.55, 1.60, 1.65, 1.70, 1.75, or 1.80 and as high as about 1.85, 1.90, 1.95, 2.00, 2.05, 2.10, 2.15, or 2.20, or within any range delimited by any pair of the foregoing values. In certain embodiments, the desired pH may be about 1.60 to about 2.00, such as about 1.80.
Exemplary solutions are presented in Table 1 below. In embodiments where the pH-adjusting agent contributes additional Sn to the solution, such as when the pH-adjusting agent is SnO, the pH of the solution may be limited by the amount of additional Sn that the solution is capable of dissolving. In Table 1, for example, a solution having a Sn(II) concentration of about 56 g Sn(II)/L to about 82 g Sn(II)/L may be capable of reaching a pH value in the range of about 1.50 to about 1.70 when the pH-adjusting agent is SnO (See Solution A below). By contrast, in embodiments where the pH-adjusting agent does not contribute additional Sn to the solution, such as when the pH-adjusting agent is NaOH, the solution may be capable of reaching a broader range of pH values while maintaining the Sn in solution, in Table 1, for example, a solution having a Sn(II) concentration of about 56 g Sn(II)/L to about 82 g Sn(II)/L may be capable of reaching a pH value in the range of about 1.50 to about 2.20 when the pH-adjusting agent is NaOH (See Solution B below).
Other exemplary solutions are presented in Table 2 below. In embodiments where the pH-adjusting agent contributes additional Sn to the solution, such as when the pH-adjusting agent is SnO, the pH of the solution is inversely related to the Sn(II) concentration of the solution. This trend is shown in Table 2 below. For example, as the desired pH of the solution increases, the maximum Sn(II) concentration of the solution decreases (See Solution A5 below). Above this maximum Sn(II) concentration, the solution may become unstable and Sn(II) may precipitate out of the solution. Similarly, as the desired Sn(II) concentration of the solution increases, the maximum pH of the solution decreases (See Solution A1 below). Above this maximum pH, the solution may become unstable and Sn(II) may precipitate out of the solution. By contrast, in embodiments where the pH-adjusting agent does not contribute additional Sn to the solution, such as when the pH-adjusting agent is NaOH, the solution may be capable of reaching various pH values at each Sn(II) concentration.
The dilution stage may also promote stability of the solution by preventing the Sn(MSA)2 from precipitating out of the solution during cooling and subsequent storage. In certain embodiments, the solution may remain stable for at least about 30 days, 60 days, 90 days, or more, for example.
In certain embodiments, the desired properties may be achieved without requiring the addition of other elements or additives besides water which could hinder the stability of Sn in the solution or the transfer efficiency of Sn through a membrane of an electroplating cell. For example, the desired properties may be achieved without requiring the addition of chelating agents, which may cause Sn to precipitate out of the solution at the desired pH levels of the present disclosure. The desired properties may also be achieved without requiring the addition of antioxidants, stabilizers, surfactants, or complexing agents, for example. Therefore, in one embodiment, the solution may lack additives such as chelating agents, antioxidants, stabilizers, surfactants, or complexing agents. As used herein, the solution may lack an additive if the additive is present in an amount less than about 0.01 weight %. In other embodiments, the solution may contain one or more additives such as chelating agents, antioxidants, stabilizers, surfactants, or complexing agents.
Metals other than tin may be present in the solution in small amounts. Such metals may include iron (Fe), cobalt (Co), copper (Cu), nickel (Ni), and lead (Pb), for example. In aggregate, these other metals may be present in the solution in amounts less than about 25, 15, or 5 ppm. The solution may also contain small amounts of sulfate (SO4) species, chlorine (Cl) species, and other species, for example.
Although the dilution stage follows the first and second reaction stages and the clarification stage in this description, the order of these steps may vary. It is also within the scope of the present disclosure that the solution may be subjected to more than one dilution stage. For example, the solution may be subjected to a first dilution stage after the first reaction stage and to a second dilution stage after the second reaction stage.
The following non-limiting Examples illustrate various features and characteristics of the present invention, which is not to be construed as limited thereto.
During a first reaction stage, Sn was reacted with an aqueous MSA solution in the presence of air to produce an aqueous Sn(MSA)2 solution. The solution contained 21.3 weight % Sn(II) and 5.8 weight % free MSA.
During a first dilution stage, 5.5 kg of the Sn(MSA)2 solution was diluted with 0.38 kg (380 g) of distilled water to reach about 20 weight % Sn(II).
During a second reaction stage, and within 20 minutes of the first dilution stage, 0.67 kg (670 g) of SnO was added to the diluted Sn(MSA)2 solution. An initial portion of SnO dissolved into the solution. A subsequent, excess portion of SnO remained un-reacted in the solution. With the addition of SnO, the solution contained 26.7 weight % Sn(II).
During a second dilution stage, the solution was diluted with 22 kg of distilled water. The diluted solution was stirred for 2 hours.
During a clarification stage, 0.9 weight % of activated charcoal was added to the solution. After 30 minutes of additional stirring, the solution was filtered with a paper filter to produce a clear, slightly yellow solution. The total weight of the filtered solution was 24.1 kg. The filtered solution contained 7.1 weight % Sn(II) and had a pH of 1.7.
During a third dilution stage, the solution was diluted with 6.9 kg of additional distilled water to produce a final solution. The total weight of the final solution was 31 kg. The final solution contained 60.2 g Sn(II)/L. (which corresponds to 5.5 weight % Sn(II) at a density of 1.095 g/mL) and had a pH of 1.79.
Based on the total weight of 31 kg, the final solution contained 1.71 kg Sn(II) (or 14.4 moles Sn(II)) and 2.19 kg MSA (or 23.1 moles MSA). The molar ratio of Sn(II):MSA was 14.4:23.1, or about 1:1.6. If the only SnxRz(MSA))y species present in the solution was Sn(MSA)2, where x is 1, y is 2, and z is 0, one would expect to see a 1:2 molar ratio of Sn(II):MSA (or x:y). However, the actual molar ratio of 1:1.6 may suggest the presence of other SnxRz(MSA)y species in the solution where y is less than 2 and z is greater than 0, such as Sn(OH)MSA where x is 1, y is 1, and z is 1. This molar ratio of 1:1.6 may further suggest that about 60 weight % of the SnxRz(MSA)y species are present with y equal to 2, and that about 40 weight % of the SnxRz(MSA)y species are present with y equal to 1, because 60%(2)+40%(1) equals 1.6.
The final solution also contained 1.4 ppm iron (Fe), less than 1.0 ppm cobalt (Co), less than 1.0 ppm copper (Cu), less than 5 ppm nickel (Ni), less than 4 ppm lead (Pb), less than 250 ppm sulfate (SO4), and less than 25 ppm chlorine (Cl).
After about 90 days, the solution was still stable with less than 0.1 weight % solids.
During a first reaction stage, tin (Sn) was reacted with an aqueous methanesulfonic acid (MSA) solution in the presence of air to produce an aqueous stannous methanesulfonate (Sn(MSA)2) solution. The solution contained 21.8 weight % Sn(II) and 2.4 weight % free MSA.
During a dilution stage, 20 g of the Sn(MSA)2 solution was diluted with 49.5 g of distilled water to reach a Sn(II) concentration of approximately 6.3 weight %.
During a second reaction stage, 10.4 g of a 10.6 weight % sodium hydroxide (NaOH) solution was added slowly to the diluted Sn(MSA)2 solution. After filtration, the solution contained 58.8 g Sn(II)/L (which corresponds to 5.3 weight % Sn(II) at a density of 1.109 g/mL) and had a pH value of 2.1.
Based on the total weight of 75 g, the final solution contained 3.975 g Sn(II) (or 0.0335 moles Sn(II)) and 7.013 g MSA (or 0.0729 moles MSA). The molar ratio of Sn(II):MSA was 0.0335:0.0729, or about 1:2. This molar ratio of about 1:2 suggests that the only SnxRz(MSA)y species present in the solution was Sn(MSA)2, where x is 1, y is 2, and z is 0.
After about 30 days, the solution was still stable with less than 0.1 weight % solids.
While this invention has been described as having a preferred design, the present invention can be further modified within the spirit and scope of this disclosure. This application is therefore intended to cover any variations, uses, or adaptations of the invention using its general principles. Further, this application is intended to cover such departures from the present disclosure as come within known or customary practice in the art to which this invention pertains and which fall within the limits of the appended claims.
This application is the U.S. national stage of PCT/US2014/068033, published as WO 2015/084778, filed Dec. 2, 2014, which claims the benefit under Title 35, U.S.C. § 119(e) of U.S. Provisional Patent Application Ser. No. 61/912,084, filed Dec. 5, 2013, each of which is hereby incorporated by reference herein in its entirety.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/US2014/068033 | 12/2/2014 | WO | 00 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2015/084778 | 6/11/2015 | WO | A |
| Number | Name | Date | Kind |
|---|---|---|---|
| 4459185 | Obata et al. | Jul 1984 | A |
| 4565610 | Nobel et al. | Jan 1986 | A |
| 5039576 | Wilson | Aug 1991 | A |
| 5162555 | Remmers et al. | Nov 1992 | A |
| 5167851 | Jamison et al. | Dec 1992 | A |
| 5562814 | Kirby | Oct 1996 | A |
| 6040362 | Mine et al. | Mar 2000 | A |
| 6096414 | Young | Aug 2000 | A |
| 6238596 | Nguyen et al. | May 2001 | B1 |
| 6339120 | Misra et al. | Jan 2002 | B1 |
| 6372997 | Hill et al. | Apr 2002 | B1 |
| 6391442 | Duvall et al. | May 2002 | B1 |
| 6400565 | Shabbir et al. | Jun 2002 | B1 |
| 6432320 | Bonsignore et al. | Aug 2002 | B1 |
| 6432497 | Bunyan | Aug 2002 | B2 |
| 6451422 | Nguyen | Sep 2002 | B1 |
| 6475962 | Khatri | Nov 2002 | B1 |
| 6496373 | Chung | Dec 2002 | B1 |
| 6500891 | Kropp et al. | Dec 2002 | B1 |
| 6562180 | Bohin et al. | May 2003 | B1 |
| 6597575 | Matayabas et al. | Jul 2003 | B1 |
| 6605238 | Nguyen et al. | Aug 2003 | B2 |
| 6610635 | Khatri | Aug 2003 | B2 |
| 6616999 | Freuler et al. | Sep 2003 | B1 |
| 6617517 | Hill et al. | Sep 2003 | B2 |
| 6620515 | Feng et al. | Sep 2003 | B2 |
| 6624224 | Misra | Sep 2003 | B1 |
| 6649325 | Gundale et al. | Nov 2003 | B1 |
| 6657297 | Jewram et al. | Dec 2003 | B1 |
| 6673434 | Nguyen | Jan 2004 | B2 |
| 6706219 | Nguyen | Mar 2004 | B2 |
| 6761928 | Hill et al. | Jul 2004 | B2 |
| 6764759 | Duvall et al. | Jul 2004 | B2 |
| 6783692 | Bhagwagar | Aug 2004 | B2 |
| 6791839 | Bhagwagar | Sep 2004 | B2 |
| 6797382 | Nguyen et al. | Sep 2004 | B2 |
| 6797758 | Misra et al. | Sep 2004 | B2 |
| 6811725 | Nguyen et al. | Nov 2004 | B2 |
| 6815486 | Bhagwagar et al. | Nov 2004 | B2 |
| 6835453 | Greenwood et al. | Dec 2004 | B2 |
| 6838182 | Kropp et al. | Jan 2005 | B2 |
| 6874573 | Collins et al. | Apr 2005 | B2 |
| 6900163 | Khatri | May 2005 | B2 |
| 6913686 | Hilgarth | Jul 2005 | B2 |
| 6926955 | Jayaraman et al. | Aug 2005 | B2 |
| 6940721 | Hill | Sep 2005 | B2 |
| 6946190 | Bunyan | Sep 2005 | B2 |
| 6984685 | Misra et al. | Jan 2006 | B2 |
| 7013965 | Zhong et al. | Mar 2006 | B2 |
| 7056566 | Freuler et al. | Jun 2006 | B2 |
| 7074490 | Feng et al. | Jul 2006 | B2 |
| 7078109 | Hill et al. | Jul 2006 | B2 |
| 7135232 | Yamada et al. | Nov 2006 | B2 |
| 7147367 | Balian et al. | Dec 2006 | B2 |
| 7172711 | Nguyen | Feb 2007 | B2 |
| 7241707 | Meagley et al. | Jul 2007 | B2 |
| 7244491 | Nguyen | Jul 2007 | B2 |
| 7291396 | Huang et al. | Nov 2007 | B2 |
| 7294394 | Jayaraman et al. | Nov 2007 | B2 |
| RE39992 | Misra et al. | Jan 2008 | E |
| 7328547 | Mehta et al. | Feb 2008 | B2 |
| 7369411 | Hill et al. | May 2008 | B2 |
| 7462294 | Kumar et al. | Dec 2008 | B2 |
| 7465605 | Raravikar et al. | Dec 2008 | B2 |
| 7550097 | Tonapi et al. | Jun 2009 | B2 |
| 7572494 | Mehta et al. | Aug 2009 | B2 |
| 7641811 | Kumar et al. | Jan 2010 | B2 |
| 7682690 | Bunyan et al. | Mar 2010 | B2 |
| 7695817 | Lin et al. | Apr 2010 | B2 |
| 7700943 | Raravikar et al. | Apr 2010 | B2 |
| 7744991 | Fischer et al. | Jun 2010 | B2 |
| RE41576 | Bunyan et al. | Aug 2010 | E |
| 7816785 | Iruvanti et al. | Oct 2010 | B2 |
| 7846778 | Rumer et al. | Dec 2010 | B2 |
| 7850870 | Ahn et al. | Dec 2010 | B2 |
| 7867609 | Nguyen | Jan 2011 | B2 |
| 7955900 | Jadhav et al. | Jun 2011 | B2 |
| 7960019 | Jayaraman et al. | Jun 2011 | B2 |
| 8039961 | Suhir et al. | Oct 2011 | B2 |
| 8076773 | Jewram et al. | Dec 2011 | B2 |
| 8081468 | Hill et al. | Dec 2011 | B2 |
| 8105504 | Gerster et al. | Jan 2012 | B2 |
| 8110919 | Jewram et al. | Feb 2012 | B2 |
| 8138239 | Prack et al. | Mar 2012 | B2 |
| 8223498 | Lima | Jul 2012 | B2 |
| 8308861 | Rolland et al. | Nov 2012 | B2 |
| 8324313 | Funahashi | Dec 2012 | B2 |
| 8431647 | Dumont et al. | Apr 2013 | B2 |
| 8431655 | Dershem | Apr 2013 | B2 |
| 8445102 | Strader et al. | May 2013 | B2 |
| 8518302 | Gerster et al. | Aug 2013 | B2 |
| 8535478 | Pouchelon et al. | Sep 2013 | B2 |
| 8535787 | Lima | Sep 2013 | B1 |
| 8586650 | Zhang et al. | Nov 2013 | B2 |
| 8587945 | Hartmann et al. | Nov 2013 | B1 |
| 8618211 | Bhagwagar et al. | Dec 2013 | B2 |
| 8632879 | Weisenberger | Jan 2014 | B2 |
| 8633478 | Cummings et al. | Jan 2014 | B2 |
| 8647752 | Strader et al. | Feb 2014 | B2 |
| 8758892 | Bergin et al. | Jun 2014 | B2 |
| 8796068 | Stender et al. | Aug 2014 | B2 |
| 8837151 | Hill et al. | Sep 2014 | B2 |
| 8865800 | Stammer et al. | Oct 2014 | B2 |
| 8917510 | Boday et al. | Dec 2014 | B2 |
| 8937384 | Bao et al. | Jan 2015 | B2 |
| 9055694 | Lima | Jun 2015 | B2 |
| 9070660 | Lowe et al. | Jun 2015 | B2 |
| 9080000 | Ahn et al. | Jul 2015 | B2 |
| 9222735 | Hill et al. | Dec 2015 | B2 |
| 9260645 | Bruzda | Feb 2016 | B2 |
| 9392730 | Hartmann et al. | Jul 2016 | B2 |
| 9481851 | Matsumoto et al. | Nov 2016 | B2 |
| 9527988 | Habimana et al. | Dec 2016 | B2 |
| 9537095 | Stender et al. | Jan 2017 | B2 |
| 9593209 | Dent et al. | Mar 2017 | B2 |
| 9593275 | Tang et al. | Mar 2017 | B2 |
| 9598575 | Bhagwagar et al. | Mar 2017 | B2 |
| 20020018885 | Takahashi et al. | Feb 2002 | A1 |
| 20020187355 | Crosby | Dec 2002 | A1 |
| 20030112603 | Roesner et al. | Jun 2003 | A1 |
| 20030151030 | Gurin | Aug 2003 | A1 |
| 20030159938 | Hradil | Aug 2003 | A1 |
| 20030203181 | Ellsworth et al. | Oct 2003 | A1 |
| 20030207064 | Bunyan et al. | Nov 2003 | A1 |
| 20030230403 | Webb | Dec 2003 | A1 |
| 20040069454 | Bonsignore et al. | Apr 2004 | A1 |
| 20040149587 | Hradil | Aug 2004 | A1 |
| 20040161571 | Duvall et al. | Aug 2004 | A1 |
| 20040206941 | Gurin | Oct 2004 | A1 |
| 20050020738 | Jackson et al. | Jan 2005 | A1 |
| 20050072334 | Czubarow et al. | Apr 2005 | A1 |
| 20050148721 | Tonapi et al. | Jul 2005 | A1 |
| 20050173255 | Bokisa | Aug 2005 | A1 |
| 20050228097 | Zhong | Oct 2005 | A1 |
| 20050287362 | Garcia-Ramirez et al. | Dec 2005 | A1 |
| 20060208354 | Liu et al. | Sep 2006 | A1 |
| 20060228542 | Czubarow | Oct 2006 | A1 |
| 20060260948 | Zschintzsch et al. | Nov 2006 | A2 |
| 20060264566 | Cassar et al. | Nov 2006 | A1 |
| 20070051773 | Ruchert et al. | Mar 2007 | A1 |
| 20070097651 | Canale et al. | May 2007 | A1 |
| 20070131913 | Cheng et al. | Jun 2007 | A1 |
| 20070164424 | Dean et al. | Jul 2007 | A1 |
| 20070179232 | Collins et al. | Aug 2007 | A1 |
| 20070249753 | Lin et al. | Oct 2007 | A1 |
| 20080044670 | Nguyen | Feb 2008 | A1 |
| 20080141629 | Alper et al. | Jun 2008 | A1 |
| 20080291634 | Weiser et al. | Nov 2008 | A1 |
| 20080302064 | Rauch | Dec 2008 | A1 |
| 20090111925 | Burnham et al. | Apr 2009 | A1 |
| 20090184283 | Chung et al. | Jul 2009 | A1 |
| 20100048435 | Yamagata et al. | Feb 2010 | A1 |
| 20100048438 | Carey et al. | Feb 2010 | A1 |
| 20100075135 | Kendall et al. | Mar 2010 | A1 |
| 20100116674 | Luo | May 2010 | A1 |
| 20100129648 | Xu et al. | May 2010 | A1 |
| 20100197533 | Kendall et al. | Aug 2010 | A1 |
| 20110141698 | Chiou et al. | Jun 2011 | A1 |
| 20110204280 | Bruzda | Aug 2011 | A1 |
| 20110265979 | Chen et al. | Nov 2011 | A1 |
| 20110294958 | Ahn et al. | Dec 2011 | A1 |
| 20110308782 | Merrill et al. | Dec 2011 | A1 |
| 20120060826 | Weisenberger | Mar 2012 | A1 |
| 20120195822 | Werner et al. | Aug 2012 | A1 |
| 20120253033 | Boucher et al. | Oct 2012 | A1 |
| 20120285673 | Cola et al. | Nov 2012 | A1 |
| 20120288725 | Tanaka et al. | Nov 2012 | A1 |
| 20130199724 | Dershem | Aug 2013 | A1 |
| 20130248163 | Bhagwagar et al. | Sep 2013 | A1 |
| 20130265721 | Strader et al. | Oct 2013 | A1 |
| 20130288462 | Stender et al. | Oct 2013 | A1 |
| 20140190672 | Swaroop et al. | Jul 2014 | A1 |
| 20150125646 | Tournilhac et al. | May 2015 | A1 |
| 20150275060 | Kuroda et al. | Oct 2015 | A1 |
| 20150279762 | Lowe et al. | Oct 2015 | A1 |
| 20160160104 | Bruzda et al. | Jun 2016 | A1 |
| 20170137685 | Liu et al. | May 2017 | A1 |
| Number | Date | Country |
|---|---|---|
| 2311067 | Jan 2001 | CA |
| 1407141 | Apr 2003 | CN |
| 1456710 | Nov 2003 | CN |
| 1549875 | Nov 2004 | CN |
| 101067030 | Nov 2007 | CN |
| 101090922 | Dec 2007 | CN |
| 101445627 | Jun 2009 | CN |
| 101735619 | Jun 2010 | CN |
| 101835830 | Sep 2010 | CN |
| 102134474 | Jul 2011 | CN |
| 102341474 | Feb 2012 | CN |
| 102627943 | Aug 2012 | CN |
| 102348763 | Apr 2013 | CN |
| 103087389 | May 2013 | CN |
| 103102689 | May 2013 | CN |
| 103131138 | Jun 2013 | CN |
| 103254647 | Aug 2013 | CN |
| 103333447 | Oct 2013 | CN |
| 103409116 | Nov 2013 | CN |
| 103436027 | Dec 2013 | CN |
| 103709757 | Apr 2014 | CN |
| 103773322 | May 2014 | CN |
| 103849356 | Jun 2014 | CN |
| 103865271 | Jun 2014 | CN |
| 104098914 | Oct 2014 | CN |
| 104140678 | Nov 2014 | CN |
| 104449550 | Mar 2015 | CN |
| 104497574 | Apr 2015 | CN |
| 104804705 | Jul 2015 | CN |
| 104861661 | Aug 2015 | CN |
| 105111750 | Dec 2015 | CN |
| 105349113 | Feb 2016 | CN |
| 105838322 | Aug 2016 | CN |
| 105980512 | Sep 2016 | CN |
| 1224669 | Jul 2002 | EP |
| 1149519 | Nov 2004 | EP |
| 1514956 | Mar 2005 | EP |
| 1629059 | Mar 2006 | EP |
| 2194165 | Jun 2010 | EP |
| 2848215 | Jun 2004 | FR |
| 2508320 | May 2014 | GB |
| 57027188 | Jun 1982 | JP |
| 3662715 | Jan 1991 | JP |
| 02611364 | May 1997 | JP |
| 2000143808 | May 2000 | JP |
| 2001139818 | May 2001 | JP |
| 4016326 | Dec 2007 | JP |
| 2008063412 | Mar 2008 | JP |
| 5269366 | Mar 2009 | JP |
| 5137538 | Jun 2009 | JP |
| 2009138036 | Jun 2009 | JP |
| 4288469 | Jul 2009 | JP |
| 5607298 | Mar 2010 | JP |
| 5390202 | Aug 2010 | JP |
| 2010248277 | Nov 2010 | JP |
| 5318733 | Jun 2011 | JP |
| 2011165792 | Aug 2011 | JP |
| 5687167 | Apr 2013 | JP |
| 5463116 | Apr 2014 | JP |
| 5944306 | Jul 2014 | JP |
| 5372270 | Sep 2014 | JP |
| 2014194006 | Oct 2014 | JP |
| 100479857 | Jul 2003 | KR |
| 20070116654 | Dec 2007 | KR |
| 201527309 | Jul 2015 | TW |
| WO0120618 | Mar 2001 | WO |
| 2003064148 | Aug 2003 | WO |
| 2004008497 | Jan 2004 | WO |
| 2005119771 | Dec 2005 | WO |
| 2007027670 | Mar 2007 | WO |
| 2008014171 | Jan 2008 | WO |
| 2008121491 | Oct 2008 | WO |
| 2008121970 | Oct 2008 | WO |
| 2009032212 | Mar 2009 | WO |
| 2013191116 | Dec 2013 | WO |
| 2014160067 | Oct 2014 | WO |
| 2015179056 | Nov 2015 | WO |
| 2016004565 | Jan 2016 | WO |
| 206103424 | Jun 2016 | WO |
| Entry |
|---|
| International Search Report and Written Opinion issued in PCT/US2014/068033, dated Mar. 26, 2015, 12 pages. |
| Vlartyak et al., On the oxidation of tin(II) in methanesulfonate solutions and the role of sulfate, Galvanotechnik (2005), 96(3), 594-601 (Abstract). |
| “Hi-Flow 225F-AC Reinforced, Phase Change Thermal Interface Material,” The Bergquist Company, 1 page, available at least as early as the filing of the present application. |
| “Therm-A-Gap HCS10,569,570,579 and 580 Thermally Conductive Gap Filler Pads,” Parker Chomerics, Engineering Your Success, pp. 11-12, available at least as early as the filing of the present application. |
| Aranzabe, Estibaliz, et al. “More than Color: Pigments with Thermal Storage Capacity; Processing and Degradation Behavior.” Advances in Materials Physics and Chemistry, 5:171-184, 2015. |
| Extended European Search Report issued in EP Application 14867847.7, dated Jun. 26, 2017, 7 pages. |
| Gowda, Arun, et al. “Choosing the Right Thermal Interface Material.” Solid State Technology, Insights for Electronics Manufacturing, Online Blog, 9 pages, 2005. Retrieved May 25, 2017 from the Internet <http://electroiq.com/blog/2005/03/choosing-the-right-thermal-interface-material/. |
| International Search Report and Written Opinion issued in PCT/CN2014/081724. dated Apr. 1, 2015, 12 pages. |
| International Search Report and Written Opinion issued in PCT/CN2014/093138, dated Sep. 6, 2015, 8 pages. |
| International Search Report and Written Opinion issued in PCT/CN2016/101874, dated Apr. 28, 2017, 12 pages. |
| Ramaswamy, C., et al. “Phase Change Materials as a Viable Thermal Interface Material for High-Power Electronic Applications.” The Ninth Intersociety Conference on Thermal and Thermomechanical Phenomena in Electronic Systems, IEEE, 2:687-691, 2004. |
| Search Report issued in CN application 201480066502.2, dated May 18, 2017, 2 pages. |
| International Search Report and Written Opinion issued in PCT/US2017/041498, dated Oct. 20, 2017, 10 pages. |
| Ping, Ding, et al. “Preparation and Application Research of Novel Silicone Gel for High-Power IGBT.” Insulating Materials, 47(2):52-55, Chinese text with English translation of Abstract, 2014. |
| Number | Date | Country | |
|---|---|---|---|
| 20170009362 A1 | Jan 2017 | US |
| Number | Date | Country | |
|---|---|---|---|
| 61912084 | Dec 2013 | US |
