WO2008073159A2 - Revêtement de protection nanoscopique pour brasures sans plomb - Google Patents

Revêtement de protection nanoscopique pour brasures sans plomb Download PDF

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Publication number
WO2008073159A2
WO2008073159A2 PCT/US2007/018121 US2007018121W WO2008073159A2 WO 2008073159 A2 WO2008073159 A2 WO 2008073159A2 US 2007018121 W US2007018121 W US 2007018121W WO 2008073159 A2 WO2008073159 A2 WO 2008073159A2
Authority
WO
WIPO (PCT)
Prior art keywords
group
silicon containing
coating
electronic assembly
containing agent
Prior art date
Application number
PCT/US2007/018121
Other languages
English (en)
Other versions
WO2008073159A3 (fr
Inventor
Joseph D. Lichtenhan
Andre Lee
Sukhendu B. Hait
Original Assignee
Hybrid Plastics, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hybrid Plastics, Inc. filed Critical Hybrid Plastics, Inc.
Priority to JP2009525565A priority Critical patent/JP5221539B2/ja
Priority to EP07870739A priority patent/EP2059349A4/fr
Publication of WO2008073159A2 publication Critical patent/WO2008073159A2/fr
Publication of WO2008073159A3 publication Critical patent/WO2008073159A3/fr

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • H01L23/296—Organo-silicon compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/285—Permanent coating compositions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/045—Polysiloxanes containing less than 25 silicon atoms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0137—Materials
    • H05K2201/0162—Silicon containing polymer, e.g. silicone
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/10—Details of components or other objects attached to or integrated in a printed circuit board
    • H05K2201/10613—Details of electrical connections of non-printed components, e.g. special leads
    • H05K2201/10954—Other details of electrical connections
    • H05K2201/10977—Encapsulated connections

Definitions

  • the present invention relates to protecting solders joints (including lead-free solders) against short circuiting via the formation of conductive whiskers.
  • the invention also provides a method for rendering the solder joint hydrophobic and resistant against corrosive damage from moisture.
  • This invention relates to the use of polyhedral oligomeric silsesquioxane, silsesquioxane, polyhedral oligomeric silicate, silicates, and silicones or metallized- polyhedral oligomeric silsesquioxane, silsesquioxane, polyhedral oligomeric silicate, silicates, and silicones in solder coatings.
  • silsesquioxane Polyhedral oligomeric silsesquioxane, silsesquioxane, polyhedral oligomeric silicate, silicates, and silicones, and metallized-polyhedral oligomeric silsesquioxane, silsesquioxane, polyhedral oligomeric silicate, silicates, and silicones are hereinafter referred to as "silicon containing agents.”
  • Silicon containing agents have previously been utilized to complex metal atom(s) and for the dispersion of nanoscopic entities. As discussed by Gilman et al., 60 J. Appl. POIV. Sci 591 (1996); Phillips et al. 37 J. Spacecraft and Rockets 463 (2000), silicon containing agents can be converted in the presence of atomic oxygen to form a glass like silica layer. Thiol-functionalized silicon containing agents have also been utilized to modify silver surfaces to render them more resistant to environmental degradation and aid their utility as sensors and for protective encapsulation, and as coatings on electroluminescent semiconductors to increase their light emission as described in US. Pat. 7,227,305.
  • solders With ongoing concern regarding environmental pollutants, leaded solders have been targeted for elimination from electronic assemblies.
  • lead-free solders are well known to spontaneously form electrically conductive tin whiskers that create short circuits at the surfaces of solder joints, and pose reliability issues for their use in long-term service applications such as aircraft, autos, missiles, satellites, appliances, and microelectronics.
  • a solution is needed to ensure their reliability at the original equipment manufacture and service-maintenance levels.
  • silicon containing agents are useful for the retrofitting of electronic components which utilize any of a number of conductive or semiconductive materials, including solders which are also subject to short circuiting via the formation of metallic whiskers or atomistic migration at or between layers, joints, and material interfaces.
  • the silicon containing agents are themselves effective when applied in either a monomeric or polymeric form directly onto the solder joint, semiconductor or interconnect.
  • the nanoscopic silicon containing agents also provide an exceptional moisture barrier, electrically insulative properties, and control the surface of material interfaces to prevent growth of metallic whiskers and atom migration.
  • Advantages of the present invention include that it is nondetectable by the human eye; can be applied by chemical adhesion to the solder joint, conductor or semiconductor; low cost spray or paint-on application to circuit boards, chip assemblies, solar cells, and internal chip components; nonconductivity; and improved hydrophobicity.
  • Nanoscopic caged chemicals do not outgas and can create a nanoscopically thin bonded coating over preassembled solder joints and board assemblies without requiring reassemble or board rework. These properties and performance assurance are useful in a number of applications including rockets, space vehicles, solar cells, terrestrial vehicles, appliances, and microelectronics.
  • the silicon containing agents of most utility in this work are best exemplified by those based on low cost silicones, silsesquioxanes, polyhedral oligomeric silsesquioxanes, and polyhedral oligomeric silicates.
  • Figure 1 illustrates some representative examples of silicon containing agents with siloxane, silsesquioxane, and silicate structures.
  • R groups in such structures can range from H, to alkane, alkene, alkyne, aromatic and substituted organic systems including ethers, acids, amines, thiols, phosphates, and halogenated and fluorinated groups.
  • the preferred silicon containing agents for this invention all share a common hybrid (i.e. organic-inorganic) composition in which the internal framework cage is primarily comprised of inorganic silicon-oxygen bonds.
  • the exterior cage of these nanostructures is covered by both reactive and nonreactive organic functionalities (R), which ensure compatibility, film formation and tailorability of the nanostructure and the coated surface.
  • R reactive and nonreactive organic functionalities
  • FIG. 1 shows representative structural examples of nonmetallized silicon containing agents.
  • FIG. 2 illustrates preferred structures for silanol cages
  • FIG. 3. illustrates preferred structures for thiol functionalized cages.
  • FIG. 4. illustrates preferred structures for silane functionalized cages.
  • FIG. 5 is a plot of whisker index versus time for three different strain levels.
  • FIG 6. illustrates solder surface modification at the grain boundary level. DEFINITION OF FORMULA REPRESENTATIONS FOR NANOSTRUCTURES
  • a subset of silicon containing agents are classified as POSS and POS nanostructure compositions are represented by the formula:
  • R is the same as defined above and X includes but is not limited to OH, Cl, Br, I, alkoxide (OR), acetate (OOCR), peroxide (OOR), amine (NR2) isocyanate (NCO), and R.
  • M refers to metallic elements within the composition that include high and low Z metals and in particular Al, B, Ga, Gd, Ce, W, Ni, Eu, Y, Zn, Mn, Os, Ir, Ta, Cd, Cu, Ag, V, As, Tb, In, Ba, Ti, Sm, Sr, Pb, Lu, Cs, Tl, Te.
  • the symbols m, n and j refer to the stoichiometry of the composition.
  • ⁇ indicates that the composition forms a nanostructure and the symbol # refers to the number of silicon atoms contained within the nanostructure.
  • the value for # is usually the sum of m+n, where n ranges typically from 1 to 24 and m ranges typically from 1 to 12. It should be noted that ⁇ # is not to be confused as a multiplier for determining stoichiometry, as it merely describes the overall nanostructural characteristics of the system (aka cage size).
  • the present invention teaches the use of nanoscopic silicon containing agents as assurance coatings and agents for the mitigation of whisker formation, atom migration, and environmental aging of solder joints and semiconductors, and for protecting electronic assemblies from short circuiting due to whisker formation between solder, semiconductor and related electrical connections.
  • the keys that enable nanostructured chemicals such as silicon containing agents to function in this capacity include: (1 ) their unique size, high surface areas, and ability to coat a surface; (2) their ability to be uniformly dispersed at the nanoscopic level and promote surface compatibility; (3) their ability to chemically incorporate metals into the cage, (4) their inherent dielectric properties; and (5) the ability of the cage to behave as a sprayable coating.
  • silicon containing agents such as the polyhedral oligomeric silsesquioxanes (POSS) illustrated in Figure 1.
  • Preferred compositions include silicon containing agents bearing reactive silanol (Figure 2), thiol ( Figure 3), and silane ( Figure 4) functionalities. These functionalities are desired because their interaction with the metals contained in semiconductors and solders is thermodynamically favored, rendering them highly effective. They are available as solids and oils, and with or without metals. Both forms dissolve in solvent, monomers, and polymers, which are desirable carriers for the agents.
  • silicon containing agents like POSS nanostructured chemicals possess spherical shapes (per single crystal X-ray diffraction studies), like molecular spheres, and because they dissolve, they are also effective at reducing the viscosity of polymer systems rendering sprayable and paintable coatings. Silicon containing agents such as POSS silanes are also vapor depositable onto a metallic surface.
  • An approach that solves the whisker formation issue for lead-free solders and that can be affordably retro-applied to existing solder connections is to spray-apply or paint a coating of nanoscopic silicon containing agents over the entire electronic assembly, thereby protecting it from whisker formation.
  • silicon containing agents such as polyhedral oligomeric silsesquioxanes (POSS) have several significant advantages.
  • POSS nanobuilding blocks are optically transparent materials, electrically nonconductive, provide increased hydrophobicity, corrosion resistance and control the surface grain of the solder to mitigate whisker growth. Further, upon oxidation these systems readily form silica glasses. Silicon containing agents have been applied to solder connections by brush, spray, dip, and vapor deposition. Thus, the ability to retrofit an already assembled circuit board at low cost provides assurance against component failure due to instability of the lead-free solder joints.
  • compositions presented herein contain two primary material combinations: (1 ) silicon containing agents including nanostructured chemicals, nanostructured oligomers, or nanostructured polymers from the chemical classes of silicones, polyhedral oligomeric silsesquioxanes, polysilsesquioxanes, polyhedral oligomeric silicates, polysilicates spherosilicates; and (2) manmade polymer systems or delivery agents including solvents such as hydrocarbons, chlorinated and fluorinated hydrocarbons; supercritical fluids; and polymeric and polymerizable carriers.
  • the method of incorporating the nanostructured chemicals onto a surface can be accomplished through vapor deposition, spraying, dipping, painting, brushing, powder coating, or spin coating and may utilize solvent assisted methods.
  • silicon containing agent with a chemical ability to bond to metallic surfaces. Therefore reactive groups such as silanols, silanes, thiols, phosphines, amines, alcohols, ethers, acids, esters, are preferred and desirable. Because of their chemical nature, silicon containing agents can be tailored to contain more than one type of such reactive group. Similarly, the compatibility of silicon containing agents with surfaces can be controlled through altering the type and number of reactive groups on the nanoscopic cage.
  • Nanostructured chemicals can also be added to a vessel containing the desired polymer, prepolymer or monomers and dissolved in a sufficient amount of an organic solvent (e.g. hexane, toluene, dichloromethane, etc.) or fluorinated solvent to effect the formation of one homogeneous phase.
  • an organic solvent e.g. hexane, toluene, dichloromethane, etc.
  • fluorinated solvent e.g. hexane, toluene, dichloromethane, etc.
  • the resulting formulation may then be used directly or for subsequent processing.
  • Example 1 Mitigation of Tin Whiskers.
  • matte Sn surfaces were utilized. Matte Sn surfaces on copper were created using immersion plating. The matte Sn coated Cu strips were bent to a fixed radius to create a compressive deformation. Three different curvatures were used: 1.31 ; 3.16; and 15.96 mm. The copper strip had a dimension of 25mm x 10mm x 0.5 mm, the bending radius corresponds to outer fiber strains of 1.5%, 7.2% and 16.1%, respectively.
  • Whisker Index (Wl)
  • Wl Whisker Index
  • Figure 5 shows a plot of whisker index versus time (in weeks). It was observed that whisker growth does require a compressive deformation, as no whiskers were observed on the tensile-side of all the bent specimens evaluated. Comparison of the whisker index for the control matte Sn to the matte Sn coated with POSS reveals that the time needed for initial whisker growth was extended by a factor of 4. Further, the thickness of whiskers was observed to be thinner by a factor of 2. Therefore, under appropriate stain conditions whisker growth could be I l mitigated or greatly slowed via the application of such silicon containing agents.
  • cages bearing reactive groups to protonate through the surface oxides in order to form metal-sulfur, metal-oxygen, and metal-silicon bonds to the POSS cage.
  • the reactivity of cages bearing thiols or silanols were found to be more effective than cages bearing silane (hydride) functionality.

Abstract

Selon l'invention, des agents nanoscopiques à base de silicium, comprenant du silsesquioxane oligomère polyédrique et du silicate oligomère polyédrique, sont utilisés pour éliminer la formation de barbes métalliques conductrices à la surface de joints à brasure sans plomb et la migration d'atomes dans des semi-conducteurs.
PCT/US2007/018121 2006-08-18 2007-08-15 Revêtement de protection nanoscopique pour brasures sans plomb WO2008073159A2 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2009525565A JP5221539B2 (ja) 2006-08-18 2007-08-15 無鉛はんだのためのナノスコピック保証被覆
EP07870739A EP2059349A4 (fr) 2006-08-18 2007-08-15 Revêtement de protection nanoscopique pour brasures sans plomb

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US82279206P 2006-08-18 2006-08-18
US60/822,792 2006-08-18

Publications (2)

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WO2008073159A2 true WO2008073159A2 (fr) 2008-06-19
WO2008073159A3 WO2008073159A3 (fr) 2008-08-07

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PCT/US2007/018121 WO2008073159A2 (fr) 2006-08-18 2007-08-15 Revêtement de protection nanoscopique pour brasures sans plomb

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EP (1) EP2059349A4 (fr)
JP (1) JP5221539B2 (fr)
KR (1) KR20090051741A (fr)
SG (1) SG176498A1 (fr)
TW (1) TW200831623A (fr)
WO (1) WO2008073159A2 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010015571A1 (fr) * 2008-08-04 2010-02-11 Tyco Electronics Amp Gmbh Paire de contacts électriques
WO2010044933A3 (fr) * 2008-07-16 2010-08-12 Schlumberger Canada Limited Outils pour champ pétrolifères comprenant des composants électroniques modifiés-soudés et des procédés de fabrication de ceux-ci
US10162393B2 (en) 2016-01-13 2018-12-25 Seagate Technology Llc Electrical connector with force balancing

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CN102019514A (zh) * 2010-06-01 2011-04-20 重庆大学 三甲基硅烷基聚倍半硅氧烷颗粒增强型锡银铜复合焊膏及其制备方法

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010044933A3 (fr) * 2008-07-16 2010-08-12 Schlumberger Canada Limited Outils pour champ pétrolifères comprenant des composants électroniques modifiés-soudés et des procédés de fabrication de ceux-ci
WO2010015571A1 (fr) * 2008-08-04 2010-02-11 Tyco Electronics Amp Gmbh Paire de contacts électriques
US10162393B2 (en) 2016-01-13 2018-12-25 Seagate Technology Llc Electrical connector with force balancing

Also Published As

Publication number Publication date
WO2008073159A3 (fr) 2008-08-07
EP2059349A4 (fr) 2010-12-22
KR20090051741A (ko) 2009-05-22
JP2010502011A (ja) 2010-01-21
JP5221539B2 (ja) 2013-06-26
TW200831623A (en) 2008-08-01
EP2059349A2 (fr) 2009-05-20
SG176498A1 (en) 2011-12-29

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