KR20070017932A - Composite metal matrix castings and solder compositions, and methods - Google Patents

Abstract

A method of making this composition is described that provides a composite composition and dispersed inorganic oxide particles having organic functional groups bound on the metal matrix and the particle surface. A method of making and using the composite solder composition and dispersed inorganic oxide particles having organic functional groups bonded on the surface of the metal matrix and particles is described. Also described are devices comprising this composite solder composition. In particular, organofunctional POSS and POS, particles are described. The composition provides the casting metal and the solder.

Description

COMPOSITE METAL MATRIX CASTINGS AND SOLDER COMPOSITIONS, AND METHODS

FIELD OF THE INVENTION The present invention generally relates to composite castings and solders comprising brazing, and more particularly to the composite castings and solders comprising organofunctional inorganic oxide particles. will be. The present invention also relates to a lead-free composite solder.

Light weight castings have increased use as a substitute for cast iron for weight reduction. Castings are especially used in the automotive and aerospace industries. Light weight castings usually do not have the performance or reliability of iron castings. One approach to this problem is to provide high strength inserts at the critical stress points of lightweight castings.

US Pat. Nos. 6,484,790 and 6,443,211 (Myers, et al.) Teach methods for forming lightweight composite metal castings incorporating metallurgically bonded inserts for various applications. The casting method coats the insert with the first layer under conditions that include sufficient temperature so that a portion of the layer is dissolved in a cast metal material and at least a portion of the first layer is diffused between the insert and the casting material. Leaving as a barrier.

Shimizu et al. Teaches an aluminum-based composite member having increased bond strength between an aluminum-based body and a portion of cast iron material included within the aluminum-based body through casting.

US Pat. No. 5,333,668 (Jorstad et al.) Discloses ferrous or aluminum articles, such as engine cylinder liner inserts, to provide a metallurgical bond with an aluminum alloy material casting around the article. Coating process is taught.

Lead-free electronic solder is a low melting point alloy system. However, their service performance in modern microelectronic applications requires that they have better thermomechanical (TMF) performance, good dimensional stability, and reduced electromigration. Good TMF performance is important in automotive, aerospace / defense, and consumer electric applications because their situations include severe thermal excursions. In a typical microelectronic system (MEMS), the dimensional stability of the interconnects is important because the lines of the printed circuit board through which the current flows are located very close to each other. The high current density in these MEMS and current generation applications ensures a solution to the electromigration problem.

Composite solder is solder with intentionally incorporated reinforcements. There have been several attempts to include compatible reinforcements for solder systems. Such methods include incorporating an intermetallic (IMC) reinforcement in situ or by mechanical mixing. Mechanical mixing can convert the metal powder added to the paste into IMC by either directly embedding the IMC in the solder paste or by reacting with molten solder during the reflow process. However, these reinforcements tend to be several microns in size. In addition, IMC reinforcements are crude during service and are likely to affect their effectiveness. Service performance improvement by IMC reinforcements is likely to vary depending on the type of IMC reinforcement, the method used to incorporate such reinforcements, and their coarsening kinetics during service. As a result, IMC particulate reinforced composite solder was not practiced on an actual electronic solder interconnect. With the rapid development of miniaturization of electronic components, the need for solder having sub-micron reinforcement has emerged.

An alternative approach is to include an inert particulate reinforcement in the solder matrix. One such attempt has been to include iron particulates in the presence of magnetic fields (M. McCormack, S. Jin, and GW Kammlott, "Enhanced Solder Alloy Performance by Magnetic Dispersions", IEEE Transactions on Components, Packaging, and Manufacturing Technology). Part A, 17 (3), pp. 452-457, 1994.). It has also been attempted to include ceramic particulates such as alumina in electronic solders. One problem with this method is the agglomeration of reinforcements during the reflow process, which increases their pore size. Due to the related problems of interfacial cracking between the reinforcement and the matrix, mechanical operations such as rolling have been attempted to break up and disperse these agglomerated particulates (H. Movoori and S. Jin, "New Creep-Resistant, Low Melting Point Solders"). with Ultrafine Oxide Dispersions ", J. Electr. Mater., 27 (11): pp. 1216-1222, 1998). Another serious problem associated with the inclusion of such inert reinforcements is the lack of any chemical bonds between the reinforcements and the solder matrix, which makes them ineffective in enhancing service performance (H. Mavoori and S. Jin). As a result, such solders with inert reinforcements have not been used in practice.

Another actively performed approach is to alloy Sn-Ag based solders with small amounts of Cu, Ni, rare earth elements, etc. (CM Miller, IE Anderson, and JF Smith, "A Viable Tin-Lead Solder Substitute: Sn-Ag- Cu ", J. Electr. Mater., 23 (7), pp. 595-601, 1994., F. Guo, S. Choi, TR Bieler, JP Lucas, A. Achari, M Paruchuri and KN Subramanian," Evaluation of Creep Behavior of Near Eutectic Sn-Ag Solders Containing Small Amount of Alloy Additions ", Materials Science and Engineering, A351, pp. 190-199, 2003, JG Lee, F. Guo, S. Choi, KN Subramanian, TR Bieler, and JP Lucas, "Residual Mechanical Behavior of Thermomechanically Fatigued Sn-Ag Based Solder Joints", J. Electr. Mater., 31 (9), pp. 946-952, 2002., CML Wu, CMT Law, DQ Yu. and L. Wang, "The Wettability and Microstructure of Sn-Zn-RE Alloys", J. Electr. Mater., 32 (2): pp. 63-69, 2003., CML Wu, DQYu, CMT Law, and L Wang, "Improvements of Microstructure, Wettability, Tensile and Creep Strength of Eute ctic Sn-Ag Alloy by Doping with Rare-Earth Elements ", Journal of Materials Research, 17 (12), pp. 3146-3154, 2002). Although these ternary and quaternary alloy solders can produce binary and ternary IMC precipitates, it is difficult to control their size and distribution during the reflow process. This alloying also changes the melting temperature, which affects the reflow parameters that ensure changes in processing parameters and methods.

As the miniaturization of electronic components proceeds rapidly, a solder having a sub-micron reinforcement is inevitably required. Such sub-micron size reinforcements, when present at the grain boundaries, can minimize grain boundary slip, significant mode of TMF damage during the high temperature dwell of the TMF cycle by adjusting the grain boundaries. This approach is used for nickel and cobalt based super alloys used in high temperature service environments. These reinforcements can minimize TMF damage and improve their service reliability, and can also improve dimensional stability, which is essential for MEMs and microelectronics applications.

In microelectronic applications, as the current density increases, ion transport between the electrodes causes voiding that breaks the solder joint. By including copper atoms at the grain boundaries of aluminum lines, similar problems have been successfully addressed in the computer industry. However, there is no known solution to the same problem with lead-free solder. Sub-micron sized reinforcements that can be obtained in the proposed method of reinforcing solder can provide a solution to the electron transfer problem.

In US Pat. No. 5,127,969 (Sekhar), a solder composition having a continuous phase and a dispersed phase is taught. The dispersed phase is a reinforcing material in the form of particulates or fibers comprising graphite, silicon carbide, metal oxides, elemental metals and / or metal alloys. The reinforcing material remains in particulate or fibrous form as the dispersed phase. Sekhar teaches particulates and fiber reinforcements in the submicron to 60 micron range, but nano-sized particle reinforcements are not taught.

US Pat. No. 5,928,404 and US Pat. No. 6,360,939 (Paruchuri, et al.) Disclose primary solder powders and additional metal powder components that do not melt during the soldering process due to having a melting point substantially higher than the melting point of the primary powders. Electric solder pastes are taught.

Avery, et al., US Pat. No. 6,340,113, teach a solder composition consisting of primary metal particles coated with a secondary metal, or a salt solution or suspension of a secondary metal. The metals are chosen such that their individual melting points are higher than the melting points of the alloys formed when they are bonded. The coated particles are heated and melting occurs at the interface between the core material and its coating. The particles are fused together in a porous metal foam.

U. S. Patent No. 6,521, 176 (Kitajima, et al.) Teaches lead-free solder alloys in which each concentration is set such that the lead-free solder alloy has a melting point lower than the predetermined heat resistance temperature of the workpiece being soldered.

US Pat. No. 6,866,044 (Saraf. Et al.) Teaches electrically conductive pastes comprising thermoplastic polymers, conductive metal powders and organic solvent systems. The thermoplastic polymer is a group consisting of poly (imide urea), poly (ether siloxane), poly (styrene butadiene), poly (styrene isoprene), poly (acrylonitrile butadiene), poly (ethylene vinyl acetate) and polyurethane Is selected.

Alternative methods of improving the service performance of solder are known in the art, but there is still a need for an excellent solution to this long-standing problem. Therefore, it is desirable to develop composite solder compositions having sub-micron reinforcements with improved service performance. More preferably, the composite solder composition is free of lead. Environmental lead emissions are a growing concern, considering the inherent toxicity of lead and the rapidly expanding use of electronic circuitry in all aspects of modern life. Solder compositions that reduce the amount of lead while maintaining properties such as melting temperature, solderability, fatigue behavior and processing parameters of the lead solder will solve long term unsolved toxic waste disposal problems.

The present invention provides a composite composition comprising an inorganic oxide particle having a metal matrix and organic functional groups chemically bonded on the surface of the particles in which the particles are dispersed in the metal matrix.

The invention also comprises introducing inorganic oxide particles having organic functional groups chemically bonded on the particle surface to a molten metal to produce a metal matrix having particles dispersed in the metal matrix, Provided are processes for preparing the composite composition.

The invention also provides such compositions and processes wherein the metal or alloy thereof melts at a temperature of about 600 ° C. or less. In some embodiments of the compositions and processes, the metal is magnesium (Mg), zinc (Zn), cadmium (Cd), aluminum (Al), indium (In), thallium (Tl), tin (Sn), lead (Pb) ), Bismuth (Bi) and mixtures thereof. Some embodiments of the compositions and processes include formula R ₇ Si ₇ O ₉ (OH) ₃ and the following structures:

(Wherein R is an organic functional group)

It provides particles that are POSS-triols having. In some embodiments of the compositions and methods, the particles are cyclohexal POSS-triols, and in other embodiments the particles are phenyl POSS-triols.

The present invention also provides a metal solder; And inorganic oxide particles having organic functional groups chemically bonded on the surface of the particles dispersed in the solder. In some embodiments, the solder is a paste that melts to form the solder as a matrix having particles dispersed in the matrix. In another embodiment, the solder is a solid preform of the solder, which includes the solder as a matrix and the particles dispersed in the matrix.

The invention also provides an embodiment of a composition in which the solder is melted at about 250 ° C. or less. In another embodiment of this composition, the solder is an alloy of metal. In some embodiments, the solder is lead free. In some embodiments, the particles form chemical bonds with the solder. In some embodiments, the particles have the formula R ₇ Si ₇ O ₉ (OH) ₃ and the following structures:

(Wherein R is an organic functional group)

POSS-triol with In some embodiments, the particles are cyclohexal POSS-triols, and in other embodiments the particles are phenyl POSS-triols. In some embodiments of the composition, the metal is tin (Sn), silver (Ag), copper (Cu), bismuth (Bi), zinc (Zn), indium (In), gold (Au), nickel (Ni), antimony (Sb), palladium (Pd), platinum (Pt), germanium (Ge) and mixtures thereof. In some embodiments, the metal matrix is Sn--Ag and in further embodiments the metal matrix is eutectic 96.5 wt% Sn-3.5 wt% Ag.

The present invention also provides a solder paste composition comprising introducing inorganic oxide particles having organic functional groups chemically bonded on the surface of the particles into the particulate metal solder, and mechanically mixing the particles and the metal solder to provide a paste. It provides a manufacturing process.

The present invention also provides a composite composition comprising a metal solder comprising inorganic oxide particles having organic functional groups chemically bonded on the surface of the particles dispersed in the solder, and melting the solder to form two or more components. Using soldering means for bonding, applying the solder to join two or more components.

The present invention also provides a composite composition comprising inorganic oxide particles having at least one part and organic functional groups chemically bonded on the surface of the metal solder and the particles dispersed in the solder when the composition is bonded to the part via heating. It provides a device comprising a.

The present invention also provides inorganic oxide particles having organic functional groups chemically bonded on the particle surface to the metal solder particles, mechanically mixing the particles and the metal solder to form a paste, and melting the paste so that the particles are formed into a metal matrix. It provides a process for producing a solder preform composition, comprising forming a preform dispersed within.

The invention also introduces inorganic oxide particles having organic functional groups chemically bonded on the surface of the particles into the metal solder and flux, mechanically mixing the particles and the metal solder, and the particles are dispersed in the metal solder A process for producing molded solder is provided, which comprises melting a molten metal solder to cast it into a desired form, cooling the form, and washing the flux from the form to provide shaped solder.

The invention also provides an embodiment of the solder method, process and apparatus, characterized in that the solder is melted at about 250 ° C. or less. In another embodiment of the solder method, process and apparatus, the solder is an alloy of a metal. In another embodiment, the solder is lead free. In some embodiments, the particles form chemical bonds with the solder. In some embodiments, the particles have the formula R ₇ Si ₇ O ₉ (OH) ₃ and the following structures:

(Wherein R is an organic functional group)

POSS-triol with In some embodiments of the solder methods, processes, and apparatus, the particles are cyclohexal POSS-triols, and in other embodiments the particles are phenyl POSS-triols. In some embodiments of the solder methods, processes, and apparatus, the metal may comprise tin (Sn), silver (Ag), copper (Cu), bismuth (Bi), zinc (Zn), indium (In), gold (Au), Nickel (Ni), antimony (Sb), palladium (Pd), platinum (Pt), germanium (Ge) and mixtures thereof. In some embodiments, the metal matrix is Sn--Ag and in further embodiments the metal matrix is eutectic 96.5 wt% Sn-3.5 wt% Ag.

Accordingly, it is an object of the present invention to achieve the desired level of particle size and dispersion in low melting metals as castings or solders, using unique organic functional inorganic oxides, to enhance their service performance.

Another object of the present invention is to provide a lead-free solder with improved service performance.

These and other objects will be apparent with reference to the following detailed description and drawings.

All patents, patent applications, government publications, government regulations, and references cited herein are hereby incorporated by reference in their entirety. In case of conflict, the present description, including definitions, will control. The following definitions of terms are provided to further understand the present invention.

"Organic-functional inorganic oxide particles" preferably range in size from nanometers to sub-microns and are preferably caged. The inorganic oxide may be based on a metalloid selected from the group consisting of transition metals, lanthanides or actinide metal atoms, or boron, silicon, germanium, arsenic and tellurium. Organic functional inorganic oxide particles include, but are not limited to, organic functional silicates as described in POSS, POS and US Pat. Nos. 6,284,696 (Koya, et al.) And 6,465,387 (Pinnavaia et al.). The particles have metal oxide cores and have organic residues covalently bonded to the core that are resistant to decomposition. Each organic moiety is independently selected from the group consisting of aliphatic and aromatic hydrocarbon groups. Organic residues may include, but are not limited to, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, and heteroaryl groups. Organic residues may include, but are not limited to, hexyl, heptyl, octyl, cyclohexal, vinyl, allyl, hexenyl, heptenyl, octenyl and phenyl groups.

The term "POSS" refers to polyhedral oligomeric silsesquioxanes and derivatives thereof. POSS has a T-cased branching structure:

General formula of _{POSS [R Si O 1 .5]} n ( where, R is the same or different organic residues in each case), and are independently selected from aliphatic and aromatic hydrocarbon group consisting of a group. Organic residues include, but are not limited to, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl and heteroaryl. One example of a POSS with n = 6 and the formula R ₆ Si ₆ O ₉ has the following structure:

The term also includes, but is not limited to, triol derivatives thereof.

The term "POS", the formula [RMe ₂ SiOSiO _{1 .5]} having _n, represents a polyhedral oligomeric silicates, and derivatives thereof of the Q- cage structure. An example of POS (n = 6) has the following structure:

(Wherein R in each case is the same or different organic moiety) and is independently selected from the group consisting of aliphatic and aromatic hydrocarbon groups. Organic residues include, but are not limited to, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl and heteroaryl. One example of POS is that the term also includes, but is not limited to, triol derivatives.

"Low melting point" is defined as having a melting point of up to 600 ° C.

The "metal matrix" includes magnesium (Mg), zinc (Zn), cadmium (Cd), aluminum (Al), indium (In), thallium (Tl), tin (Sn), lead (Pb), and mismut (Bi). ) And mixtures thereof, including but not limited to metals. In addition, it is tin (Sn), silver (Ag), copper (Cu), mismud (Bi), zinc (Zn), indium (In), gold (Au), nickel (Ni), antimony (Sb), palladium (Pd), platinum (Pt), germanium (Ge) and mixtures thereof.

The term "lead-free" means a composition having a lead weight percentage of 0.01 weight percent (0.01 wt.%) Or less.

"Composite solder" is solder containing a reinforcing material that is intentionally included. The reinforcing material of the present invention is an organofunctional inorganic oxide particle. These particles range from 0.1 to 10% by weight of the matrix.

The present invention preferably includes an inert reinforcement at the nanometer to sub-micron level that is capable of bonding with the solder matrix. Preferably, the particle size is approximately 10 to 100 nanometers. Recent developments in POSS technology have provided new means for this application. POSS nano-technology can produce suitable means to promote bonding between such reinforcements and metal matrices. In addition, there are several means by which they can be included in the solder to obtain nanometer to sub-micron size reinforcements. This composite approach does not change the solderability of a given alloy system or its reflow characteristics. Electronic packaging, MEMS and automotive / aerospace / defense electronics are some of the potential uses of the present invention. Lead-free solder in the art does not include inorganic / organic nano-sized particle reinforcements.

Soldering using the present invention can be performed by partial heating or total heating. Some heating methods include, but are not limited to, the use of soldering irons, pulse heaters, lasers, light beams, hot air and jet flow soldering. Full heating methods include, but are not limited to, infrared reflow, convection reflow, infrared convection combined, vapor phase soldering (VPS), and flow soldering.

The simplest localization method using composite solder is to use a soldering iron by providing the composite solder and heating it with the iron to melt it. The solder is then bonded to the electronic component lead. Another method of using composite solder is to use pulsed thermal solder. The composite solder is applied in advance and pressure is applied from the heater chip. Convection reflow is a method of heating the provided solder paste with hot gas flowing from the nozzle. Laser soldering is performed by melting a solder provided by applying a laser beam. Light beam soldering is performed by applying light from a xenon lamp.

Generalized soldering methods include reflow and flow (wave) soldering. Reflow melts and resolidifies the composite solder. The reflow method is performed by printing a composite solder paste on a circuit board before mounting the electronic component. Apply heat to apply solder on the lead of the part. Heat is applied using an infrared panel heater, convection heater, or a high temperature inert vapor atmosphere. Flow (wave) soldering is performed by mounting an electronic component with an adhesive or an insertion into the substrate before applying the flux. Next, the solder melted on the electronic component is pressed. The invention is applicable using single-sided or double-sided soldering process flows.

Solder can be used in combination with various types of fluxes to increase solderability, such as R (rosin) type, RMA (appropriately activated) and RA (activated) fluxes. The flux mixed with the solder can be a non-water soluble flux or a water soluble flux. Typical water-insoluble fluxes are rosin-based fluxes, but other water-insoluble fluxes may be used. Rosin can be polymerized or nonpolymerized. Flux generally consists of a base material such as rosin, a small amount of activator, and optionally a thixotropic agent in the solvent. Activators of rosin include, for example, amine hydrohalide salts, amine organic acid salts and organic acids. Thixotropic agents include, for example, hydrogenated castor oil. Solvents useful for the water-insoluble flux include glycol ethers, lower alcohols and terpenes.

It is important to clean the solder after soldering to remove solder flux, oils, waxes, greases and other organic residues formed during electronic circuit device bonding and assembly. Various cleaner compositions may be used, depending on the type of flux used, and to clean the composite solder composition after soldering. The water soluble flux can be easily removed with warm soapy water. Rosin fluxes are chlorinated hydrocarbons such as 1,1,1-trichloroethane, trichloroethylene, trichloromonofluoromethane, methylene chloride, trichlorotrifluoroethane (CFD113), tetrachlorodifluoroethane (CFC112). Solvents and other solvents can be used for removal. These cleaning compositions are described in more detail in US Pat. No. 6,569,252 (Sachdev, et al.) And US Pat. No. 5,234,506 (Winston, et al.) And incorporated herein by reference.

Using any of the soldering techniques described above, circuit devices using composite solder can be made. The solder layer connecting the two leads 11 is shown in FIG. 17, where the particles 13 are dispersed in the solder matrix 12. 33 shows a solder layer 10 having a solder joint 13 between the silicon chip 12 and the substrate 11. FIG. 34 shows a composite solder, which connects a printed circuit board (PCB) 13, coated with a molding compound 14, with a chip 11 in a Ball Grid Array (BGA) substrate 15. A microchip connection 10 with a ball 12 is shown. The circuit can be assembled using a variety of electronic components, including but not limited to integrated circuits, transistors, resistors, capacitors, diodes, rectifiers, microelectronic devices, and MEMS.

Synthesis of oligomeric silasesquioxanes is generally carried out through hydrolytic condensation of trifunctional RSiY ₃ precursors, with R being a hydrocarbon radical and Y being a hydrolyzable group such as chloride, alkoxide or siloxane. (J. Am. Chem. Soc. 1989, 111, 1741-1748; Organometallics 1991, 10, 2526-2528). This reaction generally produces a mixture of fully and incompletely condensed oligomeric silsesquioxanes. One important, fully condensed oligomeric silacesquioxane is compound R ₆ Si ₆ O ₉ . Compounds of this structure, wherein R is cyclohexal, can be reacted with RSi (OMe) _{3 in} the presence of a basic catalyst to obtain a functionalized, incompletely condensed silacesquioxane of the structure:

One example is R ₇ Si ₇ O ₉ (OH) ₃ , where R is cyclohexal (Chem. Commun. 1999, 2153-2154, Polym. Master. Sci. Eng. 2000, 82, 301-302).

In the following examples, composite solder was prepared by adding POSS to the solder matrix. Two different POSS with different active organic groups were included in eutectic 96.5 wt% tin (Sn) -3.5 wt% silver (Ag). 32 illustrates an experimental set-up 10 for solder joint manufacture. Half-dog-bone type copper strips 13 were joined to prepare a single shear-lap solder joint specimen. The solder joint made of solder paste 12 between the copper strips 13 was about 100 μm thick and about 1 mm × 1 mm solder joint area. These joints were made of an aluminum fixture 16 with an assembly of a copper strip 13 comprising a top glass plate 11 and a bottom glass 14 positioned thereon. The aluminum fixture 16 was placed on a hot plate. Once the temperature measured by the thermocouple wire 15 in the bonding region is about 30-50 ° C. above the melting point of the solder, the aluminum fixture 16 is removed from the hot plate, placed on an aluminum block and cooled. . One joint surface was metallurgically polished to observe microstructural properties after various treatments and tested by scanning electron microscopy (SEM). POSS size and distribution were examined from the sides and fracture surfaces of the mechanically tested samples.

Mechanical testing of single shear-wrap solder joints made of nanocomposite solder showed fine finely distributed POSS reinforcements and was tested using a highly sensitive thermomechanical analyzer. The primary purpose of these tests was to identify POSS reinforcements with increased shear strength. Shear ductility is a parameter that must be reduced for dimensional stability. This should be increased, in order to make the solder joint well accommodate the strain imposed, especially under impact conditions. The fracture surfaces of these shear tested specimens were used to confirm the size and distribution of the POSS particulates. In order to confirm the strain fracture and their relationship, the polished side of the solder joint was examined by SEM.

The reinforcement was strongly bonded to the metal matrix. They did not aggregate. A well distributed 100 nanometer reinforcement appeared. The absence of any compound at the interface also indicates that these POSS molecules are truly inert. These increase the strength to some extent.

1 is a plan view of the fracture surface of a solder joint with cyclohexal POSS-triol. Bars represent 5 micrometers.

2 is a plan view of the fracture surface of a solder joint with cyclohexal POSS-triol. Bars represent 10 micrometers.

3 is a side view of the fracture surface of a solder joint with cyclohexal POSS-triol. Bars represent 5 micrometers.

4 is a side view of the fracture surface of a solder joint with cyclohexal POSS-triol. Bars represent 2 micrometers.

5 is a side view of the fracture surface of a solder joint with cyclohexal POSS-triol. Bars represent 2 micrometers.

6 is an enlarged elevation view of a polished surface of a solder joint with cyclohexal POSS-triol. Bars represent 1 micrometer.

7 is an SE image of a polished surface of a solder joint with cyclohexal POSS-triol. The SE and BE images show clear Ag ₃ Sn particles in the same area. Bars represent 2 micrometers.

8 is a BE image of the polished surface of a solder joint with cyclohexal POSS-triol. The SE and BE images show clear Ag ₃ Sn particles in the same area. Bars represent 2 micrometers.

9 is a plan view of the fracture surface of a solder joint with phenyl POSS-triol. Bars represent 10 micrometers.

10 is a side view of the fracture surface of a solder joint with phenyl POSS-triol. Bars represent 5 micrometers.

11 is a side view of the fracture surface of a solder joint with phenyl POSS-triol. Bars represent 2 micrometers.

12 is a polished surface of a solder joint with phenyl POSS-triol. Bars represent 20 micrometers.

FIG. 13 is an SE image of a polished surface of a solder joint with phenyl POSS-triol showing sharp Ag ₃ Sn particles. Bars represent 2 micrometers.

FIG. 14 is a BE image of the polished surface of a solder joint with phenyl POSS-triol showing sharp Ag ₃ Sn particles. Bars represent 2 micrometers.

15 is a polished surface of a solder joint with phenyl POSS-triol. Bars represent 5 micrometers.

16 shows the structure of phenyl POSS-triol.

17 shows the structure of cyclohexal POSS-triol.

18 shows a sketch of a soldered part.

19 shows the microstructure of eutectic Sn-Ag. The rod is 10 micrometers.

20 shows the shear strength of eutectic Sn-Ag and composites.

FIG. 21 shows at low magnification the fracture surface of a cyclohexal POSS-triol / Sn-Ag solder joint. Bars represent 10 micrometers.

FIG. 22 shows at high magnification the fracture surface of a cyclohexal POSS-triol / Sn-Ag solder joint. Bars represent 2 micrometers.

FIG. 23 shows an SE image of the polished surface of a cyclohexal POSS-triol / Sn-Ag solder joint. Bars represent 5 micrometers.

24 shows a BE image of the polished surface of a cyclohexal POSS-triol / Sn-Ag solder joint. Bars represent 5 micrometers.

FIG. 25 shows at high magnification the polished surface of a cyclohexal POSS-triol / Sn-Ag solder joint. Bars represent 1 micrometer.

FIG. 26 shows at low magnification the fracture surface of a phenyl POSS-triol / Sn-Ag solder joint. Bars represent 10 micrometers.

27 shows, at high magnification, the fracture surface of a phenyl POSS-triol / Sn-Ag solder joint. Bars represent 2 micrometers.

28 shows an SE image of the polished surface of a phenyl POSS-triol / Sn-Ag solder joint. Bars represent 5 micrometers.

29 shows a BE image of the polished surface of a phenyl POSS-triol / Sn-Ag solder joint. Bars represent 5 micrometers.

30 shows at high magnification the polished surface of a phenyl POSS-triol / Sn-Ag solder joint. Bars represent 1 micrometer.

31 shows simple shear strength of eutectic Sn-Ag and composites.

32 shows an experimental arrangement for solder joint manufacture. Copper strip, top glass plate, bottom glass plate, solder paste, thermocouple wire, heated aluminum fixture.

33 shows a solder joint between a silicon chip and a substrate.

34 shows a microchip bond using composite solder.

35A-35H show SEM images of initial microstructures of various POSS containing composite solder joints.

36 shows a single shear wrap solder joint.

FIG. 37 is a graph showing the shear strength of eutectic Sn-Ag and various composite solder joints shear tested at room temperature with a strain rate of 0.01 s ⁻¹ .

38 is a graph showing the shear strength of eutectic Sn-Ag and various composite solder joints shear tested at 85 ° C. with a strain rate of 0.01 s ⁻¹ .

39 is a graph showing the shear strength of eutectic Sn-Ag and various composite solder joints shear tested at 150 ° C. with a strain rate of 0.01 s ⁻¹ .

40 is a graph showing the shear strength of eutectic Sn-Ag and various composite solder joints shear tested at room temperature at a strain rate of 0.001 / s.

41A and 41B are graphs showing shear deformation behavior of the eutectic Sn-Ag solder joint 41a and the POSS-containing composite solder joint 41b.

42A and 42B are SEM images of shear broken specimens: 42a is a eutectic Sn-Ag solder joint and 42b is a POSS containing composite solder joint.

43 is a graph showing the temperature-time profile for TMF.

44A-44D are SEM images of eutectic Sn-Ag solder joints after 0, 250, 500, and 1000 cycles of TMF.

45A-45D are SEM images of 2 wt% POSS containing solder joints after 0, 250, 500 and 1000 cycles of TMF.

46A-46D are SEM images of 3 wt% POSS containing solder joints after 0, 250, 500 and 1000 cycles of TMF.

47A-47C are SEM images of eutectic Sn-Ag based solder joints after 1000 TMF cycles.

FIG. 48 is a graph showing residual shear strength of eutectic Sn-Ag and POSS (cyclohexenyl-triol) containing solder points after TMF.

49A-49C are schematic illustrations of grain boundary slip due to shear forces applied at high temperatures. 49a: Grain boundary slip between two adjacent grains is unobstructed. 49b: Grain deforms lattice due to the presence of intermetallic particles on the grain boundary during grain boundary sliding. 49c: The slip of the grain boundary triple point shows the location of the lattice deformation. Note: Obstacles increase the resistance to slip, increasing plastic deformation.

50 is a graph showing creep at room temperature for Sn-Ag eutectic solder with and without POSS.

Example 1

The solder joints consisted of cyclohexal POSS-triol incorporated into a eutectic mixture of 96.5 wt% tin (Sn)-3.5 wt% silver (Ag) supplied as multicore solder incorporation, item number NC63 (multicore Solder is now part of Henkel). Cyclohexal POSS-triol is formula (C ₆ H ₁₁ ) ₇ Si ₇ O ₉ (OH) ₃ and structure:

Wherein Cy is a cyclohexyl moiety.

The solder joint was broken and the surface was analyzed with an electron scan spectrometer. 5 and 10 micron dimensional top views of the cyclohexal POSS-triol and solder joint fracture surfaces are shown in FIGS. 1 and 2, respectively. Particles are shown. A 5 micron dimensional side view of the cyclohexal POSS-triol and solder joint fracture surface is shown in FIG. 3 and two surface micron enlarged views are shown in FIGS. 4 and 5. Shear bands are shown in FIG. 3. The micron dimensional polished surface of the cyclohexal POSS-triol and solder joint is shown in FIG. 7 and 8 show electron scan (SE) and backside electron scattering (BE) images of the same area on the polished surface of the cyclohexal POSS-triol and solder joint. Clear Ag ₃ Sn particles are shown. 20 shows the simple shear strength of eutectic Sn-Ag and cyclohexyl POSS-triol composites.

Example 2

The solder joints consisted of phenyl POSS-triol incorporated into a eutectic mixture of 96.5 wt% tin (Sn)-3.5 wt% silver (Ag) supplied as multicore solder incorporation, item number NC63 (multicore solder Is currently part of Henkel). Phenyl POSS-triol has the formula (C ₆ H ₅ ) ₇ Si ₇ O ₉ (OH) ₃ and the structure:

Wherein Ph is a phenyl moiety.

The solder joint was broken and the surface was analyzed with an electron scan spectrometer. A 10 micron dimensional plan view of the phenyl hexal POSS-triol and solder joint fracture surface is shown in FIG. A 5 micron dimensional side view of the phenyl POSS-triol and solder joint fracture surface is shown in FIG. 10, and FIG. The 20 micron dimension polished surface of the phenyl POSS-triol and solder joint is shown in FIG. 13 and 14 show the SE and BE images of the same area on the polished surface of the phenyl POSS-triol and solder joint. Clear Ag ₃ Sn particles are shown. 20 shows the simple shear strength of eutectic Sn-Ag and phenyl POSS-triol composites.

Example 3

The experiment was repeated using Sn-Ag eutectic mixtures from another solder source (Kester; Article No. R520A). Composite solder was made using Kester eutectic Sn-3.5Ag solder, article number R520A. 0.2765 g of POSS-cyclohexyltriol was added to 5.1674 g of solder, resulting in 5.07 wt% particles mixed with eutectic Sn-3.5Ag (see Table 1). The estimated volume percentage of the microparticles mixed with eutectic Sn-3.5Ag is 20% by volume.

Table 1 shows a composite solder mechanically woven with eutectic Sn-3.5Ag.

Solder POSS POSS Phenyltriol 5.0639 g 0.2745 g POSS cyclohexyltriol 5.1674 g 0.2765 g

Weight Used in Composite Solders

Weight% of fine particles mixed with eutectic Sn-3.5Ag

POSS-phenyltriol (Tr-POSS): 5.14%

2. POSS-cyclohexyltriol (Cy-POSS): 5.07%

Volume% of fine particles mixed with eutectic Sn-3.5Ag

About 20% by volume particulates for each composite solder

The fracture surface at low magnification of the cyclohexal POSS-triol / Sn-Ag solder joint is shown in FIG. Bars represent 10 micrometers. Figure 22 shows the fracture surface at high magnification of cyclohexyl POSS-triol / Sn-Ag solder joints. Bars represent 2 micrometers. Figure 23 shows an SE image of the polished surface of a cyclohexal POSS-triol / Sn-Ag solder joint. Bars represent 5 microns. Figure 24 shows a BE image of the polished surface of a cyclohexal POSS-triol / Sn-Ag solder joint. Bars represent 5 micrometers. Figure 25 shows the polished surface of cyclohexyl POSS-triol / Sn-Ag solder joints at high magnification. Bars represent 1 micrometer. Figure 31 shows the simple shear strength of eutectic Sn-Ag and cyclohexal POSS-triol composites.

Example 4

POSS-phenyltriol composite solder was prepared using Kester eutectic Sn-3.5Ag solder, article number R20A. 0.2745 g of POSS-phenyltriol was added to 5.0639 g of solder, resulting in 5.14 wt% particles mixed with eutectic Sn-3.5Ag (see Table 1). The volume taken is 20% by volume.

The fracture surface at low magnification of the phenyl POSS-triol / Sn-Ag solder joint is shown in FIG. Bars represent 10 micrometers. Figure 27 shows the fracture surface at high magnification of phenyl POSS-triol / Sn-Ag solder joints. Bars represent 2 micrometers.

Figure 28 shows an SE image of the polished surface of a phenyl POSS-triol / Sn-Ag solder joint. Bars represent 5 micrometers. 29 shows a BE image of the polished surface of a phenyl POSS-triol / Sn-Ag solder joint. Bars represent 5 micrometers. 30 shows the polished surface of phenyl POSS-triol / Sn-Ag solder joints at high magnification. Bars represent 1 micrometer. Figure 31 shows the simple shear strength of eutectic Sn-Ag and phenyl POSS-triol composites.

Example 5

The examples below show the shear strength of eutectic Sn-Ag solder joints containing different amounts and chemical moieties of POSS molecules.

Examples of POSS Particles Producing Composite Solders

Example 5 cyclohexenyl-triol (2% by weight)

Example 6 cyclohexenyl-triol (3% by weight)

Example 7 ethyl-triol (3% by weight)

Example 8 phenyl-triol (2% by weight)

Example 9 phenyl-triol (3% by weight)

Examples 10 and 11 cyclohexyl-diol (2% and 3% by weight)

(Wherein R is cyclohexyl)

I. Initial Microstructure

In general, a POSS comprising a composite solder joint shows very finely sized particles uniformly dispersed in the solder matrix, regardless of the shape of the POSS particles (see FIGS. 35A-35H).

II. Single-shear lap test at strain rate 0.01 s ⁻¹ and room temperature (22 ° C.)

 Single-shear wrap solder joints were woven using the standard method described above and are shown in FIG. 36.

Table 3 shows the shear strengths of various POSS including solder joints at constant strain rate 0.01 s ⁻¹ and at room temperature.

(Note: All POSS, including solder joints, used eutectic Sn-Ag solder paste to form single-shear wrap solder joints.)

Type of POSS used Shear strength (MPa) Prior art Not POSS (eutectic Sn-Ag) 42 4 Example 5 2% by weight cyclohexenyltriol 58 5 Example 6 3% by weight cyclohexenyltriol 60 2 Example 8 2 wt% phenyltriol 60 3 Example 9 3 wt% phenyltriol 61 4 Example 7 3 wt% ethyltriol 60 2 Example 10 2 wt% cyclohexyldiol 64 3 Example 11 3% by weight cyclohexyldiol 62 4

37 shows the results in graphical form.

III. Shear test at strain rate 0.01s ^-1 and 85 ° C

Table 4 shows the shear strengths of various POSS with solder joints at constant strain rates of 0.01 s ⁻¹ and 85 ° C.

Type of POSS used Shear strength (MPa) Prior art Not POSS (eutectic Sn-Ag) 28 Example 5 2% by weight cyclohexenyltriol 35 2 Example 8 3 wt% phenyltriol 34 4 Example 7 3 wt% ethyltriol 36 4 Example 10 2 wt% cyclohexyldiol 32 3

38 shows the results in graphical form.

IV. Shear test at strain rate 0.01 s ^-1 and 150 ° C

Table 5 shows the shear strengths of various POSS including solder joints at constant strain rates of 0.01 s ⁻¹ and 150 ° C.

Type of POSS used Shear strength (MPa) Prior art Not POSS (eutectic Sn-Ag) 22 Example 6 3% by weight cyclohexenyltriol 28 4 Example 9 3 wt% phenyltriol 25 1 Example 8 3 wt% ethyltriol 26 2 Example 11 3% by weight cyclohexyldiol 25 2

39 shows the results in graphical form.

V. Shear Test at Strain Rate 0.001s ^-1 and Room Temperature (22 ° C)

Table 6 shows the shear strengths of various POSS including solder joints at constant strain rate of 0.001 s ⁻¹ and at room temperature.

Type of POSS used Shear strength (MPa) Prior art Not POSS (eutectic Sn-Ag) 42 Example 6 3% by weight cyclohexenyltriol 51 2 Example 8 2 wt% phenyltriol 50 3 Example 7 3 wt% ethyltriol 52 1

40 shows the results in graphical form.

Regardless of the amount and type of POSS used, POSS including eutectic Sn-Ag solder joints showed improved shear strength over unreinforced eutectic Sn-Ag solder joints at different temperatures and strain rates.

The fracture structures of the joints made of POSS including eutectic Sn—Ag solder joints as shown in FIGS. 41A and 41B and 42A and 42B show uniform deformation, while unreinforced joints show local deformation.

Comparison of POSS with Eutectic Sn-Ag and Solder Joints Following Exposure to Thermo-mechanical Fatigue (TMF)

Solder joints are used in a variety of environments. As part of this evaluation, the solder joints were exposed to actual thermal cycle conditions as shown in FIG. Surface damage was observed at different exposure times using SEM. After exposure to 1000 thermal cycles, the joints were tested at normalized shear conditions to assess residual strength. For TMF testing, eutectic Sn-Ag solder was used comprising two different weight ratios of cyclohexyl-POSS triols. The joint form is shown in FIG. The geometry of the solder joint was a single shear wrap solder joint in the form of a dog-bone.

I. Accumulation of Surface Damage

As shown in Figures 44A-44D, notable progression of surface damage was observed in eutectic Sn-Ag solder joints with an increase in the number of TMF cycles.

As shown in FIGS. 45A-45D and 46A-46D, the solder joint composites comprising POSS particles showed much less surface damage even after 1000 TMF cycles.

After up to 1000 TMF cycles, the eutectic Sn-Ag solder joints showed very local surface damage in the vicinity of the intermetallic compound (IMC) layer in the joint region as indicated in FIG. 47A. Surface damage observed in eutectic Sn-Ag solder joints (FIGS. 47B and 47C) is due to mismatches in the coefficient of thermal expansion (CTE) between the Cu substrate and the solder. Since Sn (tin) is a very anisotropic material (body centered square), the anisotropy of tin also plays an important role in the formation of damage on eutectic Sn-Ag solder joint surfaces.

However, surface damage in solder joint composites containing POSS particles was much less compared to the accumulation of damage in eutectic Sn—Ag solder joints, and as shown in FIGS. 47A and 47B, the deformation is much more uniform throughout the solder joint area. did.

II. Residual strength

Initially, POSS improves the strength of the solder joints (see Table 7 and Figure 48).

Table 7 shows the residual shear strength of POSS (cyclohexenyl-triol) with solder joints after TMF. (Tested at constant strain rate 0.01s ^-1 and room temperature)

TMF Cycle # Shear Strength (Mpa) of Eutectic Sn-Ag Shear strength (MPa) of 2% by weight POSS Shear Strength (MPa) of 3% by weight POSS 0 40 58 60 250 32 48 49 500 29 45 48 1000 26 46 43

The improved shear strength and service performance observed are believed to be related to the pinning of grain boundary sliding by the use of nano-particles. It is important to point out that the nano-particles used here should be inert so that the size of the nano-reinforcement remains unchanged throughout the working life of the solder joint. It is shown in Figures 49a, 49b and 49c.

III. Notable findings after TMF

POSS improves the strength of solder joints. TMF results in minimal uniform surface damage in POSS containing solder joints, while noticeable local damage occurs near the solder / substrate interface in joints made of solder that do not contain POSS under the same conditions.

Even after 1000 TMF cycles, the reduction in residual strength is minimal in joints made of POSS (less than 20%) containing solder as compared to the noticeable reduction in properties in joints made of solder that do not contain POSS reinforcement (40-50%).

The residual strength of joints made of POSS with solder after TMF is much higher than that made with solder without POSS reinforcement.

Summary of Findings in Lead-Free POSS Composite Solders

POSS stiffeners can be mechanically mixed with commercial solder paste.

It is evenly distributed through the solder joint without any notable micron size agglomeration.

POSS stiffeners appear in the inclined joints that exist at Sn grain boundaries. Such a form is very important in preventing grain boundary slippage and progression that causes damage to the processing thermal fatigue (TMF) of the solder joint.

The presence of POSS stabilizes the microstructure. No noticeable microstructure change was observed after about 2000 hours as a result of 1000 TMF cycles at 150 ° C. No grain growth was observed in the solder reinforced with POSS.

POSS particles are very stable under TMF conditions. It does not show any coarseness as in in-situ or IMC reinforcements introduced by mechanical means.

The addition of POSS reduces the wetting angle between the eutectic Sn—Ag solder and the copper substrate.

Addition of 2-3% by weight of POSS increases the shear strength of eutectic Sn—Ag solder by about 50% without noticeable effect on its ductility in room temperature studies.

Adding more than 3% by weight of POSS reduces the wettability of the solder on the copper substrate.

The addition of 3% by weight POSS to the eutectic Sn-Ag solder corresponds to about 15% by volume reinforcement. Increasing the POSS addition increases the wetting angle and thus reduces the solderability. Studies on composite solders suggest that 15 to 20% by volume reinforcement is optimal considering properties and solderability.

POSS stiffeners are nano-sized particles that bind very well to solder. POSS reinforcements do not fall from the solder matrix even after 1000 thermal cycles between -15 ° C. and 150 ° C. with downtime at extreme temperatures. Such a property means a very strong bond between the POSS and the solder.

Although SAC (Sn-4Ag-0.5Cu) solder joints are stronger than eutectic Sn-Ag solder joints in the jointed form, they degrade much faster than eutectic solders under TMF conditions.

Under actual TMF conditions, the TMF workability of POSS reinforced eutectic Sn-Ag solder joints is much better than that of SAC (Sn-4Ag-0.5Cu) alloy solder joints.

Even after the TMF 1000 cycles, the POSS reinforced solder joints show no noticeable surface damage. The minimum damage observed under such conditions is much more evenly distributed at the solder joint surface. Under such conditions, the lack of severe local damage in the solder near the solder / substrate IMC interface is critical for improved TMF workability.

Unlike the stiffeners present in in-situ composite solder that weakly bonds to the solder, POSS stiffeners bind very strongly to the solder.

The strong bonding of the POSS reinforcement to the solder, its nano size, its dimensional stability without any coarseness or coarseness, and its presence at the grain boundaries are the major contributors to the improved workability of POSS reinforced solder joints compared to other composite solders. Is considered.

Means, work incorporating POSS into the solder can be used for applications that use wave soldering.

POSS does not impair the electrical properties of the solder.

Table 8 shows the electrical conductivity of POSS (3 wt% cyclohexyl-triol) containing eutectic Sn-Ag and joints.

material Electrical Conductivity (μΩ.㎝) ^-1 Eutectic Sn-Ag Solder Joint ~ 0.12 (μΩ.㎝) ^-1 POSS with Composite Solder Joints ~ 0.11 (μΩ.cm) ^-1 Bulk Sn-Ag ~ 0.13 (μΩ.㎝) ^-1 Pure Bulk Sn ~ 0.09 (μΩ.㎝) ^-1

The presence of POSS has little effect on the electrical conductivity of the solder.

FIG. 50 is a graph showing creep at room temperature of solder (open cut) comprising 3% by weight POSS compared to eutectic Sn—Ag solder joints (underlined diamond). It is clear that POSS improves creep resistance at room temperature by soldering at a melting point of 0.8.

Although the present invention has been described based on the examples described above, it should not be understood that the invention is limited thereto. Those skilled in the art and approaches to what is taught herein will recognize additional variations and embodiments within the scope. Accordingly, the invention is limited only by the claims that follow.

Claims (84)

(a) a metal matrix; And (b) A composite composition comprising inorganic oxide particles having organic functional groups chemically bonded on the surface of the particles in which the particles are dispersed in the metal matrix. The method of claim 1, And the metal melts at a temperature of about 600 ° C. or less. The method of claim 1, Wherein said metal is an alloy of the metal. The method of claim 1, The metal is magnesium (Mg), zinc (Zn), cadmium (Cd), aluminum (Al), indium (In), thallium (Tl), tin (Sn), lead (Pb), bismuth (Bi) and mixtures thereof Compositions selected from the group consisting of. The method of claim 1, And wherein said particles are selected from the group consisting of POSS, POS and mixtures thereof. The method of claim 5, The particles are of the formula R ₇ Si ₇ O ₉ (OH) ₃ and have the following structure:

(Wherein R is an organic functional group) POSS-triol having a composition, characterized in that. The method of claim 6, Wherein said particles are cyclohexal POSS-triol. The method of claim 6, Wherein said particles are phenyl POSS-triols. Providing an inorganic oxide particle having an organic functional group chemically bonded on the surface of the particle in a molten metal to produce a metal matrix having particles dispersed in the metal matrix. The method of claim 9, The metal is melted at a temperature of about 600 ° C. or less. The method of claim 9, And said metal is an alloy of the metal. The method of claim 9, The metal is magnesium (Mg), zinc (Zn), cadmium (Cd), aluminum (Al), indium (In), thallium (Tl), tin (Sn), lead (Pb), bismuth (Bi) and its Process selected from the group consisting of mixtures. The method of claim 9, And said particles are selected from the group consisting of POSS, POS and mixtures thereof. The method of claim 9, The particles are of the formula R ₇ Si ₇ O ₉ (OH) ₃ and have the following structure:

(Wherein R is an organic functional group) POSS-triol having a process. The method of claim 9, And said particles are cyclohexal POSS-triols. The method of claim 9, Wherein said particle is phenyl POSS-triol. (a) metal solder; And (b) A composite composition comprising inorganic oxide particles having organic functional groups chemically bonded on the surface of the particles dispersed in the solder. The method of claim 17, Wherein said solder melts at about 250 ° C. or less. The method of claim 17, Wherein said solder is an alloy of a metal. The method of claim 17, The composition is a paste, wherein the solder is melted to form solder as a matrix having particles dispersed in the matrix. The method of claim 17, Wherein said solder is a solid preform of solder comprising solder as a matrix and particles dispersed in the matrix. The method of claim 17, The solder is lead-free composition, characterized in that. The method of claim 17, Wherein said particles form chemical bonds with solder. The method of claim 17, The particles are of the formula R ₇ Si ₇ O ₉ (OH) ₃ and have the following structure:

(Wherein R is an organic functional group) POSS-triol having a composition, characterized in that. The method of claim 17, Wherein said particles are cyclohexal POSS-triol. The method of claim 17, Wherein said particles are phenyl POSS-triols. The method of claim 17, The metal is tin (Sn), silver (Ag), copper (Cu), bismuth (Bi), zinc (Zn), indium (In), gold (Au), nickel (Ni), antimony (Sb), palladium ( Pd), platinum (Pt), germanium (Ge) and mixtures thereof. The method of claim 27, Composition wherein the metal matrix is Sn--Ag. The method of claim 27, The metal matrix is a composition characterized in that the eutectic 96.5 wt% Sn-3.5 wt% Ag. a) introducing an inorganic oxide particle into the particulate metal solder having an organic functional group chemically bonded on the surface of the particle; And b) mechanically mixing the particles and the metal solder to provide a paste. The method of claim 30, The solder is melted at about 250 ° C. or less. The method of claim 30, Wherein said solder is an alloy of a metal. The method of claim 30, And said solder is lead free. The method of claim 30, Wherein said particles form chemical bonds with solder. The method of claim 30, The particles are of the formula R ₇ Si ₇ O ₉ (OH) ₃ and have the following structure:

(Wherein R is an organic functional group) POSS-triol having a process. The method of claim 30, And said particles are cyclohexal POSS-triols. The method of claim 30, Wherein said particle is phenyl POSS-triol. The method of claim 30, The metal is tin (Sn), silver (Ag), copper (Cu), bismuth (Bi), zinc (Zn), indium (In), gold (Au), nickel (Ni), antimony (Sb), palladium ( Pd), platinum (Pt), germanium (Ge) and mixtures thereof. The method of claim 30, The metal matrix is Sn--Ag. The method of claim 30, Said metal matrix is 96.5 wt% Sn-3.5 wt% Ag. a) providing a composite composition comprising a metal solder comprising inorganic oxide particles having organic functional groups chemically bonded on the surface of the particles dispersed in the solder; b) using soldering means to melt the solder to join the two or more components, applying the solder to join the two or more components. 42. The method of claim 41 wherein The solder is melted at about 250 ° C. or less. 42. The method of claim 41 wherein The solder is an alloy of a metal. 42. The method of claim 41 wherein And the solder is lead free. 42. The method of claim 41 wherein Wherein said particles form chemical bonds with solder. 42. The method of claim 41 wherein The particles are of the formula R ₇ Si ₇ O ₉ (OH) ₃ and have the following structure:

(Wherein R is an organic functional group) POSS-triol having a method. 42. The method of claim 41 wherein And wherein said particles are cyclohexal POSS-triols. 42. The method of claim 41 wherein The particle is phenyl POSS-triol. 42. The method of claim 41 wherein The metal is tin (Sn), silver (Ag), copper (Cu), bismuth (Bi), zinc (Zn), indium (In), gold (Au), nickel (Ni), antimony (Sb), palladium ( Pd), platinum (Pt), germanium (Ge) and mixtures thereof. 42. The method of claim 41 wherein And said metal matrix is Sn-Ag. 42. The method of claim 41 wherein The metal matrix is 96.5 wt% Sn-3.5 wt% Ag. a) one or more electronic components; And b) an electronic device comprising a composite composition comprising metal solder and inorganic oxide particles having organic functional groups chemically bonded on the surface of the particles dispersed in the solder. The method of claim 52, wherein Wherein the solder is melted at about 250 ° C. or less. The method of claim 52, wherein And the solder is an alloy of a metal. The method of claim 52, wherein And the solder is lead free. The method of claim 52, wherein Wherein the particles form chemical bonds with the solder. The method of claim 52, wherein The particles are of the formula R ₇ Si ₇ O ₉ (OH) ₃ and have the following structure:

(Wherein R is an organic functional group) Device characterized in that the POSS-triol having. The method of claim 52, wherein And said particles are cyclohexal POSS-triols. The method of claim 52, wherein And said particles are phenyl POSS-triols. The method of claim 52, wherein The metal is tin (Sn), silver (Ag), copper (Cu), bismuth (Bi), zinc (Zn), indium (In), gold (Au), nickel (Ni), antimony (Sb), palladium ( Pd), platinum (Pt), germanium (Ge) and mixtures thereof. The method of claim 52, wherein And said metal matrix is Sn-Ag. The method of claim 52, wherein Wherein said metal matrix is eutectic 96.5 wt% Sn-3.5 wt% Ag. a) introducing into the metal solder particles inorganic oxide particles having organic functional groups chemically bonded on the particle surface; b) mechanically mixing the particles and the metal solder to form a paste; And c) melting the paste to form a preform in which particles are dispersed in the metal matrix. The method of claim 63, wherein The solder is melted at about 250 ° C. or less. The method of claim 63, wherein Wherein said solder is an alloy of a metal. The method of claim 63, wherein And said solder is lead free. The method of claim 63, wherein Wherein said particles form chemical bonds with solder. The method of claim 63, wherein The particles are of the formula R ₇ Si ₇ O ₉ (OH) ₃ and have the following structure:

(Wherein R is an organic functional group) POSS-triol having a process. The method of claim 63, wherein And said particles are cyclohexal POSS-triols. The method of claim 63, wherein Wherein said particle is phenyl POSS-triol. The method of claim 63, wherein The metal is tin (Sn), silver (Ag), copper (Cu), bismuth (Bi), zinc (Zn), indium (In), gold (Au), nickel (Ni), antimony (Sb), palladium ( Pd), platinum (Pt), germanium (Ge) and mixtures thereof. The method of claim 63, wherein The metal matrix is Sn--Ag. The method of claim 63, wherein Said metal matrix is 96.5 wt% Sn-3.5 wt% Ag. a) introducing inorganic oxide particles with metal functional groups on the surface of the particles into the metal solder and flux; b) mechanically mixing the particles and the metal solder; c) melting the metal solder in which the particles are dispersed in the metal solder and casting the desired shape; d) cooling this form; And e) cleaning the flux from this form to provide molded solder. The method of claim 74, wherein The solder is melted at about 250 ° C. or less. The method of claim 74, wherein Wherein said solder is an alloy of a metal. The method of claim 74, wherein And said solder is lead free. The method of claim 74, wherein Wherein said particles form chemical bonds with solder. The method of claim 74, wherein The particles are of the formula R ₇ Si ₇ O ₉ (OH) ₃ and have the following structure:

(Wherein R is an organic functional group) POSS-triol having a process. The method of claim 74, wherein And said particles are cyclohexal POSS-triols. The method of claim 74, wherein Wherein said particle is phenyl POSS-triol. The method of claim 74, wherein The metal is tin (Sn), silver (Ag), copper (Cu), bismuth (Bi), zinc (Zn), indium (In), gold (Au), nickel (Ni), antimony (Sb), palladium ( Pd), platinum (Pt), germanium (Ge) and mixtures thereof. The method of claim 74, wherein The metal matrix is Sn--Ag. The method of claim 74, wherein Said metal matrix is 96.5 wt% Sn-3.5 wt% Ag.

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