EP1716578A2 - Pate metallique nanometrique pour interconnexion et procede d'utilisation - Google Patents

Pate metallique nanometrique pour interconnexion et procede d'utilisation

Info

Publication number
EP1716578A2
EP1716578A2 EP05723019A EP05723019A EP1716578A2 EP 1716578 A2 EP1716578 A2 EP 1716578A2 EP 05723019 A EP05723019 A EP 05723019A EP 05723019 A EP05723019 A EP 05723019A EP 1716578 A2 EP1716578 A2 EP 1716578A2
Authority
EP
European Patent Office
Prior art keywords
metal
particles
metal alloy
temperature
silver
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP05723019A
Other languages
German (de)
English (en)
Other versions
EP1716578A4 (fr
Inventor
Guo-Quan Lu
John G. Bai
Jesus N. Calata
Zhiye Zhang
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Virginia Tech Intellectual Properties Inc
Original Assignee
Virginia Tech Intellectual Properties Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Virginia Tech Intellectual Properties Inc filed Critical Virginia Tech Intellectual Properties Inc
Publication of EP1716578A2 publication Critical patent/EP1716578A2/fr
Publication of EP1716578A4 publication Critical patent/EP1716578A4/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
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    • H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L24/27—Manufacturing methods
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
    • B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
    • B23K35/0244—Powders, particles or spheres; Preforms made therefrom
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
    • B23K35/3006—Ag as the principal constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
    • B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
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    • 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
    • H01L2924/10—Details of semiconductor or other solid state devices to be connected
    • H01L2924/102—Material of the semiconductor or solid state bodies
    • H01L2924/1025—Semiconducting materials
    • H01L2924/1026—Compound semiconductors
    • H01L2924/1027—IV
    • H01L2924/10272—Silicon Carbide [SiC]
    • 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
    • H01L2924/10—Details of semiconductor or other solid state devices to be connected
    • H01L2924/102—Material of the semiconductor or solid state bodies
    • H01L2924/1025—Semiconducting materials
    • H01L2924/1026—Compound semiconductors
    • H01L2924/1032—III-V
    • H01L2924/1033—Gallium nitride [GaN]
    • 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
    • H01L2924/10—Details of semiconductor or other solid state devices to be connected
    • H01L2924/11—Device type
    • H01L2924/12—Passive devices, e.g. 2 terminal devices
    • H01L2924/1204—Optical Diode
    • H01L2924/12041—LED
    • 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
    • H01L2924/10—Details of semiconductor or other solid state devices to be connected
    • H01L2924/11—Device type
    • H01L2924/14—Integrated circuits
    • 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
    • H01L2924/19—Details of hybrid assemblies other than the semiconductor or other solid state devices to be connected
    • H01L2924/1901—Structure
    • H01L2924/1904—Component type
    • H01L2924/19041—Component type being a capacitor
    • 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
    • H01L2924/19—Details of hybrid assemblies other than the semiconductor or other solid state devices to be connected
    • H01L2924/1901—Structure
    • H01L2924/1904—Component type
    • H01L2924/19043—Component type being a resistor
    • 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
    • H01L2924/30—Technical effects
    • H01L2924/301—Electrical effects
    • H01L2924/3025—Electromagnetic shielding
    • 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
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/11—Treatments characterised by their effect, e.g. heating, cooling, roughening
    • H05K2203/1126—Firing, i.e. heating a powder or paste above the melting temperature of at least one of its constituents
    • 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
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/11—Treatments characterised by their effect, e.g. heating, cooling, roughening
    • H05K2203/1131—Sintering, i.e. fusing of metal particles to achieve or improve electrical conductivity
    • 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
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/14—Related to the order of processing steps
    • H05K2203/1453—Applying the circuit pattern before another process, e.g. before filling of vias with conductive paste, before making printed resistors
    • 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
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
    • H05K3/341—Surface mounted components

Definitions

  • the present invention generally relates to materials used for interconnecting electronic devices and, particularly, devices which either generate high temperatures during use or devices which are used in high temperature applications. Furthermore, the invention is generally related to a fabrication method which reduces or eliminates the need for high pressure application during fabrication of an interconnection, such as during die attach.
  • All semiconductor chips have to be fastened or attached to a substrate to function in an electronic product.
  • the state-of-the-art technology for interconnecting these chips typically uses a lead or lead-free solder alloy, or a conductive polymeric glue, such as an epoxy.
  • solder alloys or a conductive polymeric glue, such as an epoxy.
  • conductive polymeric glue such as an epoxy.
  • these materials have poor thermal properties and do not dissipate the heat generated by the chips. They also have poor electrical properties and fail to effectively reduce loss of electrical power, and poor robustness for mechanical strength and reliability.
  • these materials may not be generally suitable for allowing some chips, such as SiC or GaN chips, to function at high temperatures.
  • VTIP 03.142 Sintering of microscale metal powder paste is commonly used in hybrid electronic packages for producing electrical circuit patterns.
  • the high processing temperatures >600°C
  • the current practice is to use solder that is reflowed at temperatures low enough for the devices to withstand.
  • the advantage of low melting temperatures becomes a liability for solder alloys because they cannot meet the requirements of high temperature operation or use in high temperature applications.
  • solder materials have relatively poor electrical and thermal properties, and poor fatigue resistance, compared to other metals such as copper and silver, which detrimentally affect the performance of the whole electronic system.
  • the nanopowder of the present invention can be prepared using known techniques, or purchased directly at a price comparable to that that of micron-size powder.
  • a dispersa ⁇ t is preferably used for reducing agglomeration of the particles which could lead to undesirable/low silver particle loading during mixing of the paste.
  • the nanopowder of the present invention preferably together with the dispersant, can be combined with a polymer binder that preferably has a volatilization temperature below the desired sintering temperature.
  • a binder that preferably does not volatilize until close to the sintering temperature for the metal or metal alloy powder assists in achieving denser interconnections since sintering occurs more uniformly throughout the composition (i.e., the binder is preferably chosen and formulated into
  • compositions of the present invention have a wide range of applications. For example, they can be used to bond silicon integrated circuit chips in computers, or silicon power chips in power supplies, or optoelectronic chips in telecommunications modules. Also, in the case of silver powder, and silver alloys, where the metal melts at temperatures over 700°C or 800°C, the invention is suitable for attaching semiconductor chips that can be operated at high temperatures, e.g., SiC or GaN power chips.
  • a dense, conductive metal interconnection is achieved that can be operated at high temperatures without risking melting of the interconnect, as would be the case with commercial lead and lead free solders as well as conductive epoxies.
  • the ability to allow these chips to operate at a high temperatures cuts down their cooling requirement, leading to savings in materials and energy in the manufacture and operations of the product.
  • the nanosilver paste of this invention due to its high melting temperature and low processing temperature, is also useful for applications other than the attachment of silicon devices and heatsinks. It may be used to attach/interconnect wide bandgap devices that need to operate at elevated temperature such as SiC, GaN and diamond. It is also useful for attaching devices that generate substantial amounts of heat such as light- emitting diodes (LED) and semiconductor lasers.
  • LED light- emitting diodes
  • Figure 1 is a schematic view of metal particles (e.g., nanosilver particles formed as a paste utilizing dispersants to prevent agglomeration and binder to prevent paste cracking during handling and dry processing);
  • Figure 2 is a schematic view showing an exemplary two step procedure for formulating a nano scale metal particle paste for use in the present invention;
  • Figure 3 is a schematic view showing the use of metal paste I according to the invention for attachment of devices to a substrate;
  • Figures 4a-c are graphs showing a comparison of the relative electrical conductivity, relative thermal conductivity, and elastic modulus, respectively, of a various prior art interconnect materials and the interconnect material of the present invention;
  • Figures 5a-b are SEM images of the nanoscale silver paste of the present invention and the commercial silver paste (Heraeus C1075) that has micrometer-sized silver, respectively after the pastes are sintered at 300°C for ten minutes
  • the metal powder in the nanoscale metal paste has a particle size less than 500 nm, and most preferably, the particle size is less than 100 nm (e.g., 1-100 nm or 1-60 nm, etc.).
  • the preferred metal or metal alloy within the practice of this invention is a silver or silver alloy. This is because of a combination of low cost, as compared to gold, and the amenability of being fired in ordinary atmosphere.
  • Nanosilver powder e.g., less than 500 or 100 nm in particle size
  • Suitable nanosilver powder is commercially available from various suppliers in various sizes at a cost of roughly $l/gram. Exemplary commercial suppliers include Nanostructured & Amorphous Materials, Inc., Inframat Advanced Materials, Inc., Sumitomo electric U.S.A., Inc., and Kemco International Associates. Nanosilver powder has been used in a variety of applications. For example, silver can be used as an antibacterial additive to fabric products such as carpets, napkins and surgical masks.
  • Silver has been medically proven to kill a wide range of disease causing organisms in the body and is also relatively safe. For this reason, numerous vendors tout the use of silver colloid for attacking bacterial organisms in the body. Samsung also uses silver nanoparticles to enhance food preservation in its refrigerator product lines. Silver nanopowder is also being used as an additive in consumer products such as toothpaste, toothbrush, and soap, as
  • Nanosilver particles are also used as a coloring additive in paints, glass, ink, and cosmetics. Suitable nanosilver pastes having application in the present invention may also be produced using a modified Carey Lea method. The Carey Lea method was first applied to making photographic emulsions.
  • a modified process can be used to synthesize nanosilver particles (see, for example, S. M. Heard, F. Grieser, C. G. Barraclough and J. V. Sanders, J. Colloid Interface Sci. 93 (2): 545-555 1983; and F. C. Meldrum, N. A. Kotov, and J. H. Fendler, "Utilization of surfactant-stabilized colloidal silver nanocraystallites in the constructruction of mono- and multiparticulate Langmuir-Boldgett films", Langmuir 10(7): 2035-2040, 1994).
  • a reducing agent is prepared by mixing solutions of sodium citrate and ferrous sulfate.
  • VTIP 03.142 raising the firing temperature of the paste and melting point of the alloy, which could be necessary in some cases.
  • a small amount of the palladium (Pd) could be added to silver to prevent the silver migration.
  • Au can also be added to form a gold-silver alloy with still considerably high melting temperature.
  • Adhesion/bonding to the die and substrate can be enhanced with the addition of small amounts of a lower-melting temperature (metal such as indium. If present in small amounts, the operating temperature will still be higher than high-temperature solder such as eutectic AuSn, yet can be processed at comparable temperature.
  • Techniques that make use of the presence of indium in the bonding layer have been developed to form high-temperature joints but typically require long processing times (see, for example, R. W.
  • the nanosilver particles 10 are preferably used in a paste which includes a dispersant 12 to disperse the silver particles 10 and prevent agglomeration, a binder 14 to prevent paste cracking during the handling and dry processing, and, in some instances, a thinner 16 to adjust the paste viscosity to allow for screen or stencil printing (the current practice of applying paste to substrates).
  • a wide variety of dispersants 12 can be used in the practice of the invention including fatty acids, fish oils, poly(diallyldimethyl ammonium chloride)(PDDA), polyacrylic acid (PAA), polystyrene sulfonate (PSS), etc.
  • PDDA poly(diallyldimethyl ammonium chloride)
  • PAA polyacrylic acid
  • PSS polystyrene sulfonate
  • the dispersant 12 can associate a polar head group with the surface of a nanosilver particle 10 by hydrogen bonding or other means, and the hydrophobic tail serves to space adjacent particles apart from one another and prevent agglomeration. Agglomeration leads to low solid loading and ultimately interconnections of poor electrical, thermal or mechanical properties.
  • the preferred binder 14 may be a low boiling organic, such as terpineol (bp of 220°C) that enables unhindered densification of the powder at up to 300°C.
  • suitable binders 14 include, for example, polyvinyl alcohol (PVA), polyvinyl butyral (PVB), and wax.
  • PVA polyvinyl alcohol
  • PVB polyvinyl butyral
  • the properties of the binder 14 e.g., volatilization temperature
  • the binder 14 need to match the sintering kinetics of the nanopowder (i.e., the binder must boil, vaporize, or otherwise decompose below the sintering temperature) and the temperature limitations imposed by the device being attached.
  • judicious selection of or, formulation of binder 14 can be used to assure more uniform sintering of the particles.
  • a thinner 16 such as RV 912 from Heraus, Inc. may be added.
  • terpineol may be used as the thinner 16.
  • the choice of thinner is wide ranging, and will depend on the needs of the fabricator, the choice of materials, and other factors. Suitable thinners may include Haraeus HVS 100, texanol, terpineol, Heraeus RV-372, Heraeus RV-507, etc.
  • FIG. 1 shows a two step procedure for formulating a nano-scale metal paste which may be used in the present invention.
  • Commercially obtained metal particles 20, of a size less than 500 nm and most preferably less than 100 nm in diameter, are combined with a fish oil or other suitable dispersant 22 that has been dissolved in acetone 24. This yields a free flowing powder (non-agglomerated) 26 of particles that have dispersant associated on their surfaces.
  • the powder 26 is combined with a solution 27 which includes binder 28 dispersed or dissolved in a carrier such as a
  • VTIP 03.142 thinner which ultimately yields a paste 30 that includes the metal particles dispersed in the binder material.
  • Dispersion of the metal particles can be aided by immersion in an ultrasonic bath using a room temperature or cold water bath to prevent heating and sintering of the metal powder. Additionally, mechanical mechanisms for stirring, vibrating, etc., can be used to assist in dispersing the metal particles in the binder. In the process shown in Figure 2, excess acetone can significantly aid in a fatty acid dispersant dispersing silver particles during ultrasonic treatment. Further, the nonpolar acetone is easily separated from a mixture of silver plus fatty acid without a centrifuge.
  • Figure 2 has the advantage of making control of paste quality easier since the particle dispersing step is separate from the paste quality adjustment. While Figure 2 illustrates the dissolved dispersant being combined with the metal particles, it should be understood that the particles made by the Carey Lea method described above may have citrate moieties hydrogen bonded to the surface, and the citrate may serve as a dispersant. Alternatively, the citrate moieties may be displaced by a longer chain fatty acid or fish oil dispersant in a manner similar to that shown in Figure 2.
  • Figure 3 illustrates an exemplary process for attaching electronic components to substrates in the practice of the invention. Initially, a nanoscale silver powder 32 is combined with polymers 34 to form a nanoscale silver paste 36.
  • nanoscale silver powder 32 can be converted to a paste 36 form by the addition of an organic solvent with a low boiling point (e.g., terpineol) and thinner (e.g., RV 912 from Heraeus).
  • Electronic devices 38 such as silicon or wide bandgap devices, can be joined to substrates 40 by sintering the nanopowder paste 36 to form a solid bond layer between the devices 38 and mounting substrate 40.
  • the process shown in Figure 3 may be employed with silver particles, silver alloys, as well as other metals and metal alloys.
  • VTIP 03.142 Gold and silver plating can be used to improve the interconnection in the practice of this invention.
  • a thin coating of gold or silver can be applied to the bonding site and/or contacts on the device (not shown) prior to screening, stenciling or printing the nanoscale silver past 36. Utilizing a coating of silver or gold will not pose a significant deviation from current practices since the copper substrates in the current commercially available high-performance electronic packages usually are gold coated already.
  • the methodology of joining electrical devices 38 to substrates 40 is similar to conventional metal paste firing techniques such as those performed for hybrid electronic packages.
  • the firing temperature due to the size of the metal particles (nano scale (preferably less than 100 nm in diameter) as opposed to micrometer sized), is preferably comparable to solder reflow, and, if required, only a moderate applied force may be necessary to maintain intimate contact with the sintering metal powder layer.
  • the nanoscale metal paste is typically screen or stencil printed on the substrate in the form of a thick film (e.g., 20 to 100 micrometers thick) pattern onto which the device is mounted. After device placement, the die may be pushed down with a moderate force and held in place while sintering takes place.
  • the sintering time and temperature will vary. In many applications, the sintering temperature will be at least 250°C and the duration will generally be 2 minutes or longer. Sintering can be carried out in a conventional belt oven in a semi-continuous operation or in a box oven/furnace in a batch type operation.
  • Figure 3 shows the electrical devices 38 mechanically affixed to the substrate 40 in electrical contact with traces or other contacts after the low temperature sintering operation.
  • VTIP 03.142 process is a dense, conductive metal which can operate at temperatures that are much higher than those used for sintering (e.g., on the order of 600°C, 700°C or 900°C or more).
  • Nanoscale silver paste versus micrometer-size silver paste compares favorably with other known interconnect materials such as solder and silver-filled conductive epoxy.
  • Eutectic Pb-Sn solder is used in the vast majority of interconnections although lead-free alternatives are gaining ground.
  • the eutectic AuSn is often recommended because they can go to higher temperatures than Pb-based or Sn-based solders.
  • LED light emitting diodes
  • Silver-filled conductive epoxies are currently used for silicon device interconnect applications.
  • conductive epoxy is used in International Rectifier's DirectFETTM to secure the silicon dice to a copper cavity. The properties of these materials are listed in Table 1 and some are also shown in Figures 4a-c.
  • VTIP 03.142 Table 1 Property comparison of some common interconnect materials with the sintered nanosilver paste of the present invention.
  • Nanoscale silver as used in the practice of the present invention instead of micron-size silver is primarily to lower the sintering temperature to the processing range of most solders. This allows it to be used as a drop-in replacement for these interconnect materials.
  • the sintering temperature is sensitive to the size and morphology of the particles. Silver, which has a very high diffusion rate, is particularly attractive because it can be sintered at well below its melting temperature (962°C) if the particle size is made small enough.
  • Current silver paste materials must be fired to above 600°C to obtain reasonable strength and density. The prescribed firing schedule is usually to take the paste to around 900°C to density it.
  • VTIP 03.142 invention where the silver particle is less than 100 nm in size, it can undergo densification starting at as low as 100°C (although this is not the desirable temperature range).
  • the onset of sintering can be delayed until such time that the preferred firing temperature is reached ( ⁇ 280 to 300°C) to enable very fast densification rates and attain not only high density, but also good adhesion onto the device and substrate. Therefore, in addition to the reduction in particle size, an important ingredient to the usability of the paste is the selection of the dispersant and binder system that can be volatilized and burned off just below the sintering temperature.
  • the binder system leaves the paste too early, the silver nanoparticles will start sintering at a lower temperature, and consequently with reduced kinetics, the activation of a non-densifying mechanism, e.g. surface diffusion, occurs resulting in a microstructure that is difficult to density even at the higher targeted sintering temperature. If the binder system components burn off at a temperature higher than the desired firing temperature, the silver particles will not sinter properly because the polymer components will prevent the widespread contact between particles.
  • a non-densifying mechanism e.g. surface diffusion
  • FIGS. 4a-b show that the nano-silver pastes of the present invention provide superior relative electrical conductivity and thermal conductivity compared to eutectic PbSn, eutectic AuSn, and conductive epoxy.
  • Figure 4c shows that the elastic modulus of the sinter nano-silver paste is satisfactory for interconnect applications.
  • Figures 5a and 5b are SEM images of silver pastes sintered at
  • Figure 5a shows an SEM image of a sintered nanoscale silver paste according to the present invention
  • Figure 5b shows an SEM image of a sintered commercially available silver paste which includes micrometer sized silver (Heraeus C1075)
  • Figure 5a shows that a relatively high density (approximately 80%) results from sintering a nanoscale silver paste at 300°C for ten minutes, which is about two times the green density (silver powder loading only before sintering; organics are not included).
  • Figure 5b shows that the commercial paste with the micrometer sized silver fired under the same condition. However, the microstructure is very porous, and there is minimal densification.
  • Figure 6 presents a graph obtained from the web site of a commercial supplier of silver powder (see Ferro's web site) which presents the shrinkage of silver powder of various sizes with increasing temperature. The data in this graph, along with the experiments presented herein, demonstrate that the nanoscale silver paste of the present invention can be sintered at lower temperatures with decreasing size.
  • solders are currently used for high-temperature semiconductor device interconnect applications.
  • eutectic Au80Sn20 solder can be reflowed at 310-330°C and used at a temperature below its melting point 280°C.
  • the major differences between the solder reflow and the nanoscale silver paste sintering of the present invention include: 1) Solder is processed by heating the alloy above its melting temperature to form the bond. The alloy undergoes melting and solidification after the
  • VTIP 03.142 completion of the procedure known as solder reflow.
  • the requirement to melt the alloy means that only those with low melting points are suitable. This restriction also limits the maximum operating temperature of the joint to below the melting point.
  • Conductive epoxy is hardened by curing above room temperature to induce the epoxy to undergo a setting reaction. While the process temperature is low and no melting is involved, the maximum working temperature is limited by the decomposition temperature of the epoxy component, which is in the range of the curing temperature.
  • the sintering temperature of silver can be drastically reduced if micrometer-size particles are replaced by ' nanoscale particles. It is then possible to lower the sintering temperature to that of the reflow temperature of many solder alloys.
  • VTIP 03.142 to be fired to a high temperature approaching the melting point of the alloy to achieve high density.
  • the recommended firing profile of silver paste is to heat it to around 900°C (although it is possible to obtain reasonably high density for mechanical strength at lower temperatures, e.g. 700°C). They are most often used to form conductive traces/patterns (package substrates) and electrodes (capacitors) for various electronics applications. They are not typically used for forming interconnects between devices and substrates, as is proposed in the present application. There are numerous vendors for these products such as DuPont, Heraeus, and Ferro. Silver paste has also been considered as a die-attach and interconnect material.
  • VTIP 03.142 increases on some key parameter values of the sintered Ag joint such as electrical conductivity, thermal conductivity and shear strength.
  • the nanoscale silver paste of this invention (less than 500 nm and more preferably less than 100 nm in size)
  • the pressure used before the silver sintering with the silver paste of the present invention may be used only for better initial interface contacts, and it is recommended that this pressure not exceed O.lMpa so that the silver paste does not get squeezed out (this procedure is very common on solder reflow die-attaching).
  • Table 2 Effect of pressure on the properties of sintered silver paste with micrometer-size silver. The astes were fired at 240°C for 5 min.
  • VTIP 03.142 nanosilver paste as discussed above, this can be achieved by substituting the binder system components with alternatives that burn out at higher temperatures to closely match the desired or target peak processing temperature (e.g., the binder system might be chosen to vaporize or otherwise decompose at a temperature that is the same as or slightly below (e.g., within 50°C or 30°C or 10°C) the sintering temperature for the metal or metal alloy particles.
  • the peak processing temperature need not be limited to 300°C or below.
  • silicon carbide may be attached at temperatures as high as 600°C using gold or its alloy(s) but with contact pad problems when fired in air.
  • the present technique can be used to make a paste that can be fired at a higher temperature to attain higher density and stronger bonding (but still lower than 600°C since it is desired to retain the nanosilver particles until the sintering temperature).
  • An illustrative example of this technique is shown in Figures 7a-7b where a nanosilver paste containing 100 nm particles and fatty acids of different carbon chain lengths (hence different burnout temperatures) was sintered at 450°C.
  • the fired paste in Figure 7a had a significantly denser microstructure than that of the paste in Figure 7b.

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Abstract

Cette invention concerne une pâte contenant des particules de métal ou d'alliage métallique (de préférence d'argent ou d'alliage d'argent), un matériau dispersant et un liant et utilisée pour former une interconnexion électrique, mécanique ou thermique entre un dispositif et un substrat. Le fait d'utiliser des particules nanométriques (autrement dit des particules dont la taille est inférieure à 500 nm et mieux encore inférieure à 100 nm) permet de fritter les particules de métal ou d'alliage métallique à basse température afin qu'une couche de métal ou d'alliage métallique soit formée, laquelle est densifiée afin qu'on obtienne une bonne liaison électrique, thermique et mécanique, la couche de métal ou d'alliage métallique pouvant par ailleurs être utilisée à haute température, ce qui est notamment souhaitable pour le SiC, le GaN ou le diamant (par exemple dans des dispositifs à large structure de bande). En outre, il n'est pas nécessaire d'appliquer une forte pression pour former les couches densifiées, contrairement aux applications utilisant des particules dont le diamètre est de l'ordre du micromètre. Le liant peut par ailleurs être modifié de façon que les particules de métal soient isolées jusqu'à ce qu'une température de frittage désirée soit atteinte, ce qui permet d'effectuer un frittage rapide et complet.
EP05723019A 2004-02-18 2005-02-14 Pate metallique nanometrique pour interconnexion et procede d'utilisation Withdrawn EP1716578A4 (fr)

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WO2005079353A2 (fr) 2005-09-01
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WO2005079353A3 (fr) 2005-12-08
CN1961381A (zh) 2007-05-09

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