SG176498A1 - Nanoscopic assurance coating for lead-free solders - Google Patents
Nanoscopic assurance coating for lead-free solders Download PDFInfo
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- SG176498A1 SG176498A1 SG2011085412A SG2011085412A SG176498A1 SG 176498 A1 SG176498 A1 SG 176498A1 SG 2011085412 A SG2011085412 A SG 2011085412A SG 2011085412 A SG2011085412 A SG 2011085412A SG 176498 A1 SG176498 A1 SG 176498A1
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- Singapore
- Prior art keywords
- coating
- electronic assembly
- silicon containing
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- containing agent
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- 229910000679 solder Inorganic materials 0.000 title claims abstract description 36
- 238000000576 coating method Methods 0.000 title claims abstract description 28
- 239000011248 coating agent Substances 0.000 title claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 47
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 42
- 239000010703 silicon Substances 0.000 claims abstract description 42
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 10
- 230000005012 migration Effects 0.000 claims abstract description 7
- 238000013508 migration Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 11
- 150000003573 thiols Chemical class 0.000 claims description 9
- 229930195733 hydrocarbon Natural products 0.000 claims description 8
- 150000002430 hydrocarbons Chemical class 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 229920001296 polysiloxane Polymers 0.000 claims description 8
- 150000004760 silicates Chemical class 0.000 claims description 8
- 150000004819 silanols Chemical class 0.000 claims description 6
- 239000012530 fluid Substances 0.000 claims description 5
- 150000004756 silanes Chemical class 0.000 claims description 5
- 238000007598 dipping method Methods 0.000 claims description 4
- 238000007740 vapor deposition Methods 0.000 claims description 4
- 238000010422 painting Methods 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- -1 sitanols Chemical class 0.000 claims description 2
- 239000011253 protective coating Substances 0.000 claims 5
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 claims 2
- 125000000524 functional group Chemical group 0.000 claims 2
- XUKUURHRXDUEBC-KAYWLYCHSA-N Atorvastatin Chemical compound C=1C=CC=CC=1C1=C(C=2C=CC(F)=CC=2)N(CC[C@@H](O)C[C@@H](O)CC(O)=O)C(C(C)C)=C1C(=O)NC1=CC=CC=C1 XUKUURHRXDUEBC-KAYWLYCHSA-N 0.000 claims 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 abstract description 7
- 239000004065 semiconductor Substances 0.000 abstract description 7
- 239000000126 substance Substances 0.000 description 15
- 239000002086 nanomaterial Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 5
- 230000000116 mitigating effect Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 4
- 238000000429 assembly Methods 0.000 description 4
- 230000000712 assembly Effects 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920000734 polysilsesquioxane polymer Polymers 0.000 description 3
- 238000009877 rendering Methods 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 235000015842 Hesperis Nutrition 0.000 description 2
- 235000012633 Iberis amara Nutrition 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000004377 microelectronic Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- QCEUXSAXTBNJGO-UHFFFAOYSA-N [Ag].[Sn] Chemical compound [Ag].[Sn] QCEUXSAXTBNJGO-UHFFFAOYSA-N 0.000 description 1
- PQIJHIWFHSVPMH-UHFFFAOYSA-N [Cu].[Ag].[Sn] Chemical compound [Cu].[Ag].[Sn] PQIJHIWFHSVPMH-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 229940124447 delivery agent Drugs 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000008570 general process Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003003 phosphines Chemical group 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 238000011158 quantitative evaluation Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000009420 retrofitting Methods 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000004467 single crystal X-ray diffraction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Power Engineering (AREA)
- Medicinal Chemistry (AREA)
- Computer Hardware Design (AREA)
- General Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Polymers & Plastics (AREA)
- Manufacturing & Machinery (AREA)
- Paints Or Removers (AREA)
- Silicon Polymers (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
- Encapsulation Of And Coatings For Semiconductor Or Solid State Devices (AREA)
Abstract
NANOSCOPIC ASSURANCE COATING FOR LEAD-FREE SOLDERSNanoscopic silicon containing agents including polyhedral oligomeric silsesquioxane and polyhedral oligomeric silicate are used to eliminate the formation of conductive metal whiskers at the surface of lead-free solders joints and atom migration in semiconductors.FIG. 5
Description
.
I
NANOSCOPIC ASSURANCE COATING FOR LEAD-FREE SOLDERS
This application claims the benefit of U.S. Provisional Patent Application
Serial No. 60/822,792 filed August 18, 2006.
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.
Description of the Prior Art
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. 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. Poly. 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.
U.S. Patent Application Serial No. 10/910,810 (“Composite Metal Matrix
Castings and Solder Compositions”) and U.S. Patent Application Serial No. 11/342,240 (“Surface Modification With POSS Silanols”), the disclosures of which are incorporated herein by reference, describe silicon containing agents as useful for the modification of metallic surfaces. U.S. Patent No. 5,585,544, also incorporated herein by reference, describes the use of silicon containing agents (referred to as spherosiloxanes) as hydrophobic agents on metals for corrosion prevention.
With ongoing concern regarding environmental pollutants, leaded solders have been targeted for elimination from electronic assemblies. However, 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.
It has surprisingly been discovered that 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.
In such capacity 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. The 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. These and other properties of nanostructured chemicals are discussed in detail in U.S. Patent No. 5,412,053 and U.S. Patent No. 5,484,867, both of which are incorporated herein by reference. These nanostructured chemicals are of low density, and can range in diameter from 0.5 nm to 5.0 nm.
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
For the purposes of understanding this invention's chemical compositions the following definition for formula representations of silicon containing agents and in particular Polyhedral Oligomeric Silsesquioxane (POSS) and Polyhedral Oligomeric
Silicate (POS) nanostructures is made.
Polysilsesquioxanes are materials represented by the formula [RSiO, gl. where «= represents molar degree of polymerization and R = represents organic substituent (H, siloxy, cyclic. or linear aliphatic or aromatic groups that may additionally contain reactive functionalities such as silanols, thiols, hydrides, alcohols, esters, acids, amines, ketones, olefins, ethers or which may contain halogens). Polysilsesquioxanes may be either homoleptic or heteroleptic.
Homoleptic systems contain only one type of R group while heteroleptic systems contain more than one type of R group.
A subset of silicon containing agents are classified as POSS and POS nanostructure compositions are represented by the formula: [(RSiOq s)nlxs for homoleptic compositions [(RSIO4 5)n(R'SiO4 5)mls 4 for heteroleptic compositions (where R = R') [(RSIO1.5)n(RSIO1.0}m(M);ls+ for heterofunctionalized heteroleptic compositions [(RSIO4 5)n(RXSiOq g)mlxy for functionalized heteroleptic compositions (where R groups can be equivalent or inequivalent)
In all of the above R is the same as defined above and X includes but is not limited to OH, Cl, Br, |, alkoxide (OR), cetate (OOCR), peroxide (OOR), amine (NRo) isocyanate (NCO), and R. The symbol 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.
The symbol 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.
Preferably among nanonostructured chemicals are 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. For
POSS, dispersion appears to be thermodynamically governed by the free energy of mixing equation (AG = AH-TAS). The nature of the R group and ability of the reactive groups on the POSS cage to react or interact with polymers and surfaces greatly contributes to a favorable enthalpic (AH) term while the entropic term (AS) is highly favorable because of the monoscopic cage size and distribution of 1.0.
Furthermore, because 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.
When applied to solder joints as a retrofit to circuit boards containing lead- free solders, 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.
The preferred 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.
Preferably, 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.
Of key importance is the use of a 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.
General Process Variables Applicable To All Processes
As is typical with all chemical processes there are a number of variables that can be used to control the purity, selectivity, rate, mechanism and economics of any process. Variables influencing the process for the use nanostructured chemicals and especially of silicon containing agents as effective coatings for lead free solders include the size, polydispersity, and composition of the nanoscopic agent. Similarly the molecular weight, polydispersity and composition of the polymer system or type of solvent that may also be utilized can also be tailored to meet requirements.
Blending processes such as melt blending, dry blending and solution mixing blending are all effective at mixing and alloying nanoscopic silica agents into a coating with desirable properties.
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. The mixture is then stirred under high shear at sufficient temperature to ensure adequate mixing, and the volatile solvent is then removed and recovered under vacuum or using a similar type of process including distillation. Note that supercritical fluids such as CO; can also be utilized as a replacement for the flammable hydrocarbon solvents. The resulting formulation may then be used directly or for subsequent processing.
Example 1. Mitigation of Tin Whiskers.
In an effort to evaluate the effectiveness of POSS coatings on whisker growth, 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.
Quantitative evaluation of the whisker growth was made using a parameter known as Whisker Index (WI), and has been described by Xu, et al., IPC SMEMA
APEX Conference, Jan. 19, 2002, pp. 506-2.1 to 506-2.6. This method assigns weight factors depending on the length of the whisker, based on the criticality for chosen line spacing. The weight factors used in this study, based on 100 mm line spacing, are ‘0’ and ‘100’ for whiskers of length less than Sum and greater than 50um, respectively. Whiskers with lengths between 5 to 10 ym, and 10 to 50 pm, are assigned weight factors of ‘1’ and ‘10’, respectively. Using this scheme, Wl = & (number of whiskers in each category) x (weight factor for the category).
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 mitigated or greatly slowed via the application of such silicon containing agents.
Since the whisker growth and atom migration are postulated to be a form of stress-relief, the effect of silicon containing agents bearing mono and polyfunctional groups was evaluated. In all cases, cages bearing polyfunctionality were more effective at mitigation than monofunctional systems. However, monofunctional cages were effective at providing mitigation and enhanced hydrophobicity of the surface. Surface hydrophobicty and whisker mitigation are desirable for non-hermitic environments.
Example 2. Coating of Preformed Solder Joints
In an effort to evaluate the effectiveness of POSS coatings on binding to solder surfaces, leaded solders, silver-tin, and silver-tin-copper solders were coated with POSS silanols, POSS thiols and POSS silanes. Both solution dipping and spray techniques were used to apply the POSS. The surfaces were then washed and examined using electron microscopy. Figure 6 shows the deposition of POSS cages within the solder grain. This verifies the ability of the cage to access the grain boundary of solders. It is recognized that all solders contain an oxide layer and this oxide layer is known to be reactive toward protonation. Hence, it is necessary to utilize cages bearing reactive groups to protonate through the surface oxides in order to form metal-sulfur, metal-oxygen, and metai-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.
While certain representative embodiments and details have been shown for purposes of illustrating the invention, it will be apparent to those skilled in the art that various changes in the methods and apparatus disclosed herein may be made
Claims (1)
- without departing from the scope of the invention which is defined in the appended claims.What is claimed is:1. A method for protecting an electronic assembly, comprising the steps of: (a) mixing a silicon containing agent with a carrier to form a coating . mixture; and (b) creating a protective coating by coating the electronic assembly with the coating mixture.2. The method of claim 1, wherein the carrier is selected from the group consisting of polymers, hydrocarbons, chlorinated hydrocarbons, fluorinated hydrocarbons, supercritical fluids, and polymerizable materials.3. A method for protecting an electronic assembly, comprising the steps of: (a) mixing a silicon containing agent with a carrier to form a coating mixture; and (b) creating a protective coating by coating the electronic assembly with the coating mixture , wherein the silicon containing agent is selected from the group consisting of nanostructured silicones, polyhedral ofigomeric silsesquioxanes, polyhedral oligomeric silicates, polysilicates, and sphereosilicates, wherein the carrier is selected from the group consisting of polymers, hydrocarbons, chlorinated hydrocarbons, fluorinated hydrocarbons, supercritical fluids, and polymerizable materials.4, The method of claim 3, wherein the silicon containing agent includes a functional group selected from the group consisting of thiols, silanols, and silanes.5. The method of claim 4, wherein the silicon containing agent is selected from the group consisting of POSS and POS.6. The method of claim 4, wherein the electronic assembly includes a lead-free solder, and the protective coating inhibits the formation of conductive metal whiskers or ator migration.7. The method of claim 4, wherein the protective coating increases hydrophobicity.8. The method of claim 4, wherein the protective coating is applied by a method selected from the group consisting of spraying, painting, dipping, or vapor deposition.9. The method of ciaim 1, wherein the mixing is nonreactive.10. The method of claim 1, wherein the mixing is reactive.11. An electronic assembly comprising: (a) an electronic component having at least one lead-free solder connection; and (b) a coating for the connection including a silicon containing agent selected from the group consisting of nanostructured silicones, polyhedral oligomeric silsesquioxanes, polyhedral oligomeric silicates, polysilicates, and sphereosilicates.12. The electronic assembly of claim 11, wherein the coating is applied with a carrier selected from the group consisting of polymers, hydrocarbons, supercritical fluids, and polymerizable materials.13. The electronic assembly of claim 11, wherein ihe coating includes a polymer.14. The electronic assembly of claim 11, wherein the silicon containing agent includes a functional group selected from the group consisting of thiols, sitanols, and silanes.16. The electronic assembly of claim 11, wherein the silicon containing agent is selected from the group consisting of POSS and POS,16. The electronic assembly of claim 11, wherein the coating inhibits the formation of conductive metal whiskers or atom migration.17. The electronic assembly of claim 11, wherein the coating increases hydrophobicity.18. The electronic assembly of claim 11, wherein the coating is applied by a method selected from the group consisting of spraying, painting, dipping, or vapor deposition.18. The electronic assembly of claim 12, wherein the carrier and the silicon containing agent are nonreactively mixed.
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JP (1) | JP5221539B2 (en) |
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US20100012708A1 (en) * | 2008-07-16 | 2010-01-21 | Schlumberger Technology Corporation | Oilfield tools comprising modified-soldered electronic components and methods of manufacturing same |
DE102008036090B4 (en) * | 2008-08-04 | 2020-01-30 | Te Connectivity Germany Gmbh | Electrical contact pairing and method for producing and contacting such |
CN102019514A (en) * | 2010-06-01 | 2011-04-20 | 重庆大学 | Trimethyl-silyl polysilsesquioxane particle reinforced type tin-silver-copper composite soldering paste and preparation method thereof |
US10162393B2 (en) | 2016-01-13 | 2018-12-25 | Seagate Technology Llc | Electrical connector with force balancing |
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JP2738303B2 (en) * | 1994-07-15 | 1998-04-08 | 株式会社デンソー | Manufacturing method of electronic component mounted circuit board |
CA2143606C (en) * | 1995-02-24 | 1999-07-20 | Peter Arrowsmith | Method of making electronic housings more reliable by preventing formation of metallic whiskers on the sheets used to fabricate them |
US5753374A (en) * | 1995-11-27 | 1998-05-19 | Dow Corning Corporation | Protective electronic coating |
US6376769B1 (en) * | 1999-05-18 | 2002-04-23 | Amerasia International Technology, Inc. | High-density electronic package, and method for making same |
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JP3975329B2 (en) * | 2001-12-14 | 2007-09-12 | 信越化学工業株式会社 | MOUNTING CIRCUIT BOARD PROTECTION COATING AGENT, MOUNTING SURFACE PREVENTION METHOD, |
US7101617B2 (en) * | 2003-07-10 | 2006-09-05 | Motorola, Inc. | Silicone dispensing with a conformal film |
JP2005322659A (en) * | 2004-05-06 | 2005-11-17 | Matsushita Electric Ind Co Ltd | Wiring board, its manufacturing method and semiconductor device |
US20060104855A1 (en) * | 2004-11-15 | 2006-05-18 | Metallic Resources, Inc. | Lead-free solder alloy |
TW200630447A (en) * | 2004-11-19 | 2006-09-01 | Showa Denko Kk | Resin cured film for flexible printed wiring board and production process thereof |
JP2008530312A (en) * | 2005-02-14 | 2008-08-07 | ハイブリッド・プラスティックス・インコーポレイテッド | Porosity control by polyhedral oligomeric silsesquioxane |
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