Patent Application
20090145764
This invention relates to methods of depositing composite coatings comprising tin and non-metallic particles, the composite coatings being characterized by increased wear resistance, corrosion resistance, and enhanced resistance to tin whisker formation.
For much of its history, the electronics industry has relied on tin-lead solders to make connections in electronic components. Under environmental, competitive, and marketing pressures, the industry is moving to alternative solders that do not contain lead. Pure tin is a preferred alternative solder because of the simplicity of a single metal system, its favorable physical properties, and its proven history as a reliable component of popular solders previously and currently used in the industry. The growth of tin whiskers is a well known but poorly understood problem with pure tin coatings. Tin whiskers may grow between a few micrometers to a few millimeters in length, which is problematic because whiskers may electrically connect multiple features resulting in electrical shorts. The problem is particularly pronounced in high pitch input/output components with closely configured features, such as lead frames and connectors.
Electrical connectors are important features of electrical components used in various applications, such as computers and other consumer electronics. Connectors provide the path whereby electrical current flows between distinct components. Connectors should be conductive, corrosion resistant, wear resistant, and for certain applications solderable. Copper and its alloys have been used as the connector base material because of their conductivity. Thin coatings of tin have been applied to connector surfaces to assist in corrosion resistance and solderability. Tin whiskers in the tin coating present a problem of shorts between electrical contacts.
Accordingly, a need continues to exist for electrical components with a coating that imparts wear resistance, corrosion resistance, and a reduced propensity for whisker growth.
Among the various aspects of the present invention may be noted methods and compositions for depositing composite coatings comprising tin and non-metallic particles onto substrates such as electrical components. The deposited composite coatings are characterized by increased corrosion resistance, decreased friction coefficient, and increased resistance to tin whisker growth.
Accordingly, the invention is directed to a method for applying a wear resistant composite coating onto a metal surface of an electrical component. The method comprises contacting the metal surface with an electrolytic plating composition comprising (a) a source of tin ions and (b) non-metallic particles having a surfactant coating and applying an external source of electrons to the electrolytic plating composition to thereby electrolytically deposit the composite coating onto the metal surface, wherein the composite coating comprises tin and the non-metallic particles.
The invention is further directed to an electrolytic plating composition for plating a wear resistant composite coating onto a metal surface of an electrical component. The composition comprises a source of tin ions and non-metallic particles having a surfactant coating.
Other objects and features of the invention will be, in part, noted hereafter, and in part, apparent.
In accordance with this invention, a composite coating comprising tin having reduced tendency for whisker formation, increased wear resistance, increased corrosion resistance, and reduced friction coefficient is formed on a metal surface of an electronic component. The method of depositing the composite coating achieves these advantages by incorporating non-metallic particles into the composite coating.
Non-metallic particles incorporated into the composite coating of the present invention in certain preferred embodiments comprise fluoropolymer particles. Unexpectedly, composite coatings comprising tin and non-metallic particles, such as fluoropolymer particles, exhibit substantially reduced tin whisker formation after aging. Without being bound to a particular theory, it is thought that fluoropolymer particles, such as Teflon®, are a soft material in the tin-coating, which serves as a stress buffer to relieve compressive stress in the tin coating and thus reduce the occurrence of tin whiskers. Moreover, fluoropolymer particles, for example, particles comprising Teflon®, function as solid lubricants in the coating of the invention, which is important in reducing the composite coating's friction coefficient. The particles, due to their hydrophobicity, increase the interfacial contact angle of the composite coating/air/water interface. Contact angle is a reliable quantitative measure of hydrophobicity, and thus measures the ability of the composite coating to repel water. The composite coatings of the present invention exhibit high contact angles and are thus hydrophobic. The hydrophobic nature of the composite coatings contributes to their enhanced corrosion resistance.
An electronic device can be formed by combining several electronic components. For example, one such component is an electronic connector as shown in
It has been discovered that composite coatings comprising, in one embodiment, tin and non-metallic particles, for example, nano-particulate fluoropolymers, may be deposited in a manner that yields smooth, bright, and glossy coatings. Moreover, the composite coatings are resistant to tin whisker formation, as well as being characterized by increased wear resistance and corrosion resistance. In another embodiment, the composite coatings may comprises larger sized particles, wherein said composite coatings are characterized by a matte appearance, due to the light scattering effect of the large particles. Yet, in some embodiments, the composite coatings comprise larger sized particles since such particles may be useful in reducing the propensity for whiskers even though they may have undesired appearance characteristics. Composite coatings comprising tin and nano-particles, on the other hand, are particularly suitable for applications requiring a glossy surface/interface, while also providing the advantages of wear resistance, tin whisker resistance, and so on. The composite coating may additionally comprise another metal co-deposited with the tin and non-metallic particle. Exemplary metals include bismuth, copper, zinc, silver, lead, and combinations thereof.
Particular fluoropolymers suitable for the plating compositions of the present invention comprise polytetrafluoroethylene (PTFE, marketed, for example, under the trade name Teflon®), fluorinated ethylene-propylene copolymer (FEP), perfluoroalkoxy resin (PFE, a copolymer of tetrafluoroethylene and perfluorovinylethers), ethylene-tetrafluoroethylene copolymer (ETFE), polychlorotrifluoroethylene (PCTFE), ethylene-chloro-trifluoroethylene copolymer (ECTFE), polyvinylidene fluoride (PVDF), and polyvinyl fluoride (PVF), with polytetrafluoroethylene currently preferred. Preferably the fluoropolymer particles are PTFE particles.
In one embodiment, the fluoropolymer particles added to the plating compositions of the present invention are nano-particles. That is, the particles have a mean particle size substantially smaller than the wavelength of visible light, i.e., less than 380 (0.38 μm) to 700 nm (0.7 μm). In one embodiment, the mean particle size of the fluoropolymer particles is preferably substantially smaller than the wavelength of visible light. Accordingly, the mean particle size is less than about 1000 nm, preferably between about 10 nm and about 500 nm, more preferably between about 10 nm and about 200 nm, and in one embodiment between 40 nm and about 120 nm. Exemplary fluoropolymer particles may have mean particle sizes from about 50 nm to about 110 nm or from about 50 nm to about 100 nm, such as between about 90 nm and about 110 nm, or between about 50 nm and about 80 nm.
The mean particle sizes stated above refer to the arithmetic mean of the diameter of particles within a population of fluoropolymer particles. A population of particles contains a wide variation of diameters. Therefore, the particles sizes may be additionally described in terms of a particle size distribution, i.e., a minimum volume percentage of particles having a diameter below a certain limit. In one embodiment, therefore, at least about 50 volume % of the particles have a particle size less than 200 nm, preferably at least about 70 volume % of the particles have a particle size less than 200 nm, more preferably at least about 80 volume % of the particles have a particle size less than 200 nm, and even more preferably at least about 90 volume % of the particles have a particle size less than 200 nm.
In one embodiment, at least about 30 volume % of the particles have a particle size less than 100 nm, preferably at least about 40 volume % of the particles have a particle size less than 100 nm, more preferably at least about 50 volume % of the particles have a particle size less than 100 nm, and even more preferably at least about 60 volume % of the particles have a particle size less than 100 nm.
In another embodiment, at least about 25 volume % of the particles have a particle size less than 90 nm, preferably at least about 35 volume % of the particles have a particle size less than 90 nm, more preferably at least about 45 volume % of the particles have a particle size less than 90 nm, and even more preferably at least about 55 volume % of the particles have a particle size less than 90 nm.
In another embodiment, at least about 20 volume % of the particles have a particle size less than 80 nm, preferably at least about 30 volume % of the particles have a particle size less than 80 nm, more preferably at least about 40 volume % of the particles have a particle size less than 80 nm, and even more preferably at least about 50 volume % of the particles have a particle size less than 80 nm.
In a further embodiment, at least about 10 volume % of the particles have a particle size less than 70 nm, preferably at least about 20 volume % of the particles have a particle size less than 70 nm, more preferably at least about 30 volume % of the particles have a particle size less than 70 nm, and even more preferably at least about 35 volume % of the particles have a particle size less than 70 nm.
The fluoropolymer particles employed in the present invention have a so-called “specific surface area” which refers to the total surface area of one gram of particles. As particle size decreases, the specific surface area of a given mass of particles increases. Accordingly, smaller particles as a general proposition provide higher specific surface areas, and the relative activity of a particle to achieve a particular function is in part a function of the particle's surface area in the same manner that a sponge with an abundance of exposed surface area has enhanced absorbance in comparison to an object with a smooth exterior. The present invention employs particles with surface area characteristics to facilitate achieving particular whisker-inhibition function as balanced against various other factors. In particular, these particles have surface area characteristics which permit the use of a lower concentration of nano-particles in solution in certain embodiments, which promotes solution stability, and even particle distribution and uniform particle size in the deposit. Although it is contemplated that greater PTFE concentration might be addressed by plating process modifications, the particular surface characteristics of this preferred embodiment require addressing stability and uniformity issues to a substantially lesser degree. Moreover, it preliminarily appears possible that higher concentrations of PTFE may have deleterious effects on hardness or ductility; and if this turns out to be true, then the preferred surface area characteristics help avoid this.
In one embodiment, the invention employs fluoropolymer particles where at least about 50 wt %, preferably at least about 90 wt %, of the particles have a specific surface area of at least about 15 m2/g (e.g., between 15 and 35 m2/g. The specific surface area of the fluoropolymer particles may be as high as about 50 m2/g, such as from about 15 m2/g to about 35 m2/g. The particles employed in this preferred embodiment of the invention, in another aspect, have a relatively high surface-area-to-volume ratio. These nano-sized particles have a relatively high percent of surface atoms per number of atoms in a particle. For example, a smaller particle having only 13 atoms has about 92% of its atoms on the surface. In contrast, a larger particle having 1415 total atoms has only 35% of its atoms on the surface. A high percentage of atoms on the surface of the particle relates to high particle surface energy, and greatly impacts properties and reactivity. Nanoparticles having relatively high specific surface area and high surface-area-to-volume ratios are advantageous since a relatively smaller proportion of fluoropolymer particles may be incorporated into the composite coating compared to larger particles, which require more particles to achieve the same surface area, and still achieve the effects of increased tin whisker resistance, wear resistance (increased lubricity and decreased coefficient of friction), corrosion resistance and so on. On the other hand, the higher surface activity prevents certain substantial challenges, such as uniform dispersion. Accordingly, as little as 10 wt. % fluoropolymer particle in the composite coating achieves the desired effects, and in some embodiments, the fluoropolymer particle component is as little as 5 wt. %, such as between about 1 wt. % and about 5 wt %. A relatively purer tin coating may be harder and more ductile than a tin coating comprising substantially more fluoropolymer particle; however, the desired characteristics are not compromised by incorporating relatively small amounts of nano-particles in the composite coating.
Fluoropolymer particles are commercially available in a form which is typically dispersed in a solvent. An exemplary source of dispersed fluoropolymer particles includes Teflon® PTFE 30 (available from DuPont), which is a dispersion of PTFE particles on the order of the wavelength of visible light or smaller. That is, PTFE 30 comprises a dispersion of PTFE particles in water at a concentration of about 60 wt. % (60 grams of particles per 100 grams of solution) in which the particles have a particle size distribution between about 50 and about 500 nm, and a mean particle size of about 220 nm. Another exemplary source of dispersed fluoropolymer particles include Teflon® TE-5070AN (available from DuPont), which is a dispersion of PTFE particles in water at a concentration of about 60 wt. % in which the particles have a mean particle size of about 80 nm. These particles are typically dispersed in a water/alcohol solvent system. Generally, the alcohol is a water soluble alcohol, having from 1 to about 4 carbon atoms, such as methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, and tert-butanol. Typically, the ratio of water to alcohol (mole:mole) is between about 10 moles of water and about 20 moles of water per one mole of alcohol, more typically between about 14 moles of water and about 18 moles of water per one mole of alcohol.
Alternatively, a solution from a source of dry PTFE particles may be prepared and then added to the electrolytic plating bath. An exemplary source of dry PTFE particles is Teflon® TE-5069AN, which comprises dry PTFE particles having a mean particle size of about 80 nm. Other sources of PTFE particles include those sold under trade name Solvay Solexis available from Solvay Solexis of Italy, and under the trade name Dyneon available from 3M of St. Paul, Minn. (U.S.).
Preferably, the fluoropolymer particles are added to the electrolytic deposition composition with a pre-mix coating, i.e., as a coated particle, in which the coating is a surfactant coating applied prior to combining the particles with the other components (i.e., tin ions, acid, water, anti-oxidants, etc.) of the electrolytic deposition composition. The fluoropolymer particles may be coated with surfactant in an aqueous dispersion by ultrasonic agitation and/or high pressure streams. The dispersion comprising fluoropolymer particles having a surfactant coating thereon may be then added to the electrolytic tin plating composition. The surfactant coating inhibits agglomeration of the particles and enhances the solubility/dispersability of the fluoropolymer particles in solution.
The surfactant may be cationic, anionic, non-ionic, or zwitterionic. A particular surfactant may be used alone or in combination with other surfactants. One class of surfactants comprises a hydrophilic head group and a hydrophobic tail. Hydrophilic head groups associated with anionic surfactants include carboxylate, sulfonate, sulfate, phosphate, and phosphonate. Hydrophilic head groups associated with cationic surfactants include quaternary amine, sulfonium, and phosphonium. Quaternary amines include quaternary ammonium, pyridinium, bipyridinium, and imidazolium. Hydrophilic head groups associated with non-ionic surfactants include alcohol and amide. Hydrophilic head groups associated with zwitterionic surfactants include betaine. The hydrophobic tail typically comprises a hydrocarbon chain. The hydrocarbon chain typically comprises between about six and about 24 carbon atoms, more typically between about eight to about 16 carbon atoms.
Exemplary anionic surfactants include alkyl phosphonates, alkyl ether phosphates, alkyl sulfates, alkyl ether sulfates, alkyl sulfonates, alkyl ether sulfonates, carboxylic acid ethers, carboxylic acid esters, alkyl aryl sulfonates, and sulfosuccinates. Anionic surfactants include any sulfate ester, such as those sold under the trade name ULTRAFAX, including, sodium lauryl sulfate, sodium laureth sulfate (2 EO), sodium laureth, sodium laureth sulfate (3 EO), ammonium lauryl sulfate, ammonium laureth sulfate, TEA-lauryl sulfate, TEA-laureth sulfate, MEA-lauryl sulfate, MEA-laureth sulfate, potassium lauryl sulfate, potassium laureth sulfate, sodium decyl sulfate, sodium octyl/decyl sulfate, sodium 2-ethylhexyl sulfate, sodium octyl sulfate, sodium nonoxynol-4 sulfate, sodium nonoxynol-6 sulfate, sodium cumene sulfate, and ammonoium nonoxynol-6 sulfate; sulfonate esters such as sodium α-olefin sulfonate, ammonium xylene sulfonate, sodium xylene sulfonate, sodium toluene sulfonate, dodecyl benzene sulfonate, and lignosulfonates; sulfosuccinate surfactants such as disodium lauryl sulfosuccinate, disodium laureth sulfosuccinate; and others including sodium cocoyl isethionate, lauryl phosphate, any of the ULTRAPHOS series of phosphate esters, Cyastat® 609 (N,N-Bis(2-hydroxyethyl)-N-(3′-Dodecyloxy-2′-Hydroxypropyl) Methyl Ammonium Methosulfate) and Cyastat® LS ((3-Lauramidopropyl) trimethylammonium methylsulfate), available from Cytec Industries.
Exemplary cationic surfactants include quaternary ammonium salts such as dodecyl trimethyl ammonium chloride, cetyl trimethyl ammonium salts of bromide and chloride, hexadecyl trimethyl ammonium salts of bromide and chloride, alkyl dimethyl benzyl ammonium salts of chloride and bromide, and the like. In this regard, surfactants such as Lodyne® S-106A (Fluoroalkyl Ammonium Chloride Cationic Surfactant 28-30%, available from Ciba Specialty Chemicals Corporation) and Ammonyx® 4002 (Octadecyl dimethyl benzyl ammonium chloride Cationic Surfactant, available from Stepan Company, Northfield, Ill.) are particularly preferred.
A class of non-ionic surfactants includes those comprising polyether groups, based on, for example, ethylene oxide (EO) repeat units and/or propylene oxide (PO) repeat units. These surfactants are typically non-ionic. Surfactants having a polyether chain may comprise between about 1 and about 36 EO repeat units, between about 1 and about 36 PO repeat units, or a combination of between about 1 and about 36 EO repeat units and PO repeat units. More typically, the polyether chain comprises between about 2 and about 24 EO repeat units, between about 2 and about 24 PO repeat units, or a combination of between about 2 and about 24 EO repeat units and PO repeat units. Even more typically, the polyether chain comprises between about 6 and about 15 EO repeat units, between about 6 and about 15 PO repeat units, or a combination of between about 6 and about 15 EO repeat units and PO repeat units. These surfactants may comprise blocks of EO repeat units and PO repeat units, for example, a block of EO repeat units encompassed by two blocks of PO repeat units or a block of PO repeat units encompassed by two blocks of EO repeat units. Another class of polyether surfactants comprises alternating PO and EO repeat units. Within these classes of surfactants are the polyethylene glycols, polypropylene glycols, and the polypropylene glycol/polyethylene glycols.
Yet another class of non-ionic surfactants comprises EO, PO, or EO/PO repeat units built upon an alcohol or phenol base group, such as glycerol ethers, butanol ethers, pentanol ethers, hexanol ethers, heptanol ethers, octanol ethers, nonanol ethers, decanol ethers, dodecanol ethers, tetradecanol ethers, phenol ethers, alkyl substituted phenol ethers, α-naphthol ethers, and β-naphthol ethers. With regard to the alkyl substituted phenol ethers, the phenol group is substituted with a hydrocarbon chain having between about 1 and about 10 carbon atoms, such as about 8 (octylphenol) or about 9 carbon atoms (nonylphenol). The polyether chain may comprise between about 1 and about 24 EO repeat units, between about 1 and about 24 PO repeat units, or a combination of between about 1 and about 24 EO and PO repeat units. More typically, the polyether chain comprises between about 8 and about 16 EO repeat units, between about 8 and about 16 PO repeat units, or a combination of between about 8 and about 16 EO and PO repeat units. Even more typically, the polyether chain comprises about 9, about 10, about 11, or about 12 EO repeat units; about 9, about 10, about 11, or about 12 PO repeat units; or a combination of about 9, about 10, about 11, or about 12 EO repeat units and PO repeat units.
An exemplary β-naphthol derivative non-ionic surfactant is Lugalvan BNO12 which is a β-naphtholethoxylate having 12 ethylene oxide monomer units bonded to the naphthol hydroxyl group. A similar surfactant is Polymax NPA-15, which is a polyethoxylated nonylphenol. Another surfactant is Triton®-X100 nonionic surfactant, which is an octylphenol ethoxylate, typically having around 9 or 10 EO repeat units. Additional commercially available non-ionic surfactants include the Pluronic® series of surfactants, available from BASF. Pluronic® surfactants include the P series of EO/PO block copolymers, including P65, P84, P85, P103, P104, P105, and P123, available from BASF; the F series of EO/PO block copolymers, including F108, F127, F38, F68, F77, F87, F88, F98, available from BASF; and the L series of EO/PO block copolymers, including L10, L101, L121, L31, L35, L44, L61, L62, L64, L81, and L92, available from BASF.
Additional commercially available non-ionic surfactants include water soluble, ethoxylated nonionic fluorosurfactants available from DuPont and sold under the trade name Zonyl®, including Zonyl® FSN (Telomar B Monoether with Polyethylene Glycol nonionic surfactant), Zonyl® FSN-100, Zonyl® FS-300, Zonyl® FS-500, Zonyl® FS-510, Zonyl® FS-610, Zonyl® FSP, and Zonyl® UR. Zonyl® FSN (Telomar B Monoether with Polyethylene Glycol nonionic surfactant) is particularly preferred. Other non-ionic surfactants include the amine condensates, such as cocoamide DEA and cocoamide MEA, sold under the trade name ULTRAFAX. Other classes of nonionic surfactants include acid ethoxylated fatty acids (polyethoxy-esters) comprising a fatty acid esterified with a polyether group typically comprising between about 1 and about 36 EO repeat units. Glycerol esters comprise one, two, or three fatty acid groups on a glycerol base.
In one preferred embodiment, non-metallic particles are in a pre-mix dispersion with a non-ionic coating on the particles prior to mixing in with the other bath components. Then the dispersion is mixed with the other ingredients, including the acid, Sn ions, and a cationic surfactant. A further surfactant coating is deposited over the non-metallic particle in a manner that imparts an overall coating charge, in this instance positive, on the fluoropolymer particles. Preferably, the surfactant coating comprises predominantly of positively charged surfactant molecules. A positively charged surfactant coating will tend to drive the particles, during electrolytic deposition, toward the cathode substrate enhancing co-deposition with tin and optionally the alloying metal. The overall charge of the surfactant coating may be quantified. The charge of a particular surfactant molecule is typically −1 (anionic), 0 (non-ionic or zwitterionic), or +1 (cationic). A population of surfactant molecules therefore has an average charge per surfactant molecule that ranges between −1 (entire population comprises anionic surfactant molecules) and +1 (entire population comprise cationic surfactant molecules). A population of surfactant molecules having an overall 0 charge may comprise 50% anionic surfactant molecules and 50% cationic surfactant molecules, for example; or, the population having an overall 0 charge may comprise 100% zwitterionic surfactant molecules or 100% non-ionic surfactant molecules.
In one embodiment, the surfactant coating comprises a cationic surfactant used alone or in combination with one or more additional cationic surfactants, such that the average charge per surfactant molecule is substantially equal to +1, i.e., the surfactant coating consists substantially entirely of cationic surfactant molecules.
It is not necessary, however, for the surfactant coating to consist entirely of cationic surfactants. In other words, the surfactant coating may comprise combinations of cationic surfactant molecules with anionic surfactant molecules, zwitterionic surfactant molecules, and non-ionic surfactant molecules. Preferably, the average charge per surfactant molecule of the population of surfactant molecules coating the non-metallic particles is greater than 0, and in a particularly preferred embodiment, the surfactant coating comprises a cationic surfactant used alone or in combination with one or more additional cationic surfactants and with one or more non-ionic surfactants. The surfactant coating comprising a population of cationic surfactant molecules and non-ionic surfactant molecules preferably has an average charge per surfactant molecule between about 0.01 (99% non-ionic surfactant molecules and 1% cationic surfactant molecules) and 1 (100% cationic surfactant molecules), preferably between about 0.1 (90% non-ionic surfactant molecules and 10% cationic surfactant molecules) and 1. The average charge per surfactant molecule of the population of surfactant molecules making up the surfactant coating over the non-metallic particles may be at least about 0.2 (80% non-ionic surfactant molecules and 20% cationic surfactant molecules), such as at least about 0.3 (70% non-ionic surfactant molecules and 30% cationic surfactant molecules), at least about 0.4 (60% non-ionic surfactant molecules and 40% cationic surfactant molecules), at least about 0.5 (50% non-ionic surfactant molecules and 50% cationic surfactant molecules), at least about 0.6 (40% non-ionic surfactant molecules and 60% cationic surfactant molecules), at least about 0.7 (30% non-ionic surfactant molecules and 70% cationic surfactant molecules), at least about 0.8 (20% non-ionic surfactant molecules and 80% cationic surfactant molecules), or even at least about 0.9 (10% non-ionic surfactant molecules and 90% cationic surfactant molecules). In each of these embodiments, the average charge per surfactant molecule is no greater than 1.
The concentration of surfactant is determined by the total particle-matrix interface area. For a given weight concentration of the particle, the smaller the mean particle size, the higher the total area of the particle surface. The total surface area is calculated by the specific particle surface (m2/g) multiplied by the particle weight in the solution (g). The calculation yields a total surface area in m2. A given concentration of nanoparticles, having a high specific particle surface area, includes a much greater total number of particles compared to micrometer-sized particles of the same weight concentration. As a result, the average interparticle distance decreases. The interaction between the particles, like the van der waals attraction, becomes more prominent. Therefore, high concentrations of surfactants are used to decrease the particles' tendency to flocculate or coagulate with each other. The surfactant concentration is therefore a function of the mass and specific surface area of the particles. Preferably, therefore, the composition comprises about one gram of surfactant for every about 100 m2 to 200 m2 of surface area of fluoropolymer particles, more preferably about one gram of surfactant for every 120 m2 to about 150 m2 of surface area of fluoropolymer particles.
For example, a dispersion of Teflon® TE-5070AN (total mass 750 grams) has about 450 grams of PTFE particles, having a specific surface area of about 23.0 m2/g and a total surface area of about 10350 m2. The mass of surfactant for coating and dispersing this total surface area is preferably between 50 grams and about 110 grams, more preferably between about 65 grams and about 90 grams. For example, a composition for dispersing about 450 grams of these PTFE particles may include between about 5 grams and about 25 grams Ammonyx® 4002 (Octadecyl dimethyl benzyl ammonium chloride Cationic Surfactant), between about 5 grams and about 25 grams Zonyl® FSN (Telomar B Monoether with Polyethylene Glycol nonionic surfactant), between about 40 grams and about 60 grams Lodyne® S-106A (Fluoroalkyl Ammonium Chloride Cationic Surfactant 28-30%), between about 30 grams and about 50 grams isopropyl alcohol, and between about 150 grams and about 250 grams H2O. The surfactant coating comprises a combination of cationic surfactant and nonionic surfactant to stabilize the fluoropolymer particles in solution. So, for example, the dispersion can be formed with the following components: PTFE particles (450 grams), Ammonyx® 4002 (10.72 g), Zonyl® FSN (14.37 g), Lodyne® S-106A (50.37 g), isopropyl alcohol (38.25 g), and water (186.29 g).
In one embodiment, the composite coating comprising tin and non-metallic particles, such as nano-particulate fluoropolymer, is deposited by an electrolytic plating method. In the electrolytic plating compositions of the present invention, the non-metallic particles preferably having a pre-mix coating comprising surfactant thereon are initially added in a concentration sufficient to impart a non-metallic particle concentration between about 0.1 wt. % and about 20 wt. % in solution, more preferably between about 1 wt. % and about 10 wt. %. To achieve these concentrations using a fluoropolymer particle source dispersed in a solvent, such as Teflon® TE-5070AN, for example, this concentration in the plating bath may be achieved by adding between about 1.5 g and about 350 g of 60 wt. % PTFE dispersion per 1 L of electrolytic plating solution, more preferably between about 15 g and about 170 g of 60 wt. % PTFE dispersion per 1 L of electrolytic plating solution. In volume terms, the concentrations in the plating bath may be achieved by adding PTFE dispersion to the solution at a volume of between about 0.5 mL and about 160 mL of PTFE dispersion per 1 L of electrolytic plating solution, more preferably between about 6 mL and about 80 mL of PTFE dispersion per 1 L of electrolytic plating solution.
In addition to the non-metallic particles having the pre-mix coating comprising surfactant thereon, the electrolytic plating composition may comprise a source of Sn2+ ions, an anti-oxidant, an acid, and a solvent. Typically, the solvent is water, but it may be modified to contain a small concentration of organic solvents. To plate a composite coating further comprising an alloying metal(s), the composition may also comprise a source of alloying metal ions. That is, the method of the present invention may be used to deposit composite coatings comprising tin, non-metallic particles, and an alloying metal selected from among bismuth, zinc, silver, copper, lead, and combinations thereof. Accordingly, the electrolytic plating composition may further comprise a source of alloying metal ions selected from among a source of Bi3+ ions, a source of Zn2+ ions, a source of Ag+ ions, a source of Cu2+ ions, a source of Pb2+ ions, and combinations thereof.
The source of Sn2+ ions may be a soluble anode comprising a Sn2+ salt, or, where an insoluble anode is used, a soluble Sn2+ salt. In one embodiment, the Sn2+ salt is Sn(CH3SO3)2 (Tin methane sulfonic acid, hereinafter “Sn(MSA)2”) Sn(MSA)2 is a preferred source of Sn ions because of its high solubility. Additionally, the pH of Sn plating baths of the present invention may be lowered using methane sulfonic acid, and the use of Sn(MSA)2 as the Sn source rather than, e.g., Sn(X), avoids the introduction of unnecessary additional anions, e.g., X2−, into the plating baths. In another embodiment, the source of Sn2+ ions is tin sulfate, and the pH of the Sn2+ plating bath is lowered using sulfuric acid. Typically, the concentration of the source of Sn2+ ions is sufficient to provide between about 10 g/L and about 100 g/L of Sn2+ ions into the bath, preferably between about 15 g/L and about 95 g/L, more preferably between about 40 g/L and about 60 g/L. For example, Sn(MSA)2 may be added to provide between about 30 g/L and about 60 g/L Sn2+ ions to the plating bath, such as between about 40 g/L and about 50 g/L Sn2+ ions (about 100 to 130 g/L as Sn(MSA)2).
Anti-oxidants may be added to the electrolytic plating compositions of the present invention to stabilize the composition against oxidation of Sn2+ ions in solution to Sn4+ ions. Reduction of Sn4+, which forms stable hydroxides and oxides, to Sn metal, being a 4-electron process, slows the reaction kinetics. Accordingly, preferred anti-oxidants including hydroquinone, catechol, any of the dihydroxyl, and trihydroxylbenzenes, and any of the hydroxyl, dihydroxyl, or trihydroxylbenzoic acids can be added in a concentration between about 0.1 g/L and about 10 g/L, more preferably between about 0.5 g/L and about 3 g/L. For example, hydroquinone can be added to the bath at a concentration of about 2 g/L.
The electrolytic plating composition of the present invention preferably has an acidic pH to inhibit anodic passivation, achieve better cathodic efficiency, and achieve a more ductile deposit. Accordingly, the composition pH is preferably between about 0 and about 3, preferably about 0. The preferred pH may be achieved using sulfuric acid, nitric acid, acetic acid, and methane sulfonic acid. The concentration of the acid is preferably between about 50 g/L and about 300 g/L, such as between about 50 g/L and about 200 g/L, more preferably between about 70 g/L and about 120 g/L. For example, between about 50 g/L and about 160 g/L methane sulfonic acid may be added to the electrolytic plating composition to achieve a composition pH 0 and act as the conductive electrolyte.
For plating a composite coating comprising tin, non-metallic particles, and bismuth, a source of Bi3+ ions is included in the composition. Sources of bismuth include bismuth sulfate, and salts of alkylsulfonates, such as bismuth methanesulfonate. Typically, the concentration of the source of Bi3+ ions is sufficient to provide between about 1 g/L and about 30 g/L of Bi3+ ions into the bath, preferably between about 5 g/L and about 20 g/L. A composite coating deposited from a composition comprising a source of Bi3+ ions may yield a coating having between about 1% by weight and about 60% by weight bismuth, with bismuth contents from about 1% by weight to about 5% by weight in some composite coatings and between about 50% by weight and about 60% by weight in other composite coatings.
For plating a composite coating comprising tin, non-metallic particles, and zinc, a source of Zn2+ ions is included in the composition. The zinc ion may be present in the bath in the form of a soluble salt such as zinc methanesulfonate, zinc sulfate, zinc chloride, stannous fluoride, zinc fluoroborate, zinc sulfamate, zinc acetate, and others. Typically, the concentration of the source of Zn2+ ions is sufficient to provide between about 0.1 g/L and about 20 g/L of Zn2+ ions into the bath, preferably between about 0.1 g/L and about 6 g/L. A composite coating deposited from a composition comprising a source of Zn2+ ions may yield a coating having between about 5% by weight and about 35% by weight zinc, typically between about 7% by weight and about 10% by weight in some composite coatings, or as high as between about 25% by weight and about 30% by weight in corrosion-resistant composite coatings.
For plating a composite coating comprising tin, non-metallic particles, and silver, a source of Ag+ ions is included in the composition. Silver compounds include silver salts of the sulfonic acids such as methanesulfonic acid, as well as, silver sulfate, silver oxide, silver chloride, silver nitrate, silver bromide, silver iodide, silver phosphate, silver pyrophosphate, silver acetate, silver formate, silver citrate, silver gluconate, silver tartrate, silver lactate, silver succinate, silver sulfamate, silver tetrafluoroborate and silver hexafluorosilicate. Each of these silver compounds may be used individually or in a mixture of two or more of them. Typically, Ag+ ions are sparingly soluble with most anions. Therefore, the source of Ag+ ions is preferably limited to salts of nitrate, acetate, and preferably methane sulfonate. Typically, the concentration of the source of Ag+ ions is sufficient to provide between about 0.1 g/L and about 1.5 g/L of Ag+ ions into the bath, preferably between about 0.3 g/L and about 0.7 g/L, more preferably between about 0.4 g/L and about 0.6 g/L. For example, Ag(MSA) may be added to provide between about 0.2 g/L and about 1.0 g/L Ag+ ions to the plating bath. A composite coating deposited from a composition comprising a source of Ag+ ions may yield a coating having between about 1% by weight and about 10% by weight silver, more typically from about 2% by weight to about 5% by weight.
For plating a composite coating comprising tin, non-metallic particles, and copper, a source of Cu2+ ions is included in the composition. Exemplary sources of Cu2+ ions include a variety of organic and inorganic salts, such as copper methanesulfonate, copper sulfate, copper oxide, copper nitrate, copper chloride, copper bromide, copper iodide, copper phosphate, copper pyrophosphate, copper acetate, copper formate, copper citrate, copper gluconate, copper tartrate, copper lactate, copper succinate, copper sulfamate, copper tetrafluoroborate and copper hexafluorosilicate, and hydrates of the foregoing compounds. Typically, the concentration of the source of Cu2+ ions is sufficient to provide between about 0.1 g/L and about 2.0 g/L of Cu2+ into the bath, preferably between about 0.2 g/L and about 1.0 g/L, such as about 0.3 g/L. A composite coating deposited from a composition comprising a source of Cu2+ ions may yield a coating having between about 1% by weight and about 10% by weight copper, more typically between about 1% by weight and about 3% by weight.
For plating a composite coating comprising tin, non-metallic particles, and lead, a source of Pb2+ ions is included in the composition. Exemplary sources of Pb2+ ions include a variety of organic and inorganic salts, such as lead sulfate, lead methanesulfonate and other lead alkylsulfonates, and lead acetate. Typically, the concentration of the source of Pb2+ ions is sufficient to provide between about 2 g/L and about 30 g/L of Pb2+ ions into the bath, preferably between about 4 g/L and about 20 g/L, more preferably between about 8 g/L and about 12 g/L. A composite coating deposited from a composition comprising a source of Pb2+ ions may yield a coating having between about 20% by weight and about 45% by weight lead, more typically around 37% by weight to about 40% by weight (eutectic tin-lead solder).
The tin-based composite coating can be plated using the Stannostar® chemistry available from Enthone Inc. of West Haven, Conn. employing Stannostar® additives (e.g., wetting agent 300, C1, C2, or others). For bright tin-based composite coatings, Stannostar® 1405 is one exemplary tin plating chemistry. For matte finishes, the tin-based composite coatings can be plated using the Stannostar® 2705 chemistry or the sulfate-based Stannostar® 3805 chemistry. Other conventionally known bright or matte tin plating chemistries are applicable to plate the tin-based composite coatings of the present invention. To plate a tin-based composite coating further comprising Bi, the Stannostar® SnBi chemistry can be used. To plate a tin-based composite coating further comprising Cu, the Stannostar® GSM chemistry may be used. A tin-based composite coating further comprising Ag can be plated using the chemistry disclosed in U.S. Pub. No. 2007/0037377.
During the electrolytic plating operation of the invention, electrons are supplied from an external source of electrons to a substrate, which acts as a cathode, and therefore, the site of reduction. The plating composition is preferably maintained at a temperature between about 20° C. and about 60° C. In one preferred embodiment, the temperature is between about 25° C. and about 35° C. The substrate is immersed in or otherwise exposed to the plating bath. The current density applied is between about 1 A/dm2 (Amps per square decimeter, hereinafter “ASD”) and about 100 ASD, preferably between about 1 ASD and about 20 ASD, more preferably between about 10 ASD and about 15 ASD. Lower current densities are preferred since higher current densities may generate foam in the composition and yield a dark deposit. The plating rate is typically between about 0.05 μm/min and about 50 μm/min, with typical plating rates of about 5 μm/min and about 6 μm/min achieved at 15 ASD and typically about 4.5 μm/min at 10 ASD. Typically, the thickness of the electrolytically deposited composite coating is between about 1 μm and about 100 μm, more preferably between about 1 μm and about 10 μm, even more preferably about 3 μm thick.
The anode may be a soluble anode or insoluble anode. If a soluble anode is used, the anode preferably comprises Sn(MSA)2, such that the source of Sn2+ ions in the plating bath is the soluble anode. Use of a soluble anode is advantageous because it allows careful control of the Sn2+ ion concentration in the bath, such that the Sn2+ ion does not become either under- or over-concentrated. An insoluble anode may be used instead of a Sn-based soluble anode. Preferable insoluble anodes include Pt/Ti, Pt/Nb, and DSAs (dimensionally stable anodes). If an insoluble anode is used, the Sn2+ ions are introduced as a soluble Sn2+ salt.
During the electrolytic plating operation, Sn2+ ions are depleted from the electrolytic plating composition due to their reduction to tin metal in the composite coating. Rapid depletion can occur especially with the high current densities achievable with the plating baths of the present invention. Therefore, Sn2+ ions can be replenished according to a variety of methods. If a Sn-based soluble anode is used, the Sn2+ ions are replenished by the dissolution of the anode during the plating operation. If an insoluble anode is used, the electrolytic plating composition may be replenished according to continuous mode plating methods or use-and-dispose plating methods. In the continuous mode, the same bath volume is used to treat a large number of substrates. In this mode, reactants must be periodically replenished, and reaction products accumulate, necessitating periodic filtering of the plating bath. Alternatively, the electrolytic plating compositions according to the present invention are suited for so-called “use-and-dispose” deposition processes. In the use-and-dispose mode, the plating composition is used to treat a substrate, and then the bath volume is directed to a waste stream. Although this latter method may be more expensive, the use-and-dispose mode requires no metrology, that is, measuring and adjusting the solution composition to maintain bath stability is not required.
The mechanism of deposition is co-deposition of the non-metallic particles and the metal particles. For example, a fluoropolymer particle is not reduced, but is trapped at the interface by the reduction of the metal ions, which reduce and deposit around the fluoropolymer particle. The surfactants assist by imparting a charge to the fluoropolymer particles, which helps to sweep them toward the cathode and temporarily and lightly adhere them to the surface until encapsulated and trapped there by the reducing metal ions. The imparted charge is typically positive since the substrate upon which the composite coating is plated is the cathode during an electrolytic plating operation.
The electrolytic plating compositions can be used to plate bright, glossy composite coatings or matte composite coatings on substrates, particularly electronic components. The composite coatings comprise non-metallic particle in an amount between about 0.1 wt. % and about 10 wt. % of the mass of the coating, preferably between about 0.5 wt. % and about 5 wt. %, even more preferably between about 1 wt. % and about 5 wt. %. Preferably, the non-metallic particles are distributed substantially evenly throughout the plated deposit. The composite coatings comprising these non-metallic particle amounts are characterized by increased wear resistance, increased corrosion resistance, a decreased friction coefficient, and an increased resistance to tin whiskers. The metal and fluorine content of pure tin coatings, tin-based composite coatings comprising non-metallic particles, and tin-based composite coatings comprising non-metallic particles and another metal can be determined by energy dispersive x-ray spectroscopy (EDS).
In one embodiment, the composite coatings comprising tin non-metallic particles are deposited by an electroless or immersion plating method. The plating solution for electroless/immersion tin may be conventional. For example, an electroless/immersion tin composition may include a source of tin ions, a mineral acid, a carboxylic acid, an alkanesulfonic acid, a complexing agent and water. Tin ion sources include those listed above, for example, tin methanesulfonate, tin oxide, and other tin salts. The tin ion concentration may be between about 1 g/L to about 120 g/L, but may be as high as the solubility limit of the particular tin salt in the particular solution. The tin ion concentration may be between about 5 g/L and about 80 g/L, preferably between about 10 g/L and about 50 g/L. In one embodiment, the tin ion concentration is between about 20 g/L and about 40 g/L, such as about 30 g/L, or about 20 g/L. In another embodiment, the tin ion concentration is between about 40 g/L and about 50 g/L.
Acids include mineral acids, carboxylic acids, alkanesulfonic acids, and combinations thereof. For example, one or more organic acids such as tartaric acid and/or citric acid may be added in a concentration between about 200 g/L to about 400 g/L. Alkanesulfonic acids include methanesulfonic acid, ethanesulfonic acid, ethanedisulfonic acid, and methanedisulfonic acid, among others. Methane sulfonic acid may be added, for example, in a concentration between about 50 g/L to about 150 g/L, between about 60 g/L and about 100 g/L, such as about 70 g/L, or about 100 g/L. In another embodiment, fluoboric acid is present in an amount of about 70 g/L. In another embodiment, fluoboric acid is present in an amount of about 100 g/L. In another embodiment, sulfuric acid is present in an amount of about 150 g/L. The acid may be added to achieve a solution with a pH between about 0 to about 3, such as about 0 to about 2, such as about 0 to about 1, or even between about 0 to about −1. Generally, it is desirable to use an acid that has an anion common to the acid salts of the metals.
The composite coatings of the present invention further demonstrate an enhanced resistance to tin whisker formation. Tin whisker resistance can be measured by accelerating the aging of the tin-based composite coatings. For example, the tin-based composite coatings can be aged at room temperature under ambient composition and pressure for 4 months and then at 50° C. for 2 months. After aging, the tin-based composite coatings comprising particles show enhanced resistance to tin whisker formation compared to pure tin deposits.
The following examples further illustrate the present invention.
A composition for electrolytically plating a bright, glossy tin-based composite coating comprising fluoropolymer particles was prepared comprising the following components:
100-130 g/L Sn(CH3SO3)2 (40 to 50 g/L Sn2+ ions)
150-225 g/L CH3SO3H
20 mL/L PTFE dispersion
80-120 mL/L Stannostar® 1405 Additives
The pH of the composition was about 0. One liter of this composition was prepared. The PTFE dispersion used in this Example and in Example 2 is the 5070AN dispersion available from DuPont which comprises nanoparticles and a non-ionic surfactant. The Stannostar additives include a cationic surfactant. So in Examples 1 and 2 the particles are pre-wet with the non-ionic surfactant, but are not pre-wet with the cationic surfactant.
A composition for electrolytically plating a bright, glossy tin-based composite coating comprising fluoropolymer nanoparticles was prepared comprising the following components:
100-130 g/L Sn(CH3SO3)2 (40 to 50 g/L Sn2+ ions)
150-225 g/L CH3SO3H
40 mL/L PTFE dispersion
80-120 mL/L Stannostar® 1405 Additives
The pH of the composition was about 0. One liter of this composition was prepared.
A composition for electrolytically plating a bright, glossy pure tin coating was prepared comprising the following components:
100-130 g/L Sn(CH3SO3)2 (40 to 50 g/L Sn2+ ions)
150-225 g/L CH3SO3H
80-120 mL/L Stannostar® 1405 Additives
The pH of the composition was about 0. One liter of this composition was prepared.
Two composite coatings comprising tin fluoropolymer nanoparticles (using the electrolytic plating compositions of Examples 1 and 2) and one pure tin deposit (using the electrolytic plating composition of Example 3) were plated onto copper foils. The samples were plated in a beaker and the agitation was provided using a stir bar. To deposit the composite coatings comprising tin and fluoropolymer nanoparticles, the applied current density was 15 ASD, the plating duration was 50 seconds, and the deposit thickness was 5 micrometers, for a plating rate 6 micrometers per minute. SEM images of the freshly deposited composite coatings were obtained and are shown in
To deposit the pure tin coating from the electrolytic composition of Comparative Example 3 to achieve a bright tin deposit, the applied current density was 15 ASD, the plating duration was 50 seconds, and the deposit thickness was 5 micrometers. Accordingly, the plating rate was 6 micrometers per minute. Three SEM images of the freshly deposited pure, bright tin coating were obtained and are shown in
The deposits plated according to the method of Example 4 were measured for tin and fluorine content using Energy Dispersive Spectroscopy (EDS).
From these spectra, it is possible to quantify the tin and fluorine content of the plated deposits. The EDS spectra shown in
A bright tin layer and a bright composite coating were analyzed for their coefficients of friction. The coefficient of friction test measured the coefficient of kinetic friction, μk, and was measured by sliding a 25 g load across a 3 mm track for 10 cycles at 4 cycles/minute.
A matte tin layer and matte composite coatings were analyzed for their coefficients of friction. The coefficient of friction test measured the coefficient of kinetic friction, μk, and was measured by sliding a 25 g load across a 2.5 mm track for 10 cycles at 5 cycles/minute.
A matte tin layer and matte composite coatings were analyzed for their coefficients of friction. The coefficient of friction test measured the coefficient of kinetic friction, μk, and was measured by sliding a 250 g load across a 2.5 mm track for 10 cycles at 5 cycles/minute.
The coefficient of friction varied from 0.36 to 0.82.
The contact angles of the deposits plated according to the method of Example 4 were measured using a Tantec Contact Angle Meter (measures contact angle by Sessile Drop Method). Contact angle was measured three times for a pure tin layer deposited from the electrolytic composition of Example 3 (Sample A), a composite coating deposited from the electrolytic composition of Example 1 (Sample B), and a composite coating deposited from the electrolytic composition of Example 2 (Sample C). The following Table shows the results:
The increased contact angles observed for Samples B and C reflect the composite coatings' increased hydrophobicity. Since water does not wet the composite coatings as well as a pure tin coating, the contact angle test may be interpreted as an indirect measure of the increased corrosion resistance of the composite coatings compared to a pure tin deposit.
The deposits plated from the compositions of Examples 1 and 2 were measured for corrosion resistance by exposing them to an ambient humidity of 85% relative humidity at 85° C. The samples were exposed for 24 hours in this ambient environment and observed for discoloration at 8 hours and at 24 hours. No discoloration was observed for the tin composite coating comprising fluoropolymer particles, indicating excellent corrosion resistance to a high heat, high humidity environment.
A bright pure tin layer and two bright composite coatings were aged for 2 months at room temperature in a non-controlled ambient and then inspected for the growth of tin whiskers.
A bright pure tin layer and two bright composite coatings were aged for 70 days at 50° C. and then for 107 days at room temperature in a non-controlled ambient and then inspected for the growth of tin whiskers.
Without being bound to a particular theory, it is thought that incorporated fluoropolymer particles 40, as shown in
The theory that fluoropolymer particles may reduce compressive stress was tested empirically.
A test was performed to demonstrate differences between an electrolytic tin composition employing PTFE particles provided in a pre-coated dispersion to an electrolytic tin composition employing PTFE particles provided in uncoated form. For a comparative sample A where no PTFE particles are present, the composition of comparative Example 3 was used. For samples B and C of electrolytic tin compositions where the PTFE particles are provided in a pre-coated dispersion, compositions prepared according to above Examples 1 and 2 were used. For a composition D where the PTFE particles are provided in uncoated form, a composition was prepared comprising the following components:
100-130 g/L Sn(CH3SO3)2 (40 to 50 g/L Sn2+ ions)
150-225 g/L CH3SO3H
16 g dry PTFE powder (Teflon® TE-5069AN)
80-120 mL/L Stannostar® 1405 Additives
The pH of the composition was about 0. The solution was vigorously stirred in an attempt to disperse the dry PTFE powder. The foregoing samples A, B, C, and D were placed in test tubes. A photograph of the freshly made solutions is shown in
A composite coating was deposited using the composition sample D of this Example and the conditions described in Example 4. SEM images of the coating are shown in
In view of the above, it will be seen that the several objects of the invention are achieved and other advantageous results attained.
When introducing elements of the present invention or the preferred embodiment(s) thereof, the articles “a”, “an”, “the” and “said” are intended to mean that there are one or more of the elements. For example, that the foregoing description and following claims refer to “an” electrical component means that there are one or more such components. The terms “comprising”, “including” and “having” are intended to be inclusive and mean that there may be additional elements other than the listed elements.
As various changes could be made in the above without departing from the scope of the invention, it is intended that all matter contained in the above description and shown in the accompanying drawings shall be interpreted as illustrative and not in a limiting sense.
