WO1999034970A1 - Ceramic composites with improved interfacial properties and methods to make such composites - Google Patents

Ceramic composites with improved interfacial properties and methods to make such composites Download PDF

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Publication number
WO1999034970A1
WO1999034970A1 PCT/US1999/000441 US9900441W WO9934970A1 WO 1999034970 A1 WO1999034970 A1 WO 1999034970A1 US 9900441 W US9900441 W US 9900441W WO 9934970 A1 WO9934970 A1 WO 9934970A1
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WIPO (PCT)
Prior art keywords
ceramic
metal
substrate
composite
oxide
Prior art date
Application number
PCT/US1999/000441
Other languages
French (fr)
Inventor
L. Pierre doing business as C?2¿ TECHNOLOGIES deROCHEMONT
Peter H. Farmer
Original Assignee
Derochemont L Pierre Doing Bus
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Publication date
Application filed by Derochemont L Pierre Doing Bus filed Critical Derochemont L Pierre Doing Bus
Publication of WO1999034970A1 publication Critical patent/WO1999034970A1/en

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    • 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
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
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    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/48—Manufacture or treatment of parts, e.g. containers, prior to assembly of the devices, using processes not provided for in a single one of the subgroups H01L21/06 - H01L21/326
    • H01L21/4803—Insulating or insulated parts, e.g. mountings, containers, diamond heatsinks
    • H01L21/4807—Ceramic parts
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    • H01L23/14—Mountings, e.g. non-detachable insulating substrates characterised by the material or its electrical properties
    • H01L23/142—Metallic substrates having insulating layers
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    • H01L23/373—Cooling facilitated by selection of materials for the device or materials for thermal expansion adaptation, e.g. carbon
    • H01L23/3735—Laminates or multilayers, e.g. direct bond copper ceramic substrates
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Definitions

  • the present invention relates generally to certain classes of ceramic composites, and, more particularly, to structural an d functional such composites and devices incorporating such composites, including, among others, printed circuit boards and other components
  • Metal-ceramic composites comprising a metallic member bonded to a ceramic member have many useful applications in areas including, but not limited to, electronic circuits, heat shielding components, structurally-reinforced composite sheeting, engine components, electromechanical actuators or micro-positioners, an d electrochemical electrodes.
  • the interface between the metal member and the ceramic member is subject to mechanical stress generated at, or close to, the interface formed between the metal and the ceramic.
  • preferred combinations of metallic composition and ceramic composition that optimize the performance of an ideal metal-ceramic composite often require an interface to be formed between a metallic composition and a ceramic composition that have poorly matched coefficients of thermal expansion.
  • the composite interface is often susceptible to thermal cycling during the operational mode in these applications.
  • Electronic circuits be they microelectronic circuitry contained o r embedded on the surface of a semiconductor chip or an integrated circuit built on a circuit board, generate both heat and electromagnetic field emissions.
  • the more powerful microelectronic circuits used in some of these devices generate significant levels of heat, which can compromise performance efficiency in units lacking efficient thermal management systems.
  • Metal-ceramic composite structures have b een used for thermal management, implemented either as a printed circuit board or as an integral member of an electronic package (both referred to herein as "printed circuit boards"). Mismatch in the linear coefficients of thermal expansion at the interface(s) between th e differing metal and ceramic materials can result in cracking within or delamination of the composite structure, leading to the eventual failure of the thermal management system.
  • the electromagnetic field emissions generated by these devices can disrupt the proper functioning of ne arby electronic equipment and/or be harmful to human safety.
  • electromagnetic radiation emitted from an operating electronic device such as a cellular telephone
  • an operating electronic device such as a cellular telephone
  • Diagnostic testing on cellular telephones has shown that the electromagnetic field emissions of one unit operated in close proximity to another unshielded unit can trigger communications failure.
  • cellular telephones which typically emit electromagnetic radiation at power levels of 600 milliwatts (mW) in close proximity to the human brain, may directly threaten human health if these emissions are actually demonstrated to harm human tissue. It is often advantageous to minimize the size and weight of electronic systems by integrating multifunctional performance into subsystems contained in the total systems package. Methods that can simultaneously protect sensitive electronic systems from disrupting electromagnetic interference or that shield human tissue from harmful electromagnetic emissions and contribute to th e thermal management of electronic systems and/or provide printed circuit board functionality in a reliable manner are, therefore, desirable. Improved interfacial properties between metal and ceramic members can also benefit many other areas, such as in electrochemical processing. Many electrochemical processes must be driven at high temperature.
  • metal- ceramic composite electrodes that simultaneously conduct ions an d electrons because of the ceramic member's higher oxidation- an d corrosion-resistance.
  • Mismatch in the linear expansion of the ceramic member and the metallic member of the electrochemical electrode during thermal cycling will eventually degrade the useful function of the component, since cracks which develop in the ceramic memb er provide a conduit through which corrosive elements can attack th e metal.
  • Metal-ceramic composites also have been contemplated for u se as components in automotive and jet engines. These applications c an subject the composite part to extreme changes in body temperature, as well as sharp temperature differentials across the body of th e composite part itself. Poor interfacial characteristics can limit the performance of the engine part.
  • Interfacial stress at a metal-ceramic interface are not limited to mechanical stresses that are thermally induced through a mismatch in linear-expansion-coefficients.
  • Metal- piezoelectric ceramic interfaces are now widely applied in electromechanical actuators and micro-positioners.
  • the metal member is used as a n electrode to convey a voltage across the piezoelectric ceramic, which, in turn, will expand (or contract) along the ceramic's crystallographic axis that is normal to the plane defining the metal-ceramic interface.
  • the piezoelectric ceramic Concurrent with the longitudinal expansion (contraction) in th e ceramic, the piezoelectric ceramic will simultaneously contract (expand) laterally along crystallographic orientations parallel to the plane defining the metal-ceramic interface.
  • Linear expansions i n high-performance piezoelectric ceramics can be as high as 1 %, which is roughly equivalent to the linear thermal expansion generated by a 1000 °C change in temperature.
  • a composite sheet used as a lightweight structural component comprised of a ceramic sheet member bonded to a metallic sheet member, wherein the ceramic member provides greater structural integrity or rigidity to the metal member, will be subject to a variety of mechanical loads and forces that stress the interface between the ceramic and metallic members.
  • methods that can be widely applied to improve the performance of bulk metal-ceramic composites subjected to extreme linear expansions along at least one interface formed between the metal member and the ceramic member in metal-ceramic composite are, therefore, also desirable.
  • a metal - ceramic (preferrably oxide ceramic) composite such that the ceramic member contains a compositional gradient, and a corresponding gradient in its coefficient-of-thermal-expansion, that reduces shear stress in the ceramic member when the metal-ceramic composite is subjected to a thermal load.
  • the method and products of the present invention overcome many of the problems associated with the production of past metal/ceramic components.
  • the examples of the present invention stated below under "Detailed Description of Preferred Embodiments" are provided for illusrative purposes and not to limit the scope of the invention.
  • the invention involves deposition of a metal precursor to a ceramic composition (e.g. ceramic oxide such as Al2 ⁇ 3 ; Ti ⁇ 2 or other single or mixed oxides, borides, carbides, nitrides, suicides) on a metal substrate at a molecular level as a finely divided form of highly adherent metalorganic compounds followed by pyrolysis.
  • the overall process is conducted at low temperature and involves the method of metalorganic chemical spray pyrolysis.
  • metal precursors to the ceramic oxide composition are introduced as metalorganic salt complexes, (i.e., metal complexes having organic ligands), into an organic solvent. Together they form the metalorganic precursor solution.
  • metalorganic salt complexes i.e., metal complexes having organic ligands
  • High molecular weight carboxylic acid salts such as 2-ethylhexanoates, or naphthenates, are the preferred metalorganic species using the process.
  • the various ceramic precursors are mixed at the molecular level and thus, in minutes, achieve a state of ultrafine subdivision that typically is only achieved after calcining a slurry of powder precursors for m any hours.
  • Ceramic precursors are generally introduced into th e metalorganic solution in concentrations in the range between 0.05% and 25% equivalent-weight oxide (eq.-wt%), although precursor concentrations in the range of 1% and 20% eq.-wt% are preferred.
  • the spray conditions can be adjusted for compositional (and physical property) uniformity throughout the thickness of the eventual ceramic layer or for graded or otherwise differentiated composition an d properties, e.g. graded coefficient of thermal expansion.
  • This state of ultrafine subdivision (wherein precursors have been mixed at the molecular level) among the precursors is retained when the metalorganic solution is nebulized into an aerosol mist and deposited as a ceramic oxide (or the like) on the surface of a heated substrate.
  • the substrate surface must be heated to a temperature that is greater than the boiling point of the organic solvent, which evaporates during ceramic deposition, and at least greater than th e decomposition temperature of the organic ligand that is most sensitive to thermal decomposition and contained in the metalorganic salt complex that, too, is most sensitive to thermal decomposition.
  • the substrate prefferably heats to a temperature that is at least equivalent to the decomposition temperature of the organic ligand which is most sensitive to thermal decomposition and contained in the metalorganic complex which is least sensitive to thermal decomposition.
  • Carboxylic acid salt precursors are preferred because of their low volatility.
  • Carboxylic acids typically form waxy solids th at will thermally decompose rather than evaporate.
  • th e metalorganic precursors decompose into highly energetic metal radicals that rapidly seek to form covalent bonds with an unbound electron.
  • Heated substrate surfaces comprise a sheet of dangling bonds that are also excited to form a lower energy bond with th e metal radicals of the decomposing metalorganic salt complex.
  • Metalorganic salt complexes typically decompose over a temperature range of 250-450° C. This process thus allows a covalent bond to b e formed between the deposited ceramic material and a heated metal member at a low temperature in the range of 250-450° C.
  • the deposited ceramic retains the state of ultrafine subdivision achieved in the metalorganic solution because the rapid pyrolysis of th e precursor droplet, cooled by adiabatic expansion during aerosol nebulization, occurs at such a high rate that the mixed precursors h ave little or no time to segregate and sequentially decompose as individual metal oxide species.
  • the ceramic deposited on the heated metal substrate is initially porous and comprised of a solid solution with randomly oriented crystalline structure.
  • the deposited ceramic member can be brought into a physical state comprised of highly oriented and densely packed crystalline grain structure using multiple short duration sequential reaction and mechanical pressurization processing steps.
  • the density of ceramic so-processed can achieve levels approaching 97% an d preferrably, for many applications over 99% of theoretical density.
  • one aspect of the present invention provides for th e dispersion of secondary phase material particles in a ceramic medi um in order to increase the crack resistance of the ceramic medium.
  • Another feature of the present invention provides for a thermally insulating ceramic member to be deposited on the metal member by spray pyrolyzing a solution of metalorganic precursors and thus permits the composition of the ceramic member to be altered by adjusting the precursor concentration of the metalorganic solution with the thickness of the deposited ceramic.
  • This reduces shear stress in a ceramic member of a thermally loaded metal-ceramic composite by introducing, as stated above, a composition profile in the ceramic member bonded to the metal member in order to produce a gradient in the coefficient-of-thermal-expansion within the ceramic member i n a manner that reduces shear stress in the ceramic member.
  • the present invention by virtue of being a low-temperature manufacturing process, also represents a further improvement over the prior art because it allows a far greater selection of constraining metal members than the prior art. Further, the ability to form a covalent bond between the deposited ceramic member and th e metallic substrate without a molten bonding agent or adhesive, as is enabled under the present invention, permits even greater improvement over the prior art by introducing stress-reducing micro- mechanical elements to the ceramic layer throughout in the thickness and/or near the metal-ceramic interface, such elements substantially retaining their compositional and physical integrity.
  • metal-ceramic composites of this invention relate to the use of the metal-ceramic composites as a metal-ceramic composite substrate for printed circuit boards.
  • high conductivity metal-alumina-high conductivity metal such as copper-alumina-copper structures, with improved crack-resistance and interfacial properties are produced by depositing an alumina-based ceramic on the high conductivity metal member .
  • the surface texture of one or both the ceramic-faces of metal-ceramic composites bonded together ceramic-face to ceramic-face can become grossly undulated. This is particularly true with hard ceramic compositions, such as alumina ceramic.
  • the excessive surface roughness may create problems when forming the low-melting temperature oxide bond, or cause the ceramic member sandwiched between the metal members and/or the final composite to have unacceptably non- uniform thickness.
  • FIG. 1 is a cross-sectional representation of a metal-ceramic composite printed circuit board as found in the prior art
  • FIG. 2. represents a cross-sectional view of a typical fracture pattern for a metal-ceramic composite interface that has b een thermally overstressed in a typical printed circuit board as shown i n FIG. 1 ;
  • FIG. 3 represents a cross-sectional view of a metal-ceramic composite of the preferred embodiments of the present invention wherein particles of at least one secondary phase material are dispersed in the composite's ceramic member to impede crack propagation and increase crack-resistance;
  • FIG. 4 represents a schematic cross-sectional view of th e coefficient of thermal expansion within a ceramic member
  • FIGS. 5 (a), (b) and (c) depict various positions of a constaining metal member within the composite of an embodiment of the present invemtion
  • FIG. 6 (a) is a cross sectional view of a metal ceramic structure
  • FIGS. 6 (b) and 6 (c) represent a model that visually simulates the thermal deformation in a metal-ceramic composite substrate printed circuit board and compares thermal deformation in the composite when the mounting area contains a molybdenum constraining-metal member to the thermal deformation in the composite when th e mounting area contains a titanium constraining-metal member.
  • FIGS. 7 (a)-(d) depict cross-sectional views of the construction of a metal-ceramic composite in which adhesion-resistant bodies are placed on a metal member substrate (a), or coated with an epoxy resin before being attached to the metal member substrate (b), a ceramic member is deposited on both the adhesion-resistant bodies and th e metal member substrate (c), and the resin epoxy is finally removed (d);
  • FIGS. 8 (a) and (b) show the top perspective of various shapes an d forms for adhesion-resistant bodies;
  • FIG. 10 shows the characteristic stress-reduction versus the depth of micro-mechanical struts formed in the ceramic member at various distances from the metal-ceramic interface;
  • FIG. 1 1 shows the characteristic stress-reduction versus the width of micro-mechanical struts formed in the ceramic member at various distances from the metal-ceramic interface
  • FIG. 12 represents a cross-sectional view of a ceramic composite of the present invention wherein particles of at least one secondary phase material are dispersed in the composite's ceramic member to impede crack propagation and increase crack-resistance;
  • FIG. 13 represents a schematic cross-sectional view of th e coefficient of thermal expansion within a ceramic member;
  • FIGS. 14 (a)-(d) depict cross-sectional views of the construction of a ceramic composite in which adhesion-resistant bodies are placed o n a substrate (a), or coated with an epoxy resin before being attached to the substrate (b), a ceramic member is deposited on both th e adhesion-resistant bodies and the substrate (c), and the resin epoxy is finally removed (d);
  • FIGS. 15 (a) and (b) depict various parameters that define a micro-mechanical strut at a ceramic oxide interface (a) and the flexure the micro-mechanical struts provide to the ceramic at the interface (b);
  • FIGS. 16 and 17(a) and (b) depict metal-ceramic composite substrates for printed circuit applications.
  • FIGS. 18(a) and (b) and 19 depict metal-ceramic composites with a ferrite ceramic attached to one major surface of the structure.
  • the term "ultrafine subdivision” is understood to represent a ceramic whose precursors have been mixed at the molecular level, a s in a solution, as opposed to a ceramic whose precursors were mixed a s particulates with a definitive particle size, as in a slurry.
  • the te rm "secondary phase material” is understood to represent a compositional state of matter dispersed in a ceramic deposited or formed on a metal member, such that the "secondary phase material” is characterized b y an elemental composition, material phase, or crystallographic structure that is different from the deposited ceramic into which it is dispersed.
  • the "secondary phase material” may be a single crystalline phase, a ceramic phase, a glass phase, graphite, a metal phase, a shape-memory alloy phase, or any composite form of said material phases that produces a Young's modulus that is less than the Young's modulus of the ceramic medium into the "secondary phase material” has been dispersed.
  • shape-memory alloy is understood to represent a metallic phase or glassy metallic phase that exhibits superior ductile properties under mechanical stress and the ability to return to its initial geometric shape and physical dimensions exhibited in an unstressed state after the application of said mechanical stress has been relieved.
  • Composite bodies that comprise a ceramic member contacted to a metallic member can significantly improve the performance of a conventional non-composite part over a wide range of applications. I n practice, however, unless special measures are taken to engineer a proper interface between the ceramic member and the metal member, the functionality of the composite bodies can be extremely limited a s the intended applications often subject the composite bodies to thermal loads or mechanical stress that cause the metal and ceramic members to become mutually incompatible in a single composite body .
  • Metals and ceramics are essentially characterized by starkly different chemical, mechanical and thermal properties. Metals are, typically, characterized by ductile properties that permit them to elastically flex and accommodate a higher degree of mechanical stress prior to reaching a point inelastic fracture.
  • Ceramics typically, exhibit thermal conductivities that are superior to those common to most ceramics. Ceramics, typically, are characterized by rigid mechanical properties that allow them to resist flexure, however, this brittle nature can make the ceramic more susceptible to inelastic fracture u nder equivalent mechanical loads.
  • a composite body comprised of a metal member bonded to a ceramic member can blend the superior properties of each member to improve device performance in a variety of applications. The ultimate performance in such a composite body will, in m an y instances, be determined by stresses generated at, or close to, the interface between the ceramic member and the metallic member, where the disparate thermal and mechanical properties of one member will oppose the other member's natural response to a n applied thermal or mechanical load beyond its natural ability to do so.
  • A represents the area of the subscripted member.
  • printed circuit boards for high power semiconductor integrated circuits generally comprise a metal- ceramic composite susbtrate consisting of a low-cost, high thermal conductivity, high electrical conductivity metal sheet 1A bonded to a low-cost, low-dielectric constant, low thermal conductivity ceramic 2 on one major surface of the ceramic, with another low-cost, high thermal conductivity, high electrical conductivity metal sheet I B bonded to the ceramic's opposing major surface.
  • the metal sheet 1A will be etched to form a network of mounting areas IC, onto which semiconductor integrated circuits 3 are mounted, and electrode areas ID, that are used to transport electrical signals across the surface of the printed circuit board.
  • Aluminum wire 4 is ultrasonically bonded between the SIC 3 and the electrode area ID to electrically connect the semiconductor chip to the electrode network on the surface of the printed circuit board.
  • Prior art has typically used aluminum oxide (alumina) as th e ceramic member 2 and copper as the metal sheets 1A and IB, although it is possible to use other metals and ceramics, such as non- oxide ceramics, to form the printed circuit board structures.
  • Equation (1) it is straightforward to determine that approximately 2 megapascals (MPa) of stress will b e generated for each degree of rise and fall in temperature at th e interface formed when alumina ceramic is directly bonded to copper metal.
  • FIG. 2 shows a fracture pattern that is typical of an over-stressed interface, comprising cracks 5 in the ceramic member 6 that is bonded to th e metal member 7.
  • Semiconductor integrated circuits are generally required to operate reliably over temperatures ranging from -40 °C to 150 °C. It is, therefore, essential that the metal-ceramic composite, when used as a printed circuit board substrate on which SIC's are mounted, have reliable function over an identical range of temperatures. Simple metal-ceramic composite structures, wherein metals having a coefficient-of-thermal-expansion comparable to th at of copper are directly bonded to the ceramic member are not sufficient to satisfy these requirements.
  • Tanaka et al. disclose, in U.S. Patents Nos. 4,959,507 and 4,987,677, that the unit failure rate of metal-ceramic composite substrate circuit boards, wherein the composite substrate circuit boards comprise copper sheets bonded through the eutectic bonding process to the opposing major surfaces of a ceramic member, can be reduced if surface roughness of the copper sheet of the metal-ceramic composite onto which electronic circuits are mounted has a median surface roughness not greater than 3 microns and a maximum surface roughness not greater than 18 microns.
  • Aluminum wire that is ultrasonically bonded to copper sheets with a Vickers hardness less than 4 0 Kg/mm ⁇ is prone to rupture in the vicinity of the bond, as th e ultrasonic energy used in the bonding process is sufficient to bury th e wire into the soft copper sheet and catastrophically elongate th e aluminum wire.
  • An ultrasonic bond formed between aluminum wire and a copper sheet with a Vickers hardness greater than 100 Kg/mm 2 frequently has poor adhesion as the ultrasonic wave is attenuated i n the hard copper sheet.
  • Metal-ceramic composite substrates that have copper mounting areas with a Vickers hardness in the range between 60 Kg/mm ⁇ to 80 Kg/mm ⁇ are preferred in printed circuit bo ard applications.
  • Interfacial stress at a metal-ceramic composite interface can b e reduced if the metal member bonded to the interface contains a constraining-metal member which acts to restrain the linear thermal expansion of the metal member.
  • Kashiba et al describes in U.S. Patent Nos. 5, 153,077 and 5,251 ,803 the use of a constraining-metal memb er integrally-bonded into a metal-ceramic composite substrate, wherein the constraining-metal member reduces thermally-generated mechanical stress at the interface between metal and ceramic members in the composite structure, or between the metal layer and a semiconductor integrated circuit mounted on the metal member.
  • the constraining-metal layer must have a higher yield strength than the copper sheet to which it is bonded.
  • Copper has a yield strength of 1 0 Kg/mm ⁇
  • molybdenum a suitable constraining-metal member
  • the ductile copper, restrained by the constraining-metal member, will not crack as its elastic properties absorb the stress generated by linear expansions a t the copper-constraining-metal interface during thermal cycling.
  • the present invention provides methods to improve the thermal and mechanical integrity of metal-ceramic composites that have a t least one interface in which the composite's metal member is directly bonded to the ceramic member. These improvements to the prior ar t relate specifically to the construction methods used to assemble the metal-ceramic composite. Additionally, the present invention improves the interfacial properties and fracture mechanics of metal- ceramic composites by allowing more fracture-resistant forms of alumina ceramic to be assembled into the composite and by adding micro-mechanical features to the bonding surface of the ceramic member in contact with the metal member that increase the flexure of the ceramic member in response to linear expansions or contractions of the metal member. The present invention also introduces methods to control the fracture mechanics of the interface.
  • i t allows the metal-ceramic composite to be formed at much lower processing temperatures.
  • Prior art construction methods utilize pre fabricated ceramic and metal members that are bonded together using processing techniques that subject the metal-ceramic composite to temperatures at least in excess of 900 °C. It is well known to practitioners skilled in the art of heat-treating sheet metal th at prolonged exposure to elevated temperatures close to the melting point of the metal sheet, i.e., within 200 °C of its melting point, will reduce its hardness. The degree to which the hardness is reduced is a function of both the temperature as well as the time period over which the metal sheet is exposed to the elevated temperature . Increasing the time period over which the metal is exposed to a n elevated temperature sufficient to soften the metal will proportionally reduce its hardness.
  • the present invention further improves upon the prior art b y being a low-temperature process and one that can be suitably engineered for continuous production.
  • These processing features not only impact the ease with which metal-ceramic composites can b e produced, they also increase the economy of industrial production.
  • Methods detailed in the prior art represent batch production techniques, in which production units are produced in units of one, or multiples of one depending on batch size. This means all th e component parts to the finished product need to be prepared to unit size prior to assembling the final product. Batch production methods are less efficient because they generally represent multiple processing and quality assurance steps for each of the components during sub - assembly prior to forming the finished good in final assembly. Continuous production methods improve the economy of an industrial process by reducing the number of processing steps and increasing production rate.
  • Metal-ceramic composite substrates for printed circuit board applications are easily assembled by rolling copper sheet into a deposition chamber where a layer of alumina ceramic is spray-pyrolyzed onto its surface to form a sheet comprising a metal layer bonded to a ceramic layer. Two such sheets, or one sheet folded onto itself, are joined through a mechanical swaging step, ceramic face to ceramic face, to form the metal-ceramic- metal composite substrate structure. Finished products are then stamped out of a continuously processed sheet.
  • i t is not necessary to start with excessively hardened copper sheets to achieve metal-ceramic composite substrates in which the copper mounting and electrode areas satisfy hardness tolerances necessary to produce a reliable printed circuit board. Since all the bonding step s utilized under the present invention can be realized at temperatures below 900°C, hardness reduction during subsequent annealing steps is mitigated by lower temperature processing, providing more control over the Vickers hardness of the metal members in the finished composite.
  • An essential feature of the present invention is that it allows a ceramic member to be bonded to any metal member, stainless steel, for example, but not limited thereto, irrespective of metal and ceramic * composition(s), through a covalent bond formed using processing temperatures that can be less than 500°C. More specifically, ceramic oxide is bonded to metal at low-temperature by the method of metalorganic chemical spray pyrolysis. Using this method, metal precursors to the ceramic oxide composition are introduced a s metalorganic salt complexes, (i.e., metal complexes having organic ligands), into an organic solvent. Together, they form the metalorganic precursor solution.
  • a s metalorganic salt complexes i.e., metal complexes having organic ligands
  • a distinguishing characteristic of metal-ceramic composites manufactured using the metalorganic spray pyrolysis process is that a direct rigid bond is formed between the metal and the ceramic members without the use of an adhesive or bonding agent th at comprises a compositional state of matter that is different from th e ceramic and the metal member, such as is the case when a solder material or a eutectic material is used to form the bond.
  • a compositional profile of the metal-ceramic interface is characterized by an abrupt termination of the metal composition and an equally abrupt beginning of the ceramic composition. These interfaces do not contain a formerly liquid phase material that has been solidified into a layer many tens of microns thick to form the bond.
  • this method of forming a "clean " interface now makes it possible to engineer micro-mechanical features bonded to the ceramic, but not to the metal, that enhance the interfacial properties of th e composite body.
  • FIG. 3 One aspect of the present invention, shown in FIG. 3, is th e incorporation of secondary phase material particles dispersed in a ceramic medium.
  • a crack 24 propagating through a brittle ceramic medium 25 that has been generated by stresses at th e interface between the brittle ceramic medium 25 and a metal member 26 will be deflected or have its energy partially absorbed when i t encounters the secondary phase material particles 27 dispersed in the brittle ceramic medium.
  • the secondary phase material particles dispersed throughout a brittle medium increase the crack resistance of the brittle medium.
  • the fracture mechanics of a composite body can also be improved if the composite body is formed in a manner that allows thermally compressive forces to pre- stress the composite body in a manner that opposes, much as is the case wi th a pre-stressed bolt, the thermal and mechanical loads anticipated from an intended application.
  • interfacial stress between a high thermal expansion coefficient metal and a lower thermal expansion coefficient ceramic can be reduced by modifying the Young's modulus of the high thermal expansion coefficient metal. Suitable modifications to the high thermal expansion coefficient metal would include perforating the high thermal expansion coefficient metal or b y making it porous.
  • the present invention allows any, or all, of these improvements now to be incorporated into th e construction of metal-ceramic composite bodies.
  • a metal-ceramic composite with improved interfacial properties according to this invention can be manufactured as follows:
  • the present invention utilizes a method to produce a metal-ceramic composite in which the ceramic member forms a covalent bond with the metal member by the method of metalorganic spray pyrolysis.
  • the ceramic member consists of a primary ceramic medium with ultrafine subdivision that has been formed on the metal member from a spray pyrolyzed metalorganic solution, and th e ceramic member contains a dispersion of previously formed particles of secondary phase materials that increase the crack resistance in th e ceramic member.
  • the particles 27 of secondary phase materials are dispersed in the ceramic medium by forming a colloidal suspension of the secondary phase materials in the metalorganic solution prior to spray pyrolyzing the metalorganic solution containing a colloidal suspension of the secondary phase material particles 27 on the metal member of the metal-ceramic composite.
  • the metalorganic precursors are pyrolyzed into oxide ceramic on the metal member subs trate heated to temperatures typically greater than 250°C, and typically less than 500°C. This range of temperatures is generally insufficient to dissolve the secondary phase material particles 27 into the ceramic medium 25.
  • particles 27 of secondary phase materials dispersed throughout the metalorganic solution become dispersed, a s secondary phase material particles, in the spray pyrolyzed ceramic.
  • I t is a preferred embodiment of this invention to use particulates of secondary phase materials that are characterized as having intrinsic mechanical properties that are less brittle, i.e., has a lower Young's modulus, than the ceramic medium 25 formed around them by th e pyrolyzed metalorganic precursor solution.
  • the secondary phase material particles 27 may comprise a metal or metal alloy, a glass phase, a shape memory alloy, graphite, an oxide or non-oxide material, or a crystalline ceramic or single crystal material phase.
  • This particular aspect of the invention has special significance for alumina-based (Al2 ⁇ 3-based) or titania (Ti ⁇ 2-based) ceramic members on metal substrates.
  • alumina-based (Al2 ⁇ 3-based) or titania (Ti ⁇ 2-based) ceramic members on metal substrates As mentioned above, the prior art instructs on the construction of metal-ceramic composites formed b y bonding a previously formed ceramic member (i.e., a ceramic memb er that already has been sintered, cut, and polished) to metal sheets .
  • Alumina represents one of the most highly refractory oxide ceramics. It liquefies at temperatures above 2054°C, and forms a partial liquid phase suitable for sintering at temperatures above 1828°C.
  • the present invention allows a colloidal suspension of secondary phase material particles to be dispersed throughout a solid solution of ceramic that is spray pyrolyzed around the secondary phase material particles a t temperatures well below 1828 °C.
  • the spray pyrolyzed ceramic m a y be crystallized and textured using a repetitive sequence of incremental reaction and mechanical swaging steps.
  • a beam of electromagnetic radiation characterized by an electromagnetic energy that is either i n the microwave frequency spectrum or in the infrared frequency spectrum, can be directed onto the ceramic member to advance its state of crystallization.
  • the metal member which is not irradiated by a suitably directed electromagnetic beam, can b e held to a temperature well below its melting point.
  • the secondary phase material particles may have spheroidal dimensions ranging between 0.05 microns and 500 microns. Secondary phase materials particles with spheroidal dimensions less than 0.05 microns will have a tendency to b e dissolved into the ceramic medium into which they have been dispersed during reaction treatments.
  • Secondary phase material particles with spheroidal dimensions greater than 500 microns are so large that their intrinsic material properties have a tendency to dominate over the material properties of the ceramic medium into which they have been dispersed.
  • a preferred embodiment of the present invention utilizes the secondary phase material particles having spheroidal dimensions in the range between 0.10 and 5 0 microns. It is often desirable to form a metal-ceramic composite comprising a metal member having a coefficient-of-thermal-expansion that is significantly greater than the coefficient-of-thermal-expansion of the ceramic member.
  • the thermal performance of the metal-ceramic composite composed of metal an d ceramic members having incompatible coefficients of thermal expansion can be improved if the ceramic member in the metal- ceramic composite is maintained in a state of compressive stress over the range of temperatures at which the metal-ceramic composite is expected to operate.
  • a state can be achieved if the metal member in the metal-ceramic composite is heated to a temperature that is greater than, or nearly equal to, the maximum temperature to which the pre-stressed metal-ceramic composite is expected to reach during an operational cycle prior to depositing the ceramic member o n the metal member.
  • the present invention provides other means to manipulate the stress response of the ceramic to steady-state thermal loads that induce a temperature differential across the deposited ceramic member.
  • a heat shield manufactured by bonding a high thermal conductivity metal sheet to a thermally insulating ceramic on one major surface and exposing the opposing major surface of the metal sheet to a heat source, can be used to diffuse heat to heat sinks located at the minor surfaces of the high thermal conductivity metal sheet, thereby impeding heat flow through the major surface at which the thermally insulating ceramic is bonded.
  • th e temperature of the thermally insulating ceramic member will b e elevated to a higher temperature on the major surface at which it is bonded to the thermally conducting metal member, and be reduced to a lower temperature on its opposing major surface.
  • the thermally insulating ceramic member will linearly expand to a greater degree at the major surface where it is bonded to the high thermal conductivity metal, and will linearly expand to a lesser degree if the thermally insulating ceramic member has uniform composition and an uniform coefficient-of- thermal-expansion. This difference in linear expansion produces a shear stress within the thermally insulating ceramic member having uniform coefficient of thermal coefficient.
  • the thermally insulating ceramic member is deposited on the metal member by spray pyrolyzing a solution of metalorganic precursors.
  • the invention permits the composition of the ceramic member to be altered b y adjusting the precursor concentration of the metalorganic solution with the thickness of the deposited ceramic.
  • it is, thus, another preferred embodiment of the pres ent invention to reduce shear stress in a ceramic member of a thermally loaded metal-ceramic composite by introducing a composition profile in the ceramic member 19 bonded to the metal member 20, to produce a gradient in the coefficient-of-thermal-expansion within the ceramic member in a manner that reduces shear stress in the ceramic member.
  • Another aspect of this invention is to reduce the Young's modulus or the effective coefficient-of- thermal-expansion of the metal member in the metal-ceramic composite having metal and ceramic members with incompatible coefficients of thermal expansion. It is a preferred embodiment of this invention to reduce the Young's modulus of the metal member having a coefficient-of- thermal-expansion that is significantly greater than the coefficient-of-thermal-expansion of th e ceramic member to which it is bonded by drilling holes in the metal member. These holes can be drilled prior to forming the ceramic o n the perforated metal member, or after the metal-ceramic composite has been formed by means of conventional press drilling or laser drilling.
  • the constraining-metal member 28 may be situated such that it is bonded on one major surface to the deposited ceramic member 29 , and bonded to the high coefficient-of-thermal-expansion metal member 30A on its other major surface as diagrammed in FIG. 5(a).
  • the constraining-metal member 28 also may be situated such that it is bonded on one major surface to the high coefficient-of-thermal- expansion metal member 30B, and the high coefficient-of-thermal- expansion metal member 30B is bonded to the deposited ceramic member 29 on its other major surface as diagrammed in FIG. 5(b).
  • the constraining-metal member 28 may be situated such that it is bonded on one major surface to a high coefficient-of- thermal-expansion metal member 30A', and is bonded to another high coefficient-of-thermal-expansion metal member 30B' on its other major surface, with the other high coefficient-of-thermal-expansion metal member 30B' bonded to the deposited ceramic member 29 on its other major surface as diagrammed in FIG. 5(c).
  • the present invention by virtue of being a low-temperature manufacturing process, represents a further improvement over the prior art because it allows a far greater selection of high coefficient- of-thermal-expansion metal member bonded to constraining-metal member combinations to be constructed.
  • any applications for metal-ceramic composites it is desirable to couple a high thermal conductivity and/or electrical conductivity metal member to a thermally insulating and/or electrically insulating ceramic member. This is particularly true for metal-ceramic composites used as substrates in printed circuit board applications. I n such instances, semiconductor integrated circuit elements are mounted on a metal member of the metal-ceramic composite substrate. The metal member is used to transport electrical current and also is u s ed to dissipate heat generated by the SIC. In such applications it is particularly useful for the metal member to maximally dissipate heat and transport maximum levels of electrical current.
  • metals that exhibit higher electrical and thermal conductivities commonly exhibit higher coefficients of thermal expansion, whereas metals with high yield strengths and low coefficients of thermal expansion, which are suitable for use as a constraining-metal member, typically exhibit poorer electrical and thermal conductivities.
  • FIG. 7 depicts magnified views of the structural response in 2 different configurations for metal-ceramic composite substrates in typical printed circuit board applications as simulated by finite element method (“FEM”) analysis.
  • FEM finite element method
  • the FEM analysis presented assumes the metal-ceramic composite structure sketched in FIG. 6(a).
  • the FEM model consists of a 150 °C heat source 31 to represent an SIC, and has heat sinking cooling fins 32 at the edge of a 3.00 mm thick copper mounting area 33, which is bonded to a 0.45 mm thick constraining-metal member 34.
  • the constraining- metal member 34 is bonded through its opposing major surface to a 1.00 mm alumina ceramic member 35, which, in turn, is bonded through its opposing major surface to a 0.30 mm thick copper ground plane member 36.
  • the model further assumes the materials properties for alumina, copper, molybdenum and titanium a s tabulated in Table I.
  • the outer edges of the model (including the cooling fins) are subject to an environmental load of 27 °C and convective heat loss of 4.33 x 10 ⁇ 6 W/mm ⁇ .
  • the system has been allowed to relax to its steady-state equilibrium values to simulate conditions of maximal thermal loading.
  • FIG. 6(b) depicts a magnified view (20x) of the FEM-simulated deformation to the metal-ceramic composite when the constraining- metal layer in the model comprises molybdenum.
  • FIG. 6(b) models the molybdenum-containing composite in the symmetrical half-plane.
  • the thermally loaded structure 37 is quite deformed from the stress-free structure 38.
  • FIG. 6(a) depicts a magnified view (20x) of the FEM-simulated deformation to the metal-ceramic composite when the constraining- metal layer in the model comprises titanium.
  • FIG. 6(c) models the composite in the symmetrical half-plane.
  • structural deformation to a metal-ceramic composite printed circuit board substrate containing a titanium constraining-metal memb er directly bonded to the ceramic member is generated by thermal loading 39 when compared to the stress-free structure 38.
  • This deformation is greatly reduced when compared to the deformation generated in the thermally loaded metal-ceramic composite th at contains a molybdenum constraining-metal member.
  • the improved structure cannot be reduced to practice using a high-temperature process, such as those described by the prior art.
  • a high-temperature process such as those described by the prior art.
  • titanium and copper form an eutectic a t temperatures greater than 880 °C. Therefore, a process that requires a copper member to be mechanically pressed to a titanium member a t a temperature of at least 900 °C for a period of at least 20 minutes will cause the members to form their eutectic and liquefy.
  • a covalent bond is formed between the deposited ceramic member and the metal member(s) at temperatures less than 550 °C.
  • the present invention makes possible th e construction of a much wider variety of high electrical or high thermal conductivity metal member bonded to constraining-metal member combinations. It is, therefore, a preferred embodiment of the pre sent invention to deposit a ceramic member on a metallic me m ber substrate, wherein the metallic member substrate comprises at least one high coefficient-of-thermal-expansion metal member consisting of a pure metal, metal alloy, or metal composite of aluminum, copper, silver, or gold, that is bonded, on at least one major surface, to a constraining metal member, wherein the constraining-metal memb er may comprise a pure metal, metal alloy or metal composite of antimony, chromium, iridium, molybdenum, tantalum, ( ⁇ -)tin, titanium, tungsten, or vanadium.
  • the high coefficient-of-thermal- expansion metal member may be characterized as having a high electrical conductivity and/or high thermal conductivity.
  • the constraining-metal member bonded to the metal member with a high coefficient-of-thermal-expansion may be characterized as having a coefficient-of-thermal-expansion that is less than the coefficient of expansion of the metal member to which it is bonded. It is preferred to have the constraining-metal member bonded to the metal memb er having a high coefficient-of-thermal-expansion through explosive pressure welding, or other metal-metal bonding techniques known to practitioners skilled in the art of metallurgy, prior to forming a covalent bond with the deposited ceramic member.
  • the ability to form a covalent bond between the deposited ceramic member and the metallic substrate without a molten bonding agent or adhesive permits even greater improvement to the prior art by introducing stress- reducing micro-mechanical elements to the interface.
  • the pre sent invention allows, as shown in FIG. 7(a) for at least one adhesion- resistant body 40 to be placed on the surface of the metal member substrate 41 onto which the ceramic member will be deposited prior to depositing the ceramic member.
  • the adhesion-resistant body can b e blown of the surface of the metal member substrate during th e ceramic deposition process, therefore it is a preferred embodiment of this invention to physically secure the at least one adhesion-resistant body on the surface of the metal member substrate without forming a permanent bond between the at least one adhesion-resistant body an d the metal member substrate by coating the adhesion-resistant body with a resin epoxy 42 as shown in FIG. 7(b)) that decomposes a t temperatures greater than the substrate deposition temperature to which the metal member substrate is heated during the ceramic deposition process.
  • the ceramic member 43 as shown in FIG.
  • the entire metal-ceramic composite can be heated to a temperature that decomposes the resin epoxy 42 that physically secures the a t least one adhesion-resistant body to the metal member substrate, (typically to a temperature in the range between 450 °C to 550 °C), to produce a metal-ceramic composite in which a rigid covalent bond h a s been formed between the metal member substrate 41 and th e deposited ceramic member 43 only at those regions of the metal- ceramic interface that are not occupied by the at least one adhesion resistant body 44 as shown in FIG. 7(d).
  • adhesion-resistant body is composed of a material composition and phase that does not liquefy and form a rigid bond through molten action, regions 45 of th e metal-ceramic interface that are occupied by the at least one adhesion resistant body will not be bonded to the adhesion-resistant body, n or to the deposited ceramic layer.
  • the adhesion-resistant body 40 will be allowed to slip relative to displacements or linear expansions of th e metal member substrate 41 at the non-bonded regions 45 of th e metal-ceramic interface.
  • This embodiment of the present invention cannot be produced using metal-ceramic bonding techniques, such a s eutectic bonding or active metal/solder bonding, which form the bond through a liquefied or molten phase that, when pressed, is smeared, and forms a rigid bond when cooled, across the entire bonding surface.
  • metal-ceramic bonding techniques such as a s eutectic bonding or active metal/solder bonding, which form the bond through a liquefied or molten phase that, when pressed, is smeared, and forms a rigid bond when cooled, across the entire bonding surface.
  • each adhesion-resistant body need not be circular as depicted in drawings and may assume an y cross-sectional geometry that improves the crack-resistance of the deposited ceramic member, or reduces the stress distribution within the metal-ceramic composite.
  • the cross-sectional geometry for th e adhesion-resistant body can be determined for a given application using computer simulation by any practitioner skilled in the art of finite element method analysis.
  • the at least one adhesion- resistant body need not be a discrete body, but a series of continuous bodies, such as whiskers, platelets or fibers. For instance, a fiber or wire mesh can be utilized to pattern a adhesion-resistant body grid a t the metal-ceramic interface.
  • FIGS. 8 (a) and (b) represent top perspectives of some, but by no means all, representative patterns of adhesion-resistant bodies 40 o n metal member substrates 41 that may be useful.
  • Such patterns of adhesion-resistant bodies can be fixed on the surface of the metal member substrate using a variety of means, including, but not limited to, screen printing or other printing techniques such as, letterpress, gravure, rotogravure, dot and or jet printing.
  • adhesion-resistant bodies will, of course, be dependent upon on the thermal and/or mechanical loads of a specific application, and can b e determined using computer simulation by any practitioner skilled i n the art of finite element method analysis or other computer simulation methods.
  • the use of adhesion-resistant bodies to construct a metal- ceramic composite with improved interfacial properties in any p attern is considered an element of, and as having been instructed by, th e present invention.
  • the adhesion-resistant bodies may be produced from a variety of materials that do not liquefy or form a molten or rigid bond with th e metal member to which the adhesion-resistant bodies are contacted i n a metal-ceramic composite. Therefore, its is recommended to compose the adhesion-resistant bodies from a material that melts a t temperatures greater than the maximum temperatures (450-880 °C) to which the metal-ceramic composite may be exposed, the adhesion- resistant bodies may be composed of materials that comprise, but are not limited to, metals or metal alloys, a glass phase, a shape memory alloy, graphite, an oxide or non-oxide material, or a crystalline ceramic or single crystal material phase.
  • FIGS. 9 (a) and (b) it is another preferred embodiment of this invention to utilize adhesion-resistant bodies composed of a material phase that can be selectively etched o r removed from the metal-ceramic composite after processing to produce voids 46 in the deposited ceramic member 43 bonded to th e metal member substrate 41 of the metal-ceramic composite where th e selectively etchable adhesion-resistant bodies were originally located as shown in FIG. 9(a).
  • This aspect of the invention allows micro- mechanical struts 47 to be produced in the ceramic member that can flex in response to lateral displacements of the bonded metal member caused by linear expansions or contractions of the bonded metal member.
  • FIG. 9(b) depicts the flexure in a thermally loaded composite 39 compared to its stress-free state 38.
  • the flexure provided by th e micro-mechanical struts in the ceramic member reduces the shear stresses normally generated in the interior of a bonded ceramic member which typical induce cracking of the bonded ceramic member.
  • the degree of stress reduction in the bonded ceramic member is dependent upon the physical dimensions of the micro- mechanical struts, which may be defined as having a width, w, a depth, d, and a spacing, s as shown in FIG. 9(a).
  • FIG. 10 graphically depicts characteristics curves for the stress reduction in the ceramic member at distances of 20 microns A , 52 microns B, and 185 microns C versus the depth parameter (d-parameter) of micro-mechanical struts that have a width (w -parameter) of 50 microns, and a spacing (s-parameter) equal to 50 microns.
  • FIG. 11 depicts characteristics curves for the stress reduction in the ceramic member at distances of 20 microns D, 52 microns E, and 185 microns F versus the width parameter (w -parameter) of micro-mechanical struts that have a depth (d-parameter) of 150 microns, and a spacing (s-parameter) equal to 50 microns.
  • Hygroscopic glass materials are preferred for use as th e selectively etchable adhesion-resistant body materials used to produce patterns of voids and micro-mechanical struts in the bonded ceramic member.
  • Hygroscopic glass materials can be dissolved i n water without risking erosion of the composites metal and ceramic members by simply immersing the composite into an aqueous ultrasonic bath medium. Glass materials can be easily shaped into microscopic geometries and patterns using methods well known to practitioners skilled in the art of producing optical fiber, fiber-optic bundles, and micro-optical components. It is a preferred embodiment of this invention to utilize phosphate-based and or borate-based hygroscopic oxide glasses as the selectively etchable adhesion- resistant bodies.
  • a problem with this solution is the general mismatch in th e coefficients of thermal expansion between the oxide coating and th e protected ceramic body which causes the coating to crack and fail over the desired temperature range. It is therefore desirable to provide means by which protective oxide coatings could be applied to such ceramics in such ways as to prevent mechanical failure which leads to the ultimate decomposition of the ceramic body.
  • the methods developed to reduce shear stresses caused b y mismatched coefficients of thermal expansion at the composite interface between a metal layer and a ceramic layer can also b e applied to relieving crack-inducing shear stresses at the interface between an oxide ceramic coating and an environmentally sensitive non-metallic substrate, such as a carbide ceramic, or a carbon-based ceramic. It is anticipated that similar benefits can be derived wh en applying protective oxide coatings to nitride ceramic substrates under appropriate conditions for that material system.
  • oxide ceramic coating to a non-metallic substrate, such as a carbide ceramic, carbon-based ceramic, or nitride ceramic, using the methods recited above so as the oxide containing coating medium contains secondary phase particles that improve the crack-resistance of the oxide coating.
  • secondary phase particles are characterized a s having intrinsic mechanical properties that are less brittle, i.e., the secondary phase has a lower Young's Modulus than the protective ceramic medium.
  • these secondary phase particles may be dispersed throughout the metalorganic solution prior to spray pyrolysis, and, as a result, become dispersed in the deposited oxide coating after spray pyrolysis upon the non-metallic substrate.
  • th e secondary phase material particles may comprise a metal or metal alloy, a glass phase, a shape memory alloy, graphite, an oxide or non- oxide material, or a crystalline ceramic or single crystal material phase.
  • the physical dimensions of the secondary phase material particles recited above are invoked by extension.
  • thermally-induced shear stresses can be reduced using a protective oxide coating that has a non-uniform coefficient of thermal expansion.
  • the invention permits the composition of th e oxide coating to be altered by adjusting the precursor concentration of the metalorganic solution with the thickness of the deposited ceramic. It is, thus, another preferred embodiment of the present invention to reduce shear stresses in the protective oxide coating on a thermally- loaded non-metallic ceramic substrate by introducing a compositional profile in the oxide coating bonded to the non-metallic substrate th at produces a gradient in the coefficient-of-thermal-expansion within th e protective oxide coating in a manner that reduces shear stresses in th e protective oxide coating.
  • adhesion-resistant bodies at the interface between the protective oxide coating and the non-metallic substrate is also a preferred embodiment of the invention.
  • the remaining components use the same reference numerals as previously used throughout th e description of the drawings.
  • at least one adhesion-resistant body 40 is place on the surface of the non-metallic substrate 41 ' onto which the protective oxide ceramic coating will be deposited prior to depositing the ceramic oxide layer.
  • the protective ceramic coating is then spray pyrolyzed from a metalorganic solution on to the non-metallic substrate 41 ' and the at least one adhesion-resistant body 40 physically attached to or placed on the non-metallic substrate an d processed to form the ceramic composite.
  • another preferred embodiment of this invention is to utilize adhesion-resistant bodies composed of material that can b e selectively etched or removed from the protective oxide ceramic-non- metallic substrate composite after processing to produce voids in th e deposited protective oxide layer where the selectively etchable adhesion-resistant bodies were originally located.
  • This aspect of the invention allows micro-mechanical struts as shown in Figs. 15(a) an d 15(b) to be produced in the protective oxide ceramic layer that can flex in response to lateral displacements of the bonded non-metallic substrate caused by linear expansions or contractions of the bonded non-metallic substrate41 ' .
  • metal-ceramic composites of thi s invention relate to the use of the metal-ceramic composites as a metal-ceramic composite substrate for printed circuit boards.
  • metal-ceramic composite substrates for printed circuit boards comprise a high conductivity metal sheet member, commonly a copper sheet on which semiconductor integrated circuits are eventually mounted.
  • the metal sheet member is bonded on a major surface to an insulating ceramic member with a low-dielectric constant, typically alumina, which, in turn, is bonded on its opposing major to another high conductivity metal (copper) sheet.
  • the copper sheet upon which SIC's are eventually mounted is required to satisfy certain tolerances for the metal-ceramic composite substrate to operate reliably as a printed circuit board, and may contain a constraining-metal member to reduce its effective coefficient-of- thermal-expansion.
  • Tolerances relating to the surface roughness of the metal member on which SIC's are mounted require the metal member to have at least a median surface roughness of 3 microns and a maximum surface of 18 microns, although a median surface roughness of 1 micron and a maximum surface roughness of 8 microns are preferred. It is also preferable to chemically polish the metal member in a mixture of sulfuric acid and hydrogen peroxide for a period of 1 to 5 minutes to attain a surface finish within these tolerances.
  • Tolerances relating to the Vickers hardness of the metal member on which SIC's are mounted require the metal member to have a Vickers hardness that is at least in the range of 40- 100 Kg/mm.2, although a Vickers hardnes s in the range of 60-80 Kg/mm ⁇ is preferred.
  • Metal-ceramic composites formed by spray pyrolyzing the ceramic member on the metal member from a metalorganic precursor solution permits the production of metal-ceramic-metal composite sheet structures by pressing together two composites ceramic face to ceramic face, wherein the composites comprise a ceramic member deposited on a metal member substrate.
  • the pressed metal-ceramic- metal composite is then thermomechanically calcined to form a uniformly rigidly bonded structure.
  • This application of the pre sent invention is suitable for composites structures in which the ceramic members can be sintered at temperatures less than the melting point of the metal member substrates. This is not possible with copper- alumina-copper structures, wherein the alumina member needs to b e sintered at a temperature of at least 1828 °C, which is well above th e melting point of copper at 1083°C.
  • high conductivity metal- alumina-high conductivity metal such as copper-alumina-copper structures, with improved crack-resistance and interfacial properties are produced by depositing an alumina-based ceramic on the high conductivity metal member.
  • i t is another preferred embodiment of the present invention for the high conductivity metal member substrate 53 upon which an alumina ceramic member 54 is deposited to contain a constraining-metal member 55, and for adhesion-resistant bodies 56 to be implanted a t the interface between the metal member substrate and the deposited ceramic member.
  • a similarly made metal-alumina ceramic composite which may or may not contain the constraining-metal member 55 o r the adhesion-resistant bodies 56, is produced to bond with the other metal-alumina ceramic composite.
  • Low temperature ( ⁇ 880 °C) bonding is achieved by introducing a layer of low-melting temperature oxide or oxyfluoride phase materials 57 that form a molten liquid phase at temperatures below 880 °C on the bonding surfaces 58 of at least one the metal-alumina ceramic composites.
  • the low-temperature oxide or oxyfluoride phases may be introduced to the bonding surface as metalorganic precursors of the spray pyrolyzed solution, as secondary phase material particles dispersed in the metalorganic solution, as secondary phase material particles no t dispersed in the metalorganic solution but still applied to the bonding surfaces 58, are as an active metal film or powders that are oxidized.
  • the bonded alumina ceramic member In printed circuit board applications it is desirable for the bonded alumina ceramic member to have a low dielectric constant, it is, therefore, preferable to use light atomic weight metal oxides. It is a preferred embodiment of this invention to utilize an phospho- alumino-borate glass phase as the low-temperature oxide bonding layer.
  • Borate glass melts at temperatures as low as 450 °C, but is sensitive to chemical attack by water.
  • Phosphoric anhydride typically melts in the range of 580-585 °C.
  • Incorporating alumina into phosphate and borate oxide glasses increases chemical resistance an d intrinsic strength.
  • Aluminophosphate glass phases typically melt a t temperatures ranging from 660- 1575 °C
  • Additions of alkali oxides or alkali fluorides are useful in depressing the melting temperature of the low-temperature oxide bonding agent, but will also decrease its resistance to chemical attack by water.
  • the low melting temperature oxide bonding layer prefferably has a thickness in th e range of 1 micron to 150 microns.
  • the two metal-alumina ceramic composites, with at least one of the metal-alumina ceramic composites containing a low-temperature oxide bonding agent on its bonding surface, are then heated to at least a temperature above which the low-temperature oxide bonding agents forms a molten phase.
  • the two metal-alumina ceramic composites are then joined at their bonding surfaces and pressed together at a pressure between 0.5 and 25 MPa. When cooled, a rigid oxide bond is formed between the two metal- alumina ceramic composites at the bonding surfaces to form the finished conducting metal-alumina ceramic-conducting metal composite.
  • the two different metal members in a composite substrate for printed circuit board applications be made to different thickness and mechanical specifications. These differences need to be considered prior to forming the final bonded composite. It is, therefore, a preferred embodiment of this invention to form the composite substrate using one metal-alumina ceramic composite that contains a conducting metal member bonded to a constraining metal member, wherein the thickness of the constraining-metal member is in the range between 0.015 mm to 1.67 mm, and the total (combined) thickness of th e conducting metal member(s) is in the range between 0.30 mm to 5.00 mm; and, another metal-alumina ceramic composite that contains a conducting member in the range of 0.01 mm to 0.3 mm.
  • the alumina- ceramic members on each of the two metal-ceramic composites m a y vary such that the combined thickness of alumina ceramic in th e bonded metal-ceramic-metal composite is in the range between 0.3 to 1.0 mm. It is, thus, preferred that the thickness of the ceramic member in the metal-ceramic composites be in the range of 0.15 to 0.85 mm.
  • Yet another particular subject of the present invention relates to the incorporation of a ferrite ceramic member into a metal-ceramic composite substrate for printed circuit board applications.
  • semiconductor integrated circuits mounted on a printed circuit board substrate may actually become radiators of harmful electromagnetic radiation, or be exceptionally sensitive to such emissions.
  • FIGS. 18(a), (b) and 19 it is desirable to have an element in close proximity to the SIC that would absorb th e electromagnetic radiation.
  • a lossy ferrite ceramic member 59 can be bonded to a major surface of a high conductivity metal sheet, which is then used, on its opposing maj or surface, as the metal member substrate for a deposited alumina ceramic member.
  • the ferrite ceramic-metal-alumina ceramic member is then bonded into a metal-ceramic composite substrate suitable for printed circuit board applications using the art described above.
  • a further particular subject of the present invention relates to the production of a metal-porous ceramic composite, wherein the porous ceramic member has ultrafine subdivision.
  • the metal-ceramic composite it is desirable for the metal-ceramic composite to function simultaneously as a heat shield and as a sound absorber.
  • a porous ceramic member can function both as a thermally insulating memb er and as a sound absorber.
  • Porous ceramics are also preferred forms of ceramic in the application of metal-ceramic composites a s electrochemical electrodes. Large organic molecules, such a s carboxylic acids, generate considerable water and carbon dioxide/carbon monoxide during thermal decomposition.
  • a porous ceramic on a metal substrate is readily realized by spray pyrolyzing carboxylic acid salt precursors to the ceramic a s the metalorganic solution. Under this aspect of the present invention, mechanical swaging steps are omitted. It may also be preferable to introduce other foaming agents to the metalorganic precursor solution, such as polyurethanes, polyvinylchorides, polyethylenes, pentanes , hexanes, or polypropylenes, that further increase the foaming actions during the deposition process.
  • foaming agents such as polyurethanes, polyvinylchorides, polyethylenes, pentanes , hexanes, or polypropylenes, that further increase the foaming actions during the deposition process.

Abstract

A ceramic composite having a metal substrate (36) banded to one surface of a ceramic oxide member (35) through a covalent bond formed at temperatures less than 880 °C. A constraining member (34) is bonded to another surface of the ceramic oxide. A thermal and/or mechanical load (31) and heat sinks (32) are attached to the constraining member through a copper mounting are (33). Ceramic composites that are constructed to control internal stresses or increase crack-resistance within the ceramic oxide member under applied thermal and/or mechanical loads (31).

Description

CERAMIC COMPOSITES WITH IMPROVED INTERFACIAL PROPERTIES AND METHODS TO MAKE SUCH COMPOSITES
BACKGROUND OF THE INVENTION
The present invention relates generally to certain classes of ceramic composites, and, more particularly, to structural an d functional such composites and devices incorporating such composites, including, among others, printed circuit boards and other components
Metal-ceramic composites comprising a metallic member bonded to a ceramic member have many useful applications in areas including, but not limited to, electronic circuits, heat shielding components, structurally-reinforced composite sheeting, engine components, electromechanical actuators or micro-positioners, an d electrochemical electrodes. In many of these applications the interface between the metal member and the ceramic member is subject to mechanical stress generated at, or close to, the interface formed between the metal and the ceramic. For instance, preferred combinations of metallic composition and ceramic composition that optimize the performance of an ideal metal-ceramic composite often require an interface to be formed between a metallic composition and a ceramic composition that have poorly matched coefficients of thermal expansion. The composite interface is often susceptible to thermal cycling during the operational mode in these applications. Thus, despite the apparent ability to readily improve performance in the intended application, the actual performance of these metal- ceramic composite structures is unreliable as interfacial stresses developed between metal and ceramic members cause the composite to crack, deform, or delaminate as a result of operational heat cycling. Methods to economically construct metal-ceramic composites with improved interfacial properties, and the composites constructed therewith, are clearly desirable.
Electronic circuits, be they microelectronic circuitry contained o r embedded on the surface of a semiconductor chip or an integrated circuit built on a circuit board, generate both heat and electromagnetic field emissions. The more powerful microelectronic circuits used in some of these devices generate significant levels of heat, which can compromise performance efficiency in units lacking efficient thermal management systems. Metal-ceramic composite structures have b een used for thermal management, implemented either as a printed circuit board or as an integral member of an electronic package (both referred to herein as "printed circuit boards"). Mismatch in the linear coefficients of thermal expansion at the interface(s) between th e differing metal and ceramic materials can result in cracking within or delamination of the composite structure, leading to the eventual failure of the thermal management system.
In many instances, the electromagnetic field emissions generated by these devices can disrupt the proper functioning of ne arby electronic equipment and/or be harmful to human safety. As a n example, electromagnetic radiation emitted from an operating electronic device, such as a cellular telephone, is known to interfere with the proper functioning of the avionics instrumentation on-board modern aircraft in a manner that risks catastrophic consequences i n flight. Diagnostic testing on cellular telephones has shown that the electromagnetic field emissions of one unit operated in close proximity to another unshielded unit can trigger communications failure. Additionally, the perception exists among some in the health sciences community that electromagnetic field emissions may actually alter cellular metabolism in a harmful way within a small, but measurable, percentage of the human population. As a result, cellular telephones, which typically emit electromagnetic radiation at power levels of 600 milliwatts (mW) in close proximity to the human brain, may directly threaten human health if these emissions are actually demonstrated to harm human tissue. It is often advantageous to minimize the size and weight of electronic systems by integrating multifunctional performance into subsystems contained in the total systems package. Methods that can simultaneously protect sensitive electronic systems from disrupting electromagnetic interference or that shield human tissue from harmful electromagnetic emissions and contribute to th e thermal management of electronic systems and/or provide printed circuit board functionality in a reliable manner are, therefore, desirable. Improved interfacial properties between metal and ceramic members can also benefit many other areas, such as in electrochemical processing. Many electrochemical processes must be driven at high temperature. In such instances it is advantageous to utilize metal- ceramic composite electrodes that simultaneously conduct ions an d electrons because of the ceramic member's higher oxidation- an d corrosion-resistance. Mismatch in the linear expansion of the ceramic member and the metallic member of the electrochemical electrode during thermal cycling will eventually degrade the useful function of the component, since cracks which develop in the ceramic memb er provide a conduit through which corrosive elements can attack th e metal. Metal-ceramic composites also have been contemplated for u se as components in automotive and jet engines. These applications c an subject the composite part to extreme changes in body temperature, as well as sharp temperature differentials across the body of th e composite part itself. Poor interfacial characteristics can limit the performance of the engine part. Interfacial stress at a metal-ceramic interface are not limited to mechanical stresses that are thermally induced through a mismatch in linear-expansion-coefficients. Metal- piezoelectric ceramic interfaces are now widely applied in electromechanical actuators and micro-positioners. In these electromechanical applications, the metal member is used as a n electrode to convey a voltage across the piezoelectric ceramic, which, in turn, will expand (or contract) along the ceramic's crystallographic axis that is normal to the plane defining the metal-ceramic interface. Concurrent with the longitudinal expansion (contraction) in th e ceramic, the piezoelectric ceramic will simultaneously contract (expand) laterally along crystallographic orientations parallel to the plane defining the metal-ceramic interface. Linear expansions i n high-performance piezoelectric ceramics can be as high as 1 %, which is roughly equivalent to the linear thermal expansion generated by a 1000 °C change in temperature. Likewise, a composite sheet used as a lightweight structural component, comprised of a ceramic sheet member bonded to a metallic sheet member, wherein the ceramic member provides greater structural integrity or rigidity to the metal member, will be subject to a variety of mechanical loads and forces that stress the interface between the ceramic and metallic members. Thus, methods that can be widely applied to improve the performance of bulk metal-ceramic composites subjected to extreme linear expansions along at least one interface formed between the metal member and the ceramic member in metal-ceramic composite are, therefore, also desirable.
The following patents are listed as examples of the prior art: Kashiba et al, U.S. Patent Nos. 5,153,077 and 5, 251 ,803; Komorita e t al, U.S. Patent No. 5, 155,665; Tanaka et al, U.S. Patent Nos. 4,959,507 and 4,987,677; Ookouchi et al, U.S. Patent No. 4,981 ,761 ; Su et al, U.S. Patent No. 5, 108,026; Simon et al, U.S. Patent No. 5,342,653. The publications of A. Goldman, in "Modern Ferrite Technology," V an Nostrand Rheinhold, New York, USA (1990) and A.J. Baden Fuller, in "Ferrites at Microwave Frequencies," Peter Peregrinus Ltd., London, U.K. ( 1987) provide reference literature on the physical properties of ferrite ceramics at low and microwave frequencies. Aspects of these references will be also described further in the Detailed Description of the present invention.
It is therefore an object of this invention to provide a metal- ceramic composite of a metal member bonded with a ceramic member, which may either be a dense or porous ceramic, preferrably an oxide, wherein the bonding is formed through a covalent bond a t temperatures less than a eutectic point for a phase disgram of a metal component of the ceramic layer or its precursor and the metal of the metal layer. It is a still further object of this invention to exploit the low- temperatures at which a bond can be formed between the ceramic oxide member and a high thermal conductivity or electrical conductivity metal member.
It is a further object of this invention to engineer stress-relief a t the interface between a ceramic oxide coating applied to a non- metallic substrate.
It is a still further object of this invention to provide metal- alumina ceramic composite substrates for printed circuit board applications. It is a still further object of this invention to provide a dispersion of secondary phase material particles in the ceramic member to increase the crack-resistance of the ceramic member. It is a still further object of this invention to provide a metal - ceramic (preferrably oxide ceramic) composite such that the ceramic member contains a compositional gradient, and a corresponding gradient in its coefficient-of-thermal-expansion, that reduces shear stress in the ceramic member when the metal-ceramic composite is subjected to a thermal load.
It is a still further object of this invention to provide increased crack-resistance by constructing the metal-ceramic (preferrably oxide ceramic) composite oxide such that the ceramic is in a state of compressive stress.
It is a still further object of this invention to provide a construction of a metal-ceramic composite in which adhesion-resistant bodies have been placed at the interface between the metal member and the ceramic oxide member to control the fracture mechanics of the metal-ceramic composite interface.
It is a still further object of this invention to provide a construction of micro-mechanical structures in the ceramic oxide member at the interface with the metal member to increase the flexure in the ceramic oxide member at the interface when the metal member expands or contracts.
SUMMARY OF THE INVENTION
The method and products of the present invention overcome many of the problems associated with the production of past metal/ceramic components. The examples of the present invention stated below under "Detailed Description of Preferred Embodiments" are provided for illusrative purposes and not to limit the scope of the invention. The invention involves deposition of a metal precursor to a ceramic composition (e.g. ceramic oxide such as Al2θ3; Tiθ2 or other single or mixed oxides, borides, carbides, nitrides, suicides) on a metal substrate at a molecular level as a finely divided form of highly adherent metalorganic compounds followed by pyrolysis. The overall process is conducted at low temperature and involves the method of metalorganic chemical spray pyrolysis. Using this method, metal precursors to the ceramic oxide composition are introduced as metalorganic salt complexes, (i.e., metal complexes having organic ligands), into an organic solvent. Together they form the metalorganic precursor solution. High molecular weight carboxylic acid salts, such as 2-ethylhexanoates, or naphthenates, are the preferred metalorganic species using the process. In solution, the various ceramic precursors are mixed at the molecular level and thus, in minutes, achieve a state of ultrafine subdivision that typically is only achieved after calcining a slurry of powder precursors for m any hours. Ceramic precursors are generally introduced into th e metalorganic solution in concentrations in the range between 0.05% and 25% equivalent-weight oxide (eq.-wt%), although precursor concentrations in the range of 1% and 20% eq.-wt% are preferred. The spray conditions can be adjusted for compositional (and physical property) uniformity throughout the thickness of the eventual ceramic layer or for graded or otherwise differentiated composition an d properties, e.g. graded coefficient of thermal expansion.
This state of ultrafine subdivision (wherein precursors have been mixed at the molecular level) among the precursors is retained when the metalorganic solution is nebulized into an aerosol mist and deposited as a ceramic oxide (or the like) on the surface of a heated substrate. The substrate surface must be heated to a temperature that is greater than the boiling point of the organic solvent, which evaporates during ceramic deposition, and at least greater than th e decomposition temperature of the organic ligand that is most sensitive to thermal decomposition and contained in the metalorganic salt complex that, too, is most sensitive to thermal decomposition. It is prefered to heat the substrate to a temperature that is at least equivalent to the decomposition temperature of the organic ligand which is most sensitive to thermal decomposition and contained in the metalorganic complex which is least sensitive to thermal decomposition. Carboxylic acid salt precursors are preferred because of their low volatility. Carboxylic acids typically form waxy solids th at will thermally decompose rather than evaporate.
During pyrolysis in an ambient oxygen atmosphere, th e metalorganic precursors decompose into highly energetic metal radicals that rapidly seek to form covalent bonds with an unbound electron. Heated substrate surfaces comprise a sheet of dangling bonds that are also excited to form a lower energy bond with th e metal radicals of the decomposing metalorganic salt complex. Metalorganic salt complexes typically decompose over a temperature range of 250-450° C. This process thus allows a covalent bond to b e formed between the deposited ceramic material and a heated metal member at a low temperature in the range of 250-450° C. The deposited ceramic retains the state of ultrafine subdivision achieved in the metalorganic solution because the rapid pyrolysis of th e precursor droplet, cooled by adiabatic expansion during aerosol nebulization, occurs at such a high rate that the mixed precursors h ave little or no time to segregate and sequentially decompose as individual metal oxide species.
The ceramic deposited on the heated metal substrate is initially porous and comprised of a solid solution with randomly oriented crystalline structure. The deposited ceramic member can be brought into a physical state comprised of highly oriented and densely packed crystalline grain structure using multiple short duration sequential reaction and mechanical pressurization processing steps. The density of ceramic so-processed can achieve levels approaching 97% an d preferrably, for many applications over 99% of theoretical density. For example, one aspect of the present invention provides for th e dispersion of secondary phase material particles in a ceramic medi um in order to increase the crack resistance of the ceramic medium.
Another feature of the present invention provides for a thermally insulating ceramic member to be deposited on the metal member by spray pyrolyzing a solution of metalorganic precursors and thus permits the composition of the ceramic member to be altered by adjusting the precursor concentration of the metalorganic solution with the thickness of the deposited ceramic. This reduces shear stress in a ceramic member of a thermally loaded metal-ceramic composite by introducing, as stated above, a composition profile in the ceramic member bonded to the metal member in order to produce a gradient in the coefficient-of-thermal-expansion within the ceramic member i n a manner that reduces shear stress in the ceramic member.
The present invention, by virtue of being a low-temperature manufacturing process, also represents a further improvement over the prior art because it allows a far greater selection of constraining metal members than the prior art. Further, the ability to form a covalent bond between the deposited ceramic member and th e metallic substrate without a molten bonding agent or adhesive, as is enabled under the present invention, permits even greater improvement over the prior art by introducing stress-reducing micro- mechanical elements to the ceramic layer throughout in the thickness and/or near the metal-ceramic interface, such elements substantially retaining their compositional and physical integrity.
Another particular aspect of the metal-ceramic composites of this invention relates to the use of the metal-ceramic composites as a metal-ceramic composite substrate for printed circuit boards. Also under the present invention, high conductivity metal-alumina-high conductivity metal, such as copper-alumina-copper structures, with improved crack-resistance and interfacial properties are produced by depositing an alumina-based ceramic on the high conductivity metal member . In making complete metal-ceramic-metal printed circuit boards, it is preferred to separately produce single metal-ceramic composites and bond them, ceramic face to ceramic face, with heat/pressure assisted self bonding or via an intermediate layer.
Under certain processing conditions, the surface texture of one or both the ceramic-faces of metal-ceramic composites bonded together ceramic-face to ceramic-face can become grossly undulated. This is particularly true with hard ceramic compositions, such as alumina ceramic. In such instances, the excessive surface roughness may create problems when forming the low-melting temperature oxide bond, or cause the ceramic member sandwiched between the metal members and/or the final composite to have unacceptably non- uniform thickness. In these cases, one can grind the surface of the bonded ceramic face(s) prior to bonding. Surfaces with controlled roughness will generally produce better bonding. It is recommended, but not strictly necessary, to produce a ceramic-face bonding surface that has a mean surface roughness of 25-50 microns, and a maximum surface roughness of 40-100 microns. Ground surfaces with controlled surface roughness can be produced using a variety of techniques, such as abrasion blasting, that are well known to practitioners skilled in relevant art.
For a better understanding of the present invention, together with other and further objects, reference is made to the following description taken in conjunction with the accompanying drawings, in which:
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a cross-sectional representation of a metal-ceramic composite printed circuit board as found in the prior art;
FIG. 2. represents a cross-sectional view of a typical fracture pattern for a metal-ceramic composite interface that has b een thermally overstressed in a typical printed circuit board as shown i n FIG. 1 ;
FIG. 3 represents a cross-sectional view of a metal-ceramic composite of the preferred embodiments of the present invention wherein particles of at least one secondary phase material are dispersed in the composite's ceramic member to impede crack propagation and increase crack-resistance;
FIG. 4 represents a schematic cross-sectional view of th e coefficient of thermal expansion within a ceramic member;
FIGS. 5 (a), (b) and (c) depict various positions of a constaining metal member within the composite of an embodiment of the present invemtion;
FIG. 6 (a) is a cross sectional view of a metal ceramic structure; FIGS. 6 (b) and 6 (c) represent a model that visually simulates the thermal deformation in a metal-ceramic composite substrate printed circuit board and compares thermal deformation in the composite when the mounting area contains a molybdenum constraining-metal member to the thermal deformation in the composite when th e mounting area contains a titanium constraining-metal member.
FIGS. 7 (a)-(d) depict cross-sectional views of the construction of a metal-ceramic composite in which adhesion-resistant bodies are placed on a metal member substrate (a), or coated with an epoxy resin before being attached to the metal member substrate (b), a ceramic member is deposited on both the adhesion-resistant bodies and th e metal member substrate (c), and the resin epoxy is finally removed (d);
FIGS. 8 (a) and (b) show the top perspective of various shapes an d forms for adhesion-resistant bodies; FIGS. 9 (a) and (b) depict various parameters that define a micro- mechanical strut at a metal-ceramic oxide interface (a) and the flexure the micro-mechanical struts provide to the ceramic at the interface (b); FIG. 10 shows the characteristic stress-reduction versus the depth of micro-mechanical struts formed in the ceramic member at various distances from the metal-ceramic interface;
FIG. 1 1 shows the characteristic stress-reduction versus the width of micro-mechanical struts formed in the ceramic member at various distances from the metal-ceramic interface;
FIG. 12 represents a cross-sectional view of a ceramic composite of the present invention wherein particles of at least one secondary phase material are dispersed in the composite's ceramic member to impede crack propagation and increase crack-resistance; FIG. 13 represents a schematic cross-sectional view of th e coefficient of thermal expansion within a ceramic member;
FIGS. 14 (a)-(d) depict cross-sectional views of the construction of a ceramic composite in which adhesion-resistant bodies are placed o n a substrate (a), or coated with an epoxy resin before being attached to the substrate (b), a ceramic member is deposited on both th e adhesion-resistant bodies and the substrate (c), and the resin epoxy is finally removed (d);
FIGS. 15 (a) and (b) depict various parameters that define a micro-mechanical strut at a ceramic oxide interface (a) and the flexure the micro-mechanical struts provide to the ceramic at the interface (b);
FIGS. 16 and 17(a) and (b) depict metal-ceramic composite substrates for printed circuit applications; and
FIGS. 18(a) and (b) and 19 depict metal-ceramic composites with a ferrite ceramic attached to one major surface of the structure.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The following brief analyisis is provided in order to better understand the present invention. In addition, a number of terms used throughout this description are also provided below. The term "ultrafine subdivision" is understood to represent a ceramic whose precursors have been mixed at the molecular level, a s in a solution, as opposed to a ceramic whose precursors were mixed a s particulates with a definitive particle size, as in a slurry. The te rm "secondary phase material" is understood to represent a compositional state of matter dispersed in a ceramic deposited or formed on a metal member, such that the "secondary phase material" is characterized b y an elemental composition, material phase, or crystallographic structure that is different from the deposited ceramic into which it is dispersed. The "secondary phase material" may be a single crystalline phase, a ceramic phase, a glass phase, graphite, a metal phase, a shape-memory alloy phase, or any composite form of said material phases that produces a Young's modulus that is less than the Young's modulus of the ceramic medium into the "secondary phase material" has been dispersed. The term "shape-memory alloy" is understood to represent a metallic phase or glassy metallic phase that exhibits superior ductile properties under mechanical stress and the ability to return to its initial geometric shape and physical dimensions exhibited in an unstressed state after the application of said mechanical stress has been relieved.
Composite bodies that comprise a ceramic member contacted to a metallic member can significantly improve the performance of a conventional non-composite part over a wide range of applications. I n practice, however, unless special measures are taken to engineer a proper interface between the ceramic member and the metal member, the functionality of the composite bodies can be extremely limited a s the intended applications often subject the composite bodies to thermal loads or mechanical stress that cause the metal and ceramic members to become mutually incompatible in a single composite body . Metals and ceramics are essentially characterized by starkly different chemical, mechanical and thermal properties. Metals are, typically, characterized by ductile properties that permit them to elastically flex and accommodate a higher degree of mechanical stress prior to reaching a point inelastic fracture. Metals, typically, exhibit thermal conductivities that are superior to those common to most ceramics. Ceramics, typically, are characterized by rigid mechanical properties that allow them to resist flexure, however, this brittle nature can make the ceramic more susceptible to inelastic fracture u nder equivalent mechanical loads. A composite body, comprised of a metal member bonded to a ceramic member can blend the superior properties of each member to improve device performance in a variety of applications. The ultimate performance in such a composite body will, in m an y instances, be determined by stresses generated at, or close to, the interface between the ceramic member and the metallic member, where the disparate thermal and mechanical properties of one member will oppose the other member's natural response to a n applied thermal or mechanical load beyond its natural ability to do so. An example of a failure mode in a metal-ceramic composite body is easily demonstrated when a typical composite body is subject to strong variations in temperature, and/or large temperature differential across the composite body itself, and the metal-ceramic interface in particular. Under such circumstances, applications failure typically relates to interfacial stress caused by the mismatch in th e coefficients of thermal expansion between the ceramic member an d the metal member. When both members are restrained at th e interface, a simple expression, using the product of the Young's modulus, E, [E = Newtons/mm^], the coefficient-of-thermal-expansion, α [α = K-l (in.(cm)/in.(cm)-°K)], and the temperature differential to which DT, [DT] = K, can be used to assess the thermal dependence of interfacial stress, DS:
AS = KEacemm,AT ( 1 ) where,
"■ ~ _
Figure imgf000014_0001
i. a) and, A represents the area of the subscripted member.
It is straightforward to evaluate the thermal incompatibility of pertinent metal-ceramic composite bodies. For instance, as shown i n FIG. 1 of the drawings, printed circuit boards for high power semiconductor integrated circuits ("SIC's") generally comprise a metal- ceramic composite susbtrate consisting of a low-cost, high thermal conductivity, high electrical conductivity metal sheet 1A bonded to a low-cost, low-dielectric constant, low thermal conductivity ceramic 2 on one major surface of the ceramic, with another low-cost, high thermal conductivity, high electrical conductivity metal sheet I B bonded to the ceramic's opposing major surface. In the printed circuit board application, the metal sheet 1A will be etched to form a network of mounting areas IC, onto which semiconductor integrated circuits 3 are mounted, and electrode areas ID, that are used to transport electrical signals across the surface of the printed circuit board. Aluminum wire 4 is ultrasonically bonded between the SIC 3 and the electrode area ID to electrically connect the semiconductor chip to the electrode network on the surface of the printed circuit board. Prior art has typically used aluminum oxide (alumina) as th e ceramic member 2 and copper as the metal sheets 1A and IB, although it is possible to use other metals and ceramics, such as non- oxide ceramics, to form the printed circuit board structures. Copper has a coefficient-of-thermal-expansion of copper = 16.5 x 10"6 K"1, and a Young's modulus of ECOpper = 11 x 10*4 (Newtons)/mm2, whereas th e coefficient-of-thermal-expansion for alumina ceramic is occemmc= 8.8 x 1 0 "6 K"l , and it has a Young's modulus of Eceramic = 1 60 - 300 (Newtons)/mm2. Using equation (1), it is straightforward to determine that approximately 2 megapascals (MPa) of stress will b e generated for each degree of rise and fall in temperature at th e interface formed when alumina ceramic is directly bonded to copper metal. This means that a 10-15° K (°C) rise or fall in temperature will bring the alumina ceramic to a point of internal fracture. FIG. 2 shows a fracture pattern that is typical of an over-stressed interface, comprising cracks 5 in the ceramic member 6 that is bonded to th e metal member 7. Semiconductor integrated circuits are generally required to operate reliably over temperatures ranging from -40 °C to 150 °C. It is, therefore, essential that the metal-ceramic composite, when used as a printed circuit board substrate on which SIC's are mounted, have reliable function over an identical range of temperatures. Simple metal-ceramic composite structures, wherein metals having a coefficient-of-thermal-expansion comparable to th at of copper are directly bonded to the ceramic member are not sufficient to satisfy these requirements.
In order to achieve reliable function as a printed circuit board, i t is also necessary that the metal member on which semiconductor integrated circuits are mounted satisfy other physical tolerances related to surface roughness and Vickers hardness. Tanaka et al. disclose, in U.S. Patents Nos. 4,959,507 and 4,987,677, that the unit failure rate of metal-ceramic composite substrate circuit boards, wherein the composite substrate circuit boards comprise copper sheets bonded through the eutectic bonding process to the opposing major surfaces of a ceramic member, can be reduced if surface roughness of the copper sheet of the metal-ceramic composite onto which electronic circuits are mounted has a median surface roughness not greater than 3 microns and a maximum surface roughness not greater than 18 microns. Although, the specifications for surface roughness are sufficient, copper members having median surface roughness not greater than 1 micron and a maximum surface roughness not greater than 8 microns are preferred. The reduced surface roughness improves the quality of a solder bond between the semiconductor integrated circuit and the metal surface comprising the mounting area of the metal-ceramic composite substrate onto which it is mounted. Komorita et al. (U.S. Patent No. 5, 155,665) disclose th at the unit failure rate of metal-ceramic composite substrate circuit boards, wherein the composite substrate circuit boards comprise copper sheets with the copper sheets bonded through the eutectic bonding process to the opposing major surfaces of a ceramic member, can be reduced if the Vickers hardness of the copper sheet onto which microelectronic circuits are eventually mounted lies in the range of 4 0 Kg/mm^ to 100 Kg/mm^. Aluminum wire that is ultrasonically bonded to copper sheets with a Vickers hardness less than 4 0 Kg/mm ^ is prone to rupture in the vicinity of the bond, as th e ultrasonic energy used in the bonding process is sufficient to bury th e wire into the soft copper sheet and catastrophically elongate th e aluminum wire. An ultrasonic bond formed between aluminum wire and a copper sheet with a Vickers hardness greater than 100 Kg/mm 2 frequently has poor adhesion as the ultrasonic wave is attenuated i n the hard copper sheet. Metal-ceramic composite substrates that have copper mounting areas with a Vickers hardness in the range between 60 Kg/mm^ to 80 Kg/mm^ are preferred in printed circuit bo ard applications.
Interfacial stress at a metal-ceramic composite interface can b e reduced if the metal member bonded to the interface contains a constraining-metal member which acts to restrain the linear thermal expansion of the metal member. Kashiba et al, describes in U.S. Patent Nos. 5, 153,077 and 5,251 ,803 the use of a constraining-metal memb er integrally-bonded into a metal-ceramic composite substrate, wherein the constraining-metal member reduces thermally-generated mechanical stress at the interface between metal and ceramic members in the composite structure, or between the metal layer and a semiconductor integrated circuit mounted on the metal member. I n addition to having a lower coefficient-of-thermal-expansion, the constraining-metal layer must have a higher yield strength than the copper sheet to which it is bonded. Copper has a yield strength of 1 0 Kg/mm^, whereas molybdenum, a suitable constraining-metal member, has a yield strength of 50 Kg/mm^. The ductile copper, restrained by the constraining-metal member, will not crack as its elastic properties absorb the stress generated by linear expansions a t the copper-constraining-metal interface during thermal cycling. The ceramic member in such a metal-ceramic composite structure is subject to a reduced level of mechanical stress as thermally generated linear expansions of the modified metal member are determined b y the constraining-metal member's coefficient-of-thermal-expansion. Thus, a constraining-metal modified metal-ceramic composite comprising an alumina ceramic, aceramιc= 8.8 x 10~6 K~ l and Eceramjc =
160-300 N/mm2, and molybdenum as the constraining-metal member, molybdenun = 5Λ3 x 1 0" 6 K" l and Emolybdenum = 33.1 x 10*4 N/mm2, will experience 0.7 MPa of stress for each degree of rise an d fall in temperature, according to equation (1). This means that a 3 0 - 45 K (°C) rise or fall in temperature will bring the alumina ceramic to a point of internal fracture. While this represents a substantial improvement over metal-ceramic composites that do not contain constraining-metal layers, improvements upon the prior art are clearly desirable for semiconductor applications, as well as o ther applications in which the metal-ceramic composite is subjected to even greater thermal or mechanical loads.
The present invention provides methods to improve the thermal and mechanical integrity of metal-ceramic composites that have a t least one interface in which the composite's metal member is directly bonded to the ceramic member. These improvements to the prior ar t relate specifically to the construction methods used to assemble the metal-ceramic composite. Additionally, the present invention improves the interfacial properties and fracture mechanics of metal- ceramic composites by allowing more fracture-resistant forms of alumina ceramic to be assembled into the composite and by adding micro-mechanical features to the bonding surface of the ceramic member in contact with the metal member that increase the flexure of the ceramic member in response to linear expansions or contractions of the metal member. The present invention also introduces methods to control the fracture mechanics of the interface.
Another significant attribute of the present invention is that i t allows the metal-ceramic composite to be formed at much lower processing temperatures. Prior art construction methods utilize pre fabricated ceramic and metal members that are bonded together using processing techniques that subject the metal-ceramic composite to temperatures at least in excess of 900 °C. It is well known to practitioners skilled in the art of heat-treating sheet metal th at prolonged exposure to elevated temperatures close to the melting point of the metal sheet, i.e., within 200 °C of its melting point, will reduce its hardness. The degree to which the hardness is reduced is a function of both the temperature as well as the time period over which the metal sheet is exposed to the elevated temperature . Increasing the time period over which the metal is exposed to a n elevated temperature sufficient to soften the metal will proportionally reduce its hardness.
The present invention further improves upon the prior art b y being a low-temperature process and one that can be suitably engineered for continuous production. These processing features not only impact the ease with which metal-ceramic composites can b e produced, they also increase the economy of industrial production. Methods detailed in the prior art represent batch production techniques, in which production units are produced in units of one, or multiples of one depending on batch size. This means all th e component parts to the finished product need to be prepared to unit size prior to assembling the final product. Batch production methods are less efficient because they generally represent multiple processing and quality assurance steps for each of the components during sub - assembly prior to forming the finished good in final assembly. Continuous production methods improve the economy of an industrial process by reducing the number of processing steps and increasing production rate. As detailed below, the present invention can b e easily engineered into a continuous process. Metal-ceramic composite substrates for printed circuit board applications are easily assembled by rolling copper sheet into a deposition chamber where a layer of alumina ceramic is spray-pyrolyzed onto its surface to form a sheet comprising a metal layer bonded to a ceramic layer. Two such sheets, or one sheet folded onto itself, are joined through a mechanical swaging step, ceramic face to ceramic face, to form the metal-ceramic- metal composite substrate structure. Finished products are then stamped out of a continuously processed sheet. By virtue of the present invention comprising a low-temperature continuous process, i t is not necessary to start with excessively hardened copper sheets to achieve metal-ceramic composite substrates in which the copper mounting and electrode areas satisfy hardness tolerances necessary to produce a reliable printed circuit board. Since all the bonding step s utilized under the present invention can be realized at temperatures below 900°C, hardness reduction during subsequent annealing steps is mitigated by lower temperature processing, providing more control over the Vickers hardness of the metal members in the finished composite.
An essential feature of the present invention is that it allows a ceramic member to be bonded to any metal member, stainless steel, for example, but not limited thereto, irrespective of metal and ceramic * composition(s), through a covalent bond formed using processing temperatures that can be less than 500°C. More specifically, ceramic oxide is bonded to metal at low-temperature by the method of metalorganic chemical spray pyrolysis. Using this method, metal precursors to the ceramic oxide composition are introduced a s metalorganic salt complexes, (i.e., metal complexes having organic ligands), into an organic solvent. Together, they form the metalorganic precursor solution.
A distinguishing characteristic of metal-ceramic composites manufactured using the metalorganic spray pyrolysis process is that a direct rigid bond is formed between the metal and the ceramic members without the use of an adhesive or bonding agent th at comprises a compositional state of matter that is different from th e ceramic and the metal member, such as is the case when a solder material or a eutectic material is used to form the bond. By virtue of covalent bonding between the metal and the ceramic members, a compositional profile of the metal-ceramic interface is characterized by an abrupt termination of the metal composition and an equally abrupt beginning of the ceramic composition. These interfaces do not contain a formerly liquid phase material that has been solidified into a layer many tens of microns thick to form the bond. As will be shown below, this method of forming a "clean " interface now makes it possible to engineer micro-mechanical features bonded to the ceramic, but not to the metal, that enhance the interfacial properties of th e composite body.
One aspect of the present invention, shown in FIG. 3, is th e incorporation of secondary phase material particles dispersed in a ceramic medium. For example, a crack 24 propagating through a brittle ceramic medium 25 that has been generated by stresses at th e interface between the brittle ceramic medium 25 and a metal member 26 will be deflected or have its energy partially absorbed when i t encounters the secondary phase material particles 27 dispersed in the brittle ceramic medium. As a result, the secondary phase material particles dispersed throughout a brittle medium increase the crack resistance of the brittle medium. The fracture mechanics of a composite body can also be improved if the composite body is formed in a manner that allows thermally compressive forces to pre- stress the composite body in a manner that opposes, much as is the case wi th a pre-stressed bolt, the thermal and mechanical loads anticipated from an intended application. Similarly, interfacial stress between a high thermal expansion coefficient metal and a lower thermal expansion coefficient ceramic can be reduced by modifying the Young's modulus of the high thermal expansion coefficient metal. Suitable modifications to the high thermal expansion coefficient metal would include perforating the high thermal expansion coefficient metal or b y making it porous. As set forth below, the present invention allows any, or all, of these improvements now to be incorporated into th e construction of metal-ceramic composite bodies.
A metal-ceramic composite with improved interfacial properties according to this invention can be manufactured as follows:
Specifically, the present invention utilizes a method to produce a metal-ceramic composite in which the ceramic member forms a covalent bond with the metal member by the method of metalorganic spray pyrolysis. The ceramic member consists of a primary ceramic medium with ultrafine subdivision that has been formed on the metal member from a spray pyrolyzed metalorganic solution, and th e ceramic member contains a dispersion of previously formed particles of secondary phase materials that increase the crack resistance in th e ceramic member. The particles 27 of secondary phase materials are dispersed in the ceramic medium by forming a colloidal suspension of the secondary phase materials in the metalorganic solution prior to spray pyrolyzing the metalorganic solution containing a colloidal suspension of the secondary phase material particles 27 on the metal member of the metal-ceramic composite. The metalorganic precursors are pyrolyzed into oxide ceramic on the metal member subs trate heated to temperatures typically greater than 250°C, and typically less than 500°C. This range of temperatures is generally insufficient to dissolve the secondary phase material particles 27 into the ceramic medium 25. As a result, particles 27 of secondary phase materials dispersed throughout the metalorganic solution become dispersed, a s secondary phase material particles, in the spray pyrolyzed ceramic. I t is a preferred embodiment of this invention to use particulates of secondary phase materials that are characterized as having intrinsic mechanical properties that are less brittle, i.e., has a lower Young's modulus, than the ceramic medium 25 formed around them by th e pyrolyzed metalorganic precursor solution. The secondary phase material particles 27 may comprise a metal or metal alloy, a glass phase, a shape memory alloy, graphite, an oxide or non-oxide material, or a crystalline ceramic or single crystal material phase.
This particular aspect of the invention has special significance for alumina-based (Al2θ3-based) or titania (Tiθ2-based) ceramic members on metal substrates. As mentioned above, the prior art instructs on the construction of metal-ceramic composites formed b y bonding a previously formed ceramic member (i.e., a ceramic memb er that already has been sintered, cut, and polished) to metal sheets . Alumina represents one of the most highly refractory oxide ceramics. It liquefies at temperatures above 2054°C, and forms a partial liquid phase suitable for sintering at temperatures above 1828°C. Given these highly refractory properties, it is exceedingly difficult to disperse particles of a mechanically "softer" secondary phase material within a solid solution of alumina ceramic without completely dissolving the secondary phase material particles completely into a ceramic formed from sinter-reacted powders. The present invention allows a colloidal suspension of secondary phase material particles to be dispersed throughout a solid solution of ceramic that is spray pyrolyzed around the secondary phase material particles a t temperatures well below 1828 °C. The spray pyrolyzed ceramic m a y be crystallized and textured using a repetitive sequence of incremental reaction and mechanical swaging steps. During th e formation of metal-ceramic composites that comprise a ceramic member possessing a thermal reaction temperature in excess of th e melting temperature of the metal member to which it is bonded, it is preferred to utilize electromagnetic radiation to react and crystallize the ceramic member. In this embodiment a beam of electromagnetic radiation, characterized by an electromagnetic energy that is either i n the microwave frequency spectrum or in the infrared frequency spectrum, can be directed onto the ceramic member to advance its state of crystallization. Simultaneously, the metal member, which is not irradiated by a suitably directed electromagnetic beam, can b e held to a temperature well below its melting point. It is now well known to practitioners skilled in the art of microwave annealing of ceramic and other materials, that certain frequencies of radiation will preferentially react certain chemical species of the irradiated material. It is a preferred embodiment of this invention to utilize a microwave frequency that induces strong crystallization in the alumina ceramic, but induces only a mild reaction with the secondary phase materials particles. The secondary phase material particles may have spheroidal dimensions ranging between 0.05 microns and 500 microns. Secondary phase materials particles with spheroidal dimensions less than 0.05 microns will have a tendency to b e dissolved into the ceramic medium into which they have been dispersed during reaction treatments. Secondary phase material particles with spheroidal dimensions greater than 500 microns are so large that their intrinsic material properties have a tendency to dominate over the material properties of the ceramic medium into which they have been dispersed. A preferred embodiment of the present invention utilizes the secondary phase material particles having spheroidal dimensions in the range between 0.10 and 5 0 microns. It is often desirable to form a metal-ceramic composite comprising a metal member having a coefficient-of-thermal-expansion that is significantly greater than the coefficient-of-thermal-expansion of the ceramic member. As mentioned above, the thermal performance of the metal-ceramic composite composed of metal an d ceramic members having incompatible coefficients of thermal expansion can be improved if the ceramic member in the metal- ceramic composite is maintained in a state of compressive stress over the range of temperatures at which the metal-ceramic composite is expected to operate. Such a state can be achieved if the metal member in the metal-ceramic composite is heated to a temperature that is greater than, or nearly equal to, the maximum temperature to which the pre-stressed metal-ceramic composite is expected to reach during an operational cycle prior to depositing the ceramic member o n the metal member. It is a preferred embodiment of this invention to maintain the metal member and the deposited ceramic member at the elevated temperature until the pre-stressed metal-ceramic composite is fully constructed. Upon cooling to room temperature, the metal member in the pre-stressed metal-ceramic composite will contract to a much greater degree than the ceramic member, leaving the ceramic member in a state of compressive stress.
Furthermore, since the metal-ceramic composite is produced b y depositing the ceramic member on the metal member, the present invention provides other means to manipulate the stress response of the ceramic to steady-state thermal loads that induce a temperature differential across the deposited ceramic member. For instance, a heat shield, manufactured by bonding a high thermal conductivity metal sheet to a thermally insulating ceramic on one major surface and exposing the opposing major surface of the metal sheet to a heat source, can be used to diffuse heat to heat sinks located at the minor surfaces of the high thermal conductivity metal sheet, thereby impeding heat flow through the major surface at which the thermally insulating ceramic is bonded. Under steady-state conditions, th e temperature of the thermally insulating ceramic member will b e elevated to a higher temperature on the major surface at which it is bonded to the thermally conducting metal member, and be reduced to a lower temperature on its opposing major surface. As a consequence of this temperature profile across the thermally insulating member, the thermally insulating ceramic member will linearly expand to a greater degree at the major surface where it is bonded to the high thermal conductivity metal, and will linearly expand to a lesser degree if the thermally insulating ceramic member has uniform composition and an uniform coefficient-of- thermal-expansion. This difference in linear expansion produces a shear stress within the thermally insulating ceramic member having uniform coefficient of thermal coefficient. Under the present invention, the thermally insulating ceramic member is deposited on the metal member by spray pyrolyzing a solution of metalorganic precursors. The invention permits the composition of the ceramic member to be altered b y adjusting the precursor concentration of the metalorganic solution with the thickness of the deposited ceramic. As shown graphically i n FIG. 4, it is, thus, another preferred embodiment of the pres ent invention to reduce shear stress in a ceramic member of a thermally loaded metal-ceramic composite by introducing a composition profile in the ceramic member 19 bonded to the metal member 20, to produce a gradient in the coefficient-of-thermal-expansion within the ceramic member in a manner that reduces shear stress in the ceramic member.
Another aspect of this invention is to reduce the Young's modulus or the effective coefficient-of- thermal-expansion of the metal member in the metal-ceramic composite having metal and ceramic members with incompatible coefficients of thermal expansion. It is a preferred embodiment of this invention to reduce the Young's modulus of the metal member having a coefficient-of- thermal-expansion that is significantly greater than the coefficient-of-thermal-expansion of th e ceramic member to which it is bonded by drilling holes in the metal member. These holes can be drilled prior to forming the ceramic o n the perforated metal member, or after the metal-ceramic composite has been formed by means of conventional press drilling or laser drilling.
It is also a preferred embodiment of this invention to reduce th e effective linear expansion of the metal member having a coefficient- of-thermal-expansion that is significantly greater than the coefficient- of-thermal-expansion of the ceramic member to which it is bonded i n the metal-ceramic composite, by incorporating a constraining-metal member 28 into the metal member as shown in FIGS. 5 (a), (b) and (c), such that the constraining-metal member 28 incorporated into th e metal member has a thickness that is l/20Lfa to 1/3^ the thickness of the metal member having a high coefficient-of-thermal-expansion. The constraining-metal member 28 may be situated such that it is bonded on one major surface to the deposited ceramic member 29 , and bonded to the high coefficient-of-thermal-expansion metal member 30A on its other major surface as diagrammed in FIG. 5(a). The constraining-metal member 28 also may be situated such that it is bonded on one major surface to the high coefficient-of-thermal- expansion metal member 30B, and the high coefficient-of-thermal- expansion metal member 30B is bonded to the deposited ceramic member 29 on its other major surface as diagrammed in FIG. 5(b). Alternatively, the constraining-metal member 28 may be situated such that it is bonded on one major surface to a high coefficient-of- thermal-expansion metal member 30A', and is bonded to another high coefficient-of-thermal-expansion metal member 30B' on its other major surface, with the other high coefficient-of-thermal-expansion metal member 30B' bonded to the deposited ceramic member 29 on its other major surface as diagrammed in FIG. 5(c). The present invention, by virtue of being a low-temperature manufacturing process, represents a further improvement over the prior art because it allows a far greater selection of high coefficient- of-thermal-expansion metal member bonded to constraining-metal member combinations to be constructed. Furthermore, in m any applications for metal-ceramic composites it is desirable to couple a high thermal conductivity and/or electrical conductivity metal member to a thermally insulating and/or electrically insulating ceramic member. This is particularly true for metal-ceramic composites used as substrates in printed circuit board applications. I n such instances, semiconductor integrated circuit elements are mounted on a metal member of the metal-ceramic composite substrate. The metal member is used to transport electrical current and also is u s ed to dissipate heat generated by the SIC. In such applications it is particularly useful for the metal member to maximally dissipate heat and transport maximum levels of electrical current. As shown in Table I, metals that exhibit higher electrical and thermal conductivities commonly exhibit higher coefficients of thermal expansion, whereas metals with high yield strengths and low coefficients of thermal expansion, which are suitable for use as a constraining-metal member, typically exhibit poorer electrical and thermal conductivities. In order to achieve maximal operating performance in the printed circuit applications, it is preferable to configure the metal-ceramic composite with the constraining-metal member bonded between the ceramic member and the high thermal conductivity and/or high electrical conductivity metal member a s shown in FIG. 6(a). It is straightforward to ascertain that the constraining-metal member in configurations of metal-ceramic composites such as those depicted in FIGS. 6(b), (c) will hinder the transport of electrical current to and from, or the dissipation of heat from, a semiconductor integrated circuit mounted on the exposed major surface of the metal member. However, in many practical applications it is preferable to utilize the less optimal configuration shown in FIG. 6(c) when the thermal expansion of, and stres s distribution in, the metal-ceramic composite during an operational cycle is considered. These points are most clearly demonstrated using computer simulations that visually plot the stress distributions an d mechanical deformation which results when a given composite design is subjected to a thermal load typical of an operational cycle.
TABLE I
Electrical Thermal Coefficient of Elastic Modulus
Resistivity Conductivity Thermal Expansion Poission Shear Tensile
Material (Ω-m) (Wm 'K 1) (HT K ') Ratio (GPa) (GPa) Hardness
Conducting Metal
Aluminum 2.65 x 104 237 23.03 0.40 25 62 200 HV
Copper 1.67 x Ϊ0 401 16.5 0.343 46.8 125 37 HRB
Silver 1.59 x 10** 429 19.2 0.37 46.3 125 25 HV
Gold 2.35 x 10** 317 14.2 — — 378
Constraining Metal
Antimony 39 x 10** 243 8.5 0.25 19 77.7 —
Chromium 12.7 x 10** 93.7 8.5 — — 154
Indium 5.3 x 10** 147 6.2 0.26 0.21 1.2 200 HV
Molybdenum 5.2 x 10*1 138 5.43 0.307 107 350 —
Tantalum 12.45 x 10** 57.5 6.6 0.35 69 186 120 HV
Tin (α-phase) l l.O x 10* 66.6 5.34 0.33 13.7 41.6, —
- Titanium 42.0 x 10** 21.9 8.33 0.34 80 235 70 HB
Tungsten 5.65 x 10*1 174 4.59 0.28 155 400 150 HV
Vanadium 24.8 x 10** 30.7 8.3 0.36 46.4 130 70 HB
Ceramic
Alumina 10*" 0.42 ■8.8 — — 0.04 —
Ferrite 4 lO ' - lO*10 4.0 7-10 — 36 0.02 6 (Mohs ;
FIG. 7 depicts magnified views of the structural response in 2 different configurations for metal-ceramic composite substrates in typical printed circuit board applications as simulated by finite element method ("FEM") analysis. The FEM analysis presented assumes the metal-ceramic composite structure sketched in FIG. 6(a). As shown on FIG. 6(a) the FEM model consists of a 150 °C heat source 31 to represent an SIC, and has heat sinking cooling fins 32 at the edge of a 3.00 mm thick copper mounting area 33, which is bonded to a 0.45 mm thick constraining-metal member 34. The constraining- metal member 34 is bonded through its opposing major surface to a 1.00 mm alumina ceramic member 35, which, in turn, is bonded through its opposing major surface to a 0.30 mm thick copper ground plane member 36. The model further assumes the materials properties for alumina, copper, molybdenum and titanium a s tabulated in Table I. The outer edges of the model (including the cooling fins) are subject to an environmental load of 27 °C and convective heat loss of 4.33 x 10~6 W/mm^. The system has been allowed to relax to its steady-state equilibrium values to simulate conditions of maximal thermal loading. FIG. 6(b) depicts a magnified view (20x) of the FEM-simulated deformation to the metal-ceramic composite when the constraining- metal layer in the model comprises molybdenum. FIG. 6(b) models the molybdenum-containing composite in the symmetrical half-plane. As is clearly shown, the thermally loaded structure 37 is quite deformed from the stress-free structure 38. In this case, the molybdenum metal layer linearly expands at a rate ( t.molybdenum= 5.43 x 10" 6 °C~ 1 ) that is less than both the rates for the ceramic member ( «a.umina= 8.8 x 10"6 °C"1 ) and the copper member ( o copper= 16.5 x 1 0- 6 °C-1) to which it is attached. In fact, stress analysis shows that the von Mises stresses in a metal-ceramic composite printed circuit board substrate containing a molybdenum constraining-metal layer situated as depicted in FIG. 6(a) are, in fact, greater than the von Mises stresses for a metal-ceramic composite printed circuit board substrate th at does not contain the molybdenum constraining-metal member. FIG. 6(c) depicts a magnified view (20x) of the FEM-simulated deformation to the metal-ceramic composite when the constraining- metal layer in the model comprises titanium. Again, FIG. 6(c) models the composite in the symmetrical half-plane. As is clearly shown, structural deformation to a metal-ceramic composite printed circuit board substrate containing a titanium constraining-metal memb er directly bonded to the ceramic member is generated by thermal loading 39 when compared to the stress-free structure 38. This deformation is greatly reduced when compared to the deformation generated in the thermally loaded metal-ceramic composite th at contains a molybdenum constraining-metal member. Titanium has a coefficient-of-thermal-expansion ( «„tan,„„,= 8.33 x 1 0*~6 °C_ 1) that is a far better match with alumina ( αa,umιna= 8.8 x 10 "6 °C~1), and, as a result, reduces von Mises stress in the ceramic by more than 50%.
The improved structure cannot be reduced to practice using a high-temperature process, such as those described by the prior art. As reported by Kashiba et al., titanium and copper form an eutectic a t temperatures greater than 880 °C. Therefore, a process that requires a copper member to be mechanically pressed to a titanium member a t a temperature of at least 900 °C for a period of at least 20 minutes will cause the members to form their eutectic and liquefy. Under th e present invention, a covalent bond is formed between the deposited ceramic member and the metal member(s) at temperatures less than 550 °C. As such, the present invention makes possible th e construction of a much wider variety of high electrical or high thermal conductivity metal member bonded to constraining-metal member combinations. It is, therefore, a preferred embodiment of the pre sent invention to deposit a ceramic member on a metallic me m ber substrate, wherein the metallic member substrate comprises at least one high coefficient-of-thermal-expansion metal member consisting of a pure metal, metal alloy, or metal composite of aluminum, copper, silver, or gold, that is bonded, on at least one major surface, to a constraining metal member, wherein the constraining-metal memb er may comprise a pure metal, metal alloy or metal composite of antimony, chromium, iridium, molybdenum, tantalum, (α-)tin, titanium, tungsten, or vanadium. The high coefficient-of-thermal- expansion metal member may be characterized as having a high electrical conductivity and/or high thermal conductivity. The constraining-metal member bonded to the metal member with a high coefficient-of-thermal-expansion may be characterized as having a coefficient-of-thermal-expansion that is less than the coefficient of expansion of the metal member to which it is bonded. It is preferred to have the constraining-metal member bonded to the metal memb er having a high coefficient-of-thermal-expansion through explosive pressure welding, or other metal-metal bonding techniques known to practitioners skilled in the art of metallurgy, prior to forming a covalent bond with the deposited ceramic member.
The ability to form a covalent bond between the deposited ceramic member and the metallic substrate without a molten bonding agent or adhesive, as is enabled under the present invention, permits even greater improvement to the prior art by introducing stress- reducing micro-mechanical elements to the interface. The pre sent invention allows, as shown in FIG. 7(a) for at least one adhesion- resistant body 40 to be placed on the surface of the metal member substrate 41 onto which the ceramic member will be deposited prior to depositing the ceramic member. The adhesion-resistant body can b e blown of the surface of the metal member substrate during th e ceramic deposition process, therefore it is a preferred embodiment of this invention to physically secure the at least one adhesion-resistant body on the surface of the metal member substrate without forming a permanent bond between the at least one adhesion-resistant body an d the metal member substrate by coating the adhesion-resistant body with a resin epoxy 42 as shown in FIG. 7(b)) that decomposes a t temperatures greater than the substrate deposition temperature to which the metal member substrate is heated during the ceramic deposition process. The ceramic member 43 as shown in FIG. 7(c) is then spray pyrolyzed from a metalorganic solution on to the metal member substrate 41 and the at least one adhesion-resistant body 4 0 physically attached to or placed on the metal member substrate an d processed to form the metal-ceramic composite. After the deposited ceramic member 43 has been formed to a sufficient thickness on th e metal member substrate and the at least one adhesion-resistant body, the entire metal-ceramic composite can be heated to a temperature that decomposes the resin epoxy 42 that physically secures the a t least one adhesion-resistant body to the metal member substrate, (typically to a temperature in the range between 450 °C to 550 °C), to produce a metal-ceramic composite in which a rigid covalent bond h a s been formed between the metal member substrate 41 and th e deposited ceramic member 43 only at those regions of the metal- ceramic interface that are not occupied by the at least one adhesion resistant body 44 as shown in FIG. 7(d). If the adhesion-resistant body is composed of a material composition and phase that does not liquefy and form a rigid bond through molten action, regions 45 of th e metal-ceramic interface that are occupied by the at least one adhesion resistant body will not be bonded to the adhesion-resistant body, n or to the deposited ceramic layer. The adhesion-resistant body 40 will be allowed to slip relative to displacements or linear expansions of th e metal member substrate 41 at the non-bonded regions 45 of th e metal-ceramic interface. This embodiment of the present invention cannot be produced using metal-ceramic bonding techniques, such a s eutectic bonding or active metal/solder bonding, which form the bond through a liquefied or molten phase that, when pressed, is smeared, and forms a rigid bond when cooled, across the entire bonding surface.
The cross-sectional geometry of each adhesion-resistant body need not be circular as depicted in drawings and may assume an y cross-sectional geometry that improves the crack-resistance of the deposited ceramic member, or reduces the stress distribution within the metal-ceramic composite. The cross-sectional geometry for th e adhesion-resistant body can be determined for a given application using computer simulation by any practitioner skilled in the art of finite element method analysis. Similarly, the at least one adhesion- resistant body need not be a discrete body, but a series of continuous bodies, such as whiskers, platelets or fibers. For instance, a fiber or wire mesh can be utilized to pattern a adhesion-resistant body grid a t the metal-ceramic interface. In certain specific applications specific patterns of adhesion-resistant bodies, which might comprise adhesion- resistant bodies of differing cross-sectional geometry, or a combination of discrete and continuous adhesion-resistant bodies of varying shapes and sizes, are preferred. FIGS. 8 (a) and (b) represent top perspectives of some, but by no means all, representative patterns of adhesion-resistant bodies 40 o n metal member substrates 41 that may be useful. Such patterns of adhesion-resistant bodies can be fixed on the surface of the metal member substrate using a variety of means, including, but not limited to, screen printing or other printing techniques such as, letterpress, gravure, rotogravure, dot and or jet printing. A particular pattern of adhesion-resistant bodies will, of course, be dependent upon on the thermal and/or mechanical loads of a specific application, and can b e determined using computer simulation by any practitioner skilled i n the art of finite element method analysis or other computer simulation methods. The use of adhesion-resistant bodies to construct a metal- ceramic composite with improved interfacial properties in any p attern is considered an element of, and as having been instructed by, th e present invention.
The adhesion-resistant bodies may be produced from a variety of materials that do not liquefy or form a molten or rigid bond with th e metal member to which the adhesion-resistant bodies are contacted i n a metal-ceramic composite. Therefore, its is recommended to compose the adhesion-resistant bodies from a material that melts a t temperatures greater than the maximum temperatures (450-880 °C) to which the metal-ceramic composite may be exposed, the adhesion- resistant bodies may be composed of materials that comprise, but are not limited to, metals or metal alloys, a glass phase, a shape memory alloy, graphite, an oxide or non-oxide material, or a crystalline ceramic or single crystal material phase.
As shown in FIGS. 9 (a) and (b) it is another preferred embodiment of this invention to utilize adhesion-resistant bodies composed of a material phase that can be selectively etched o r removed from the metal-ceramic composite after processing to produce voids 46 in the deposited ceramic member 43 bonded to th e metal member substrate 41 of the metal-ceramic composite where th e selectively etchable adhesion-resistant bodies were originally located as shown in FIG. 9(a). This aspect of the invention allows micro- mechanical struts 47 to be produced in the ceramic member that can flex in response to lateral displacements of the bonded metal member caused by linear expansions or contractions of the bonded metal member. FIG. 9(b) depicts the flexure in a thermally loaded composite 39 compared to its stress-free state 38. The flexure provided by th e micro-mechanical struts in the ceramic member reduces the shear stresses normally generated in the interior of a bonded ceramic member which typical induce cracking of the bonded ceramic member. The degree of stress reduction in the bonded ceramic member is dependent upon the physical dimensions of the micro- mechanical struts, which may be defined as having a width, w, a depth, d, and a spacing, s as shown in FIG. 9(a). FIG. 10 graphically depicts characteristics curves for the stress reduction in the ceramic member at distances of 20 microns A , 52 microns B, and 185 microns C versus the depth parameter (d-parameter) of micro-mechanical struts that have a width (w -parameter) of 50 microns, and a spacing (s-parameter) equal to 50 microns. FIG. 11 depicts characteristics curves for the stress reduction in the ceramic member at distances of 20 microns D, 52 microns E, and 185 microns F versus the width parameter (w -parameter) of micro-mechanical struts that have a depth (d-parameter) of 150 microns, and a spacing (s-parameter) equal to 50 microns. Hygroscopic glass materials are preferred for use as th e selectively etchable adhesion-resistant body materials used to produce patterns of voids and micro-mechanical struts in the bonded ceramic member. Hygroscopic glass materials can be dissolved i n water without risking erosion of the composites metal and ceramic members by simply immersing the composite into an aqueous ultrasonic bath medium. Glass materials can be easily shaped into microscopic geometries and patterns using methods well known to practitioners skilled in the art of producing optical fiber, fiber-optic bundles, and micro-optical components. It is a preferred embodiment of this invention to utilize phosphate-based and or borate-based hygroscopic oxide glasses as the selectively etchable adhesion- resistant bodies.
Non-metallic Substrates
In many desired applications of ceramics, particularly carbide o r carbon-based ceramics, it is desirable to apply an oxide coating to the carbon-containing ceramic body for the purposes of environmental protection. For instance, applications that may expose such ceramics to temperatures in excess of 800° C in oxygen-containing atmospheres can lead to the combustion of the ceramic body. The application of a n oxide ceramic coating to the carbon-containing ceramic body could protect the body from oxidative corrosion and/or combustion as th e coating is inert to those atmospheric conditions and could be used to impede the diffusion of oxygen to the protected ceramic body.
A problem with this solution is the general mismatch in th e coefficients of thermal expansion between the oxide coating and th e protected ceramic body which causes the coating to crack and fail over the desired temperature range. It is therefore desirable to provide means by which protective oxide coatings could be applied to such ceramics in such ways as to prevent mechanical failure which leads to the ultimate decomposition of the ceramic body. The methods developed to reduce shear stresses caused b y mismatched coefficients of thermal expansion at the composite interface between a metal layer and a ceramic layer can also b e applied to relieving crack-inducing shear stresses at the interface between an oxide ceramic coating and an environmentally sensitive non-metallic substrate, such as a carbide ceramic, or a carbon-based ceramic. It is anticipated that similar benefits can be derived wh en applying protective oxide coatings to nitride ceramic substrates under appropriate conditions for that material system.
It is therefore a preferred embodiment of this invention to apply an oxide ceramic coating to a non-metallic substrate, such as a carbide ceramic, carbon-based ceramic, or nitride ceramic, using the methods recited above so as the oxide containing coating medium contains secondary phase particles that improve the crack-resistance of the oxide coating. These secondary phase particles are characterized a s having intrinsic mechanical properties that are less brittle, i.e., the secondary phase has a lower Young's Modulus than the protective ceramic medium. As recited above, these secondary phase particles may be dispersed throughout the metalorganic solution prior to spray pyrolysis, and, as a result, become dispersed in the deposited oxide coating after spray pyrolysis upon the non-metallic substrate. Since the present invention allows the oxide coatings to be deposited over a relatively low-temperature range, typically greater than 250° C and less than 500° C, the substrate's exposure to oxidizing atmospheres during deposition does not threaten oxidative decomposition or combustion of the non-metallic substrate. As recited above, th e secondary phase material particles may comprise a metal or metal alloy, a glass phase, a shape memory alloy, graphite, an oxide or non- oxide material, or a crystalline ceramic or single crystal material phase. The physical dimensions of the secondary phase material particles recited above are invoked by extension.
Similarly, thermally-induced shear stresses can be reduced using a protective oxide coating that has a non-uniform coefficient of thermal expansion. The invention permits the composition of th e oxide coating to be altered by adjusting the precursor concentration of the metalorganic solution with the thickness of the deposited ceramic. It is, thus, another preferred embodiment of the present invention to reduce shear stresses in the protective oxide coating on a thermally- loaded non-metallic ceramic substrate by introducing a compositional profile in the oxide coating bonded to the non-metallic substrate th at produces a gradient in the coefficient-of-thermal-expansion within th e protective oxide coating in a manner that reduces shear stresses in th e protective oxide coating. Likewise, as for the case with metallic substrates described above, the use of adhesion-resistant bodies at the interface between the protective oxide coating and the non-metallic substrate is also a preferred embodiment of the invention. Reference is now made to Figures 12, 13 andl4(a-d) to illustrate and describe the use of a non- metallic substrate or member 26' and 41' . The remaining components use the same reference numerals as previously used throughout th e description of the drawings. Using identical methods, modified for a non-metallic ceramic substrate 41 ', at least one adhesion-resistant body 40 is place on the surface of the non-metallic substrate 41 ' onto which the protective oxide ceramic coating will be deposited prior to depositing the ceramic oxide layer.
It is a preferred embodiment of this invention to physically secure the at least one adhesion-resistant body 40 on the surface of the non-metallic substrate 41 ' without forming a permanent bond between the at least one adhesion-resistant body and the non-metallic substrate by coating the adhesion-resistant body with a resin epoxy that decomposes at temperatures greater than the substrate deposition to which the non-metallic substrate is heated during the ceramic deposition process. The protective ceramic coating is then spray pyrolyzed from a metalorganic solution on to the non-metallic substrate 41 ' and the at least one adhesion-resistant body 40 physically attached to or placed on the non-metallic substrate an d processed to form the ceramic composite.
As a result, a rigid covalent bond has been formed between the non-metallic substrate 41 ' and the deposited protective ceramic oxide layer only at those regions of the oxide ceramic-non-metallic substrate interface that are not occupied by the at least one adhesion-resistant body. The same physical specifications, such as shape, pattern distribution, and physical properties, for adhesion-resistant body recited above for the case of the metallic substrate are invoked in this description.
Similarly, another preferred embodiment of this invention is to utilize adhesion-resistant bodies composed of material that can b e selectively etched or removed from the protective oxide ceramic-non- metallic substrate composite after processing to produce voids in th e deposited protective oxide layer where the selectively etchable adhesion-resistant bodies were originally located. This aspect of the invention allows micro-mechanical struts as shown in Figs. 15(a) an d 15(b) to be produced in the protective oxide ceramic layer that can flex in response to lateral displacements of the bonded non-metallic substrate caused by linear expansions or contractions of the bonded non-metallic substrate41 ' .
Printed Circuit Boards
Another particular aspect of the metal-ceramic composites of thi s invention relates to the use of the metal-ceramic composites as a metal-ceramic composite substrate for printed circuit boards. As discussed above, metal-ceramic composite substrates for printed circuit boards comprise a high conductivity metal sheet member, commonly a copper sheet on which semiconductor integrated circuits are eventually mounted. The metal sheet member is bonded on a major surface to an insulating ceramic member with a low-dielectric constant, typically alumina, which, in turn, is bonded on its opposing major to another high conductivity metal (copper) sheet. The copper sheet upon which SIC's are eventually mounted is required to satisfy certain tolerances for the metal-ceramic composite substrate to operate reliably as a printed circuit board, and may contain a constraining-metal member to reduce its effective coefficient-of- thermal-expansion.
Tolerances relating to the surface roughness of the metal member on which SIC's are mounted require the metal member to have at least a median surface roughness of 3 microns and a maximum surface of 18 microns, although a median surface roughness of 1 micron and a maximum surface roughness of 8 microns are preferred. It is also preferable to chemically polish the metal member in a mixture of sulfuric acid and hydrogen peroxide for a period of 1 to 5 minutes to attain a surface finish within these tolerances. Tolerances relating to the Vickers hardness of the metal member on which SIC's are mounted require the metal member to have a Vickers hardness that is at least in the range of 40- 100 Kg/mm.2, although a Vickers hardnes s in the range of 60-80 Kg/mm^ is preferred.
Metal-ceramic composites formed by spray pyrolyzing the ceramic member on the metal member from a metalorganic precursor solution permits the production of metal-ceramic-metal composite sheet structures by pressing together two composites ceramic face to ceramic face, wherein the composites comprise a ceramic member deposited on a metal member substrate. The pressed metal-ceramic- metal composite is then thermomechanically calcined to form a uniformly rigidly bonded structure. This application of the pre sent invention is suitable for composites structures in which the ceramic members can be sintered at temperatures less than the melting point of the metal member substrates. This is not possible with copper- alumina-copper structures, wherein the alumina member needs to b e sintered at a temperature of at least 1828 °C, which is well above th e melting point of copper at 1083°C.
Also under the present invention, high conductivity metal- alumina-high conductivity metal, such as copper-alumina-copper structures, with improved crack-resistance and interfacial properties are produced by depositing an alumina-based ceramic on the high conductivity metal member. As shown in FIGS. 16 and 17(a) and (b) i t is another preferred embodiment of the present invention for the high conductivity metal member substrate 53 upon which an alumina ceramic member 54 is deposited to contain a constraining-metal member 55, and for adhesion-resistant bodies 56 to be implanted a t the interface between the metal member substrate and the deposited ceramic member. A similarly made metal-alumina ceramic composite, which may or may not contain the constraining-metal member 55 o r the adhesion-resistant bodies 56, is produced to bond with the other metal-alumina ceramic composite. Low temperature (<880 °C) bonding is achieved by introducing a layer of low-melting temperature oxide or oxyfluoride phase materials 57 that form a molten liquid phase at temperatures below 880 °C on the bonding surfaces 58 of at least one the metal-alumina ceramic composites. The low-temperature oxide or oxyfluoride phases may be introduced to the bonding surface as metalorganic precursors of the spray pyrolyzed solution, as secondary phase material particles dispersed in the metalorganic solution, as secondary phase material particles no t dispersed in the metalorganic solution but still applied to the bonding surfaces 58, are as an active metal film or powders that are oxidized. In printed circuit board applications it is desirable for the bonded alumina ceramic member to have a low dielectric constant, it is, therefore, preferable to use light atomic weight metal oxides. It is a preferred embodiment of this invention to utilize an phospho- alumino-borate glass phase as the low-temperature oxide bonding layer. Borate glass melts at temperatures as low as 450 °C, but is sensitive to chemical attack by water. Phosphoric anhydride typically melts in the range of 580-585 °C. Incorporating alumina into phosphate and borate oxide glasses increases chemical resistance an d intrinsic strength. Aluminophosphate glass phases typically melt a t temperatures ranging from 660- 1575 °C Thus, it is preferable to ad d borate glass phases to the low-temperature bonding materials wh en the metallic substrate member in the bonded metal-ceramic composite contains an aluminum member which melts at 660 °C. Additions of alkali oxides or alkali fluorides are useful in depressing the melting temperature of the low-temperature oxide bonding agent, but will also decrease its resistance to chemical attack by water.
It is a further preferred embodiment of this invention for the low melting temperature oxide bonding layer to have a thickness in th e range of 1 micron to 150 microns. The two metal-alumina ceramic composites, with at least one of the metal-alumina ceramic composites containing a low-temperature oxide bonding agent on its bonding surface, are then heated to at least a temperature above which the low-temperature oxide bonding agents forms a molten phase. The two metal-alumina ceramic composites are then joined at their bonding surfaces and pressed together at a pressure between 0.5 and 25 MPa. When cooled, a rigid oxide bond is formed between the two metal- alumina ceramic composites at the bonding surfaces to form the finished conducting metal-alumina ceramic-conducting metal composite. It is generally preferred that the two different metal members in a composite substrate for printed circuit board applications be made to different thickness and mechanical specifications. These differences need to be considered prior to forming the final bonded composite. It is, therefore, a preferred embodiment of this invention to form the composite substrate using one metal-alumina ceramic composite that contains a conducting metal member bonded to a constraining metal member, wherein the thickness of the constraining-metal member is in the range between 0.015 mm to 1.67 mm, and the total (combined) thickness of th e conducting metal member(s) is in the range between 0.30 mm to 5.00 mm; and, another metal-alumina ceramic composite that contains a conducting member in the range of 0.01 mm to 0.3 mm. The alumina- ceramic members on each of the two metal-ceramic composites m a y vary such that the combined thickness of alumina ceramic in th e bonded metal-ceramic-metal composite is in the range between 0.3 to 1.0 mm. It is, thus, preferred that the thickness of the ceramic member in the metal-ceramic composites be in the range of 0.15 to 0.85 mm.
Yet another particular subject of the present invention relates to the incorporation of a ferrite ceramic member into a metal-ceramic composite substrate for printed circuit board applications. In m any applications, semiconductor integrated circuits mounted on a printed circuit board substrate may actually become radiators of harmful electromagnetic radiation, or be exceptionally sensitive to such emissions. Thus, as shown in FIGS. 18(a), (b) and 19, it is desirable to have an element in close proximity to the SIC that would absorb th e electromagnetic radiation. Under the present invention a lossy ferrite ceramic member 59 can be bonded to a major surface of a high conductivity metal sheet, which is then used, on its opposing maj or surface, as the metal member substrate for a deposited alumina ceramic member. The ferrite ceramic-metal-alumina ceramic member is then bonded into a metal-ceramic composite substrate suitable for printed circuit board applications using the art described above.
A further particular subject of the present invention relates to the production of a metal-porous ceramic composite, wherein the porous ceramic member has ultrafine subdivision. In certain applications it is desirable for the metal-ceramic composite to function simultaneously as a heat shield and as a sound absorber. A porous ceramic member can function both as a thermally insulating memb er and as a sound absorber. Porous ceramics are also preferred forms of ceramic in the application of metal-ceramic composites a s electrochemical electrodes. Large organic molecules, such a s carboxylic acids, generate considerable water and carbon dioxide/carbon monoxide during thermal decomposition. The formation of a porous ceramic on a metal substrate is readily realized by spray pyrolyzing carboxylic acid salt precursors to the ceramic a s the metalorganic solution. Under this aspect of the present invention, mechanical swaging steps are omitted. It may also be preferable to introduce other foaming agents to the metalorganic precursor solution, such as polyurethanes, polyvinylchorides, polyethylenes, pentanes , hexanes, or polypropylenes, that further increase the foaming actions during the deposition process.
Although the invention has been described with reference to particular embodiments, it will be understood that this invention is also capable of further and other embodiments within the spirit and scope of the appended claims such as the use of AI2O 3 and • Tiθ2 containg ceramics.
What is claimed is:

Claims

1 . A ceramic composite as made by
(a) dispersion of a metal organic precursor of the ceramic on a substrate,
(b) pyrolysis of the precursor at 500┬░ C or less to form the ceramic with a direct covalent bond to the substrate and a n absence of intermetallic eutectic or an adhesive agent at th e substrate-ceramic interface, and
(c) densification of the ceramic.
2. The ceramic composite as in claim 1 with holes (perforations) i n the substrate to reduce the effective differences between its Young's modulus and/or coefficient thermal exansion and such property or properties of the ceramic.
3. The ceramic composite, comprising adjacent substrate and ceramic primary phase portions, the ceramic being a porous ceramic, wherein the substrate phase portion in the ceramic composite is rigidly attached through a direct covalent bond to a porous ceramic secondary phase portion whose precursors h ave been mixed at the molecular level, the bond being made by spray pyrolyzing the ceramic from a metalorganic precursor solution to form a direct covalent bond at the substrate ceramic interface.
4. The ceramic composite as in claim 3 wherein the porous ceramic primary phase contains secondary phase material particles dispersed throughout a substantial portion of its volume, the secondary phase material particles comprising material selected from the group consisting of metals, metal alloys, glass, shape memory alloys, graphite, oxides, non-oxide inert compounds, crystalline ceramics, a single crystalline phase, and combinations of these materials phases.
A ceramic composite comprising adjacent substrate and ceramic primary phase portions, the ceramic being a dense ceramic, wherein the substrate phase portion in the ceramic composite is rigidly attached through a direct covalent bond to a dense ceramic phase portion whose precursors have been mixed a t the molecular level, the bond being made by spray pyrolyzing the oxide ceramic from a metalorganic precursor solution to form a direct covalent bond at the metal ceramic interface, and th e densifying and crystallizing the spray pyrolyzed ceramic through a repetitive sequence of reaction and mechanical deformation processing steps.
6. The ceramic composite as in claim 5, wherein the dense ceramic primary phase contains secondary phase material particles dispersed substantially throughout a substantial portion of its volume, the secondary phase material particles comprising material selected from the group consisting of metals, metal alloys, glass, shape memory alloys, graphite, oxide, non-oxide materials, crystalline ceramics, a single crystalline phase, and combinations of these material phases.
7. The ceramic composite as in claim 6, wherein the secondary phase material particles dispersed in the oxide ceramic primary phase portion bonded to the substrate phase portion have a size defined by a major axis of such particles with a length ranging between 0.05 and 500 microns.
8. The ceramic composite as in claim 7, wherein the secondary phase material particles dispersed in the oxide ceramic primary phase part bonded to the substrate have a size defined by a maj or axis with a length ranging between 0.10 and 50 microns.
9. The ceramic composite as in claim 5, wherein the oxide ceramic is constructed and arranged with a gradient composition that causes the coefficient-of-thermal-expansion of the oxide ceramic to be greater at distances further away from the surface(s) at which the oxide ceramic member is bonded to the substrate, and lower a t the surface(s) at which the oxide ceramic member is bonded to th e substrate.
10. The ceramic composite as in claims 6 where the primary ceramic is an oxide.
1 1 . The ceramic composite as in claim 10 wherein the oxide ceramic contains AI2O3.
1 2. The ceramic composite as in claim 10 wherein the oxide ceramic contains Ti╬╕2-
1 3. A metal-ceramic composite as in claim 5 and further comprising adhesion-resistant means between the substrate and oxide ceramic primary phase portions.
14. The ceramic composite as in claim 13 with means for bonding the adhesion-resistant means to the substrate.
15. The ceramic composite as in claim 5 wherein the substrate comprises a high electrical and/or thermal conductivity material selected from the group consisting of:
(a) elemental metals,
(b) metal alloys, and
(c) metal composites of aluminum, copper, gold, or silver, bonded to a constraining-metal member that is l/20th to l/3rd the thickness of the high electrical and/or thermal conductivity substrate, wherein the constraining-metal member comprises a metal, metal alloy, or metal composite, of antimony, chromium, iridium, molybdenum, tantalum, tin, titanium, tungsten, or vanadium.
16. The ceramic composite as in claim 5 as made by temporarily bonding an adhesion resistant material to the substrate in selected surface regions, spray pyrolizing ceramic over the substrate an d the adhesion resistant material and later dissipating the adhesion resistant material to form cavities or a pattern of cavities at th e ceramic-substrate interface.
17. The ceramic composite as in claim 5 as applied to two ceramic containing pieces, at least one of which is a ceramic composite, the two pieces bonded at respective ceramic surfaces by a n intermediate low-melting temperature oxide phase.
18. The ceramic composite as in claim 17, wherein the low-melting temperature oxide phase used to bond the two pieces together ceramic-face to ceramic-face is a phospho-alumino-borate glass phase.
19. The ceramic composite as in claim 18, comprising two such ceramic composites, wherein the ceramic containing alumina an d the substrate comprising metal are bonded together to form a metal-ceramic composite substrate suitable for printed circuit board usage.
20. A printed circuit board constructed as in claim 19 having a metal portion on which SIC's can be mounted, with a total (combined) thickness of 0.3 mm to 5.00 mm bonded to a constraining metal member that is 0.015 mm to 1.67 mm thick; a n alumina ceramic member having thickness in the range between 0.3 mm to 1.00 mm; and a conducting metal member that is 0.01 mm to 0.3 mm thick.
21 . The ceramic composite as in claim 5 wherein the substrate portion is a metal.
22. The ceramic composite as in claim 5 wherein the substrate portion is a metal alloy.
23. The ceramic composite as in claim 5 wherein the substrate portion is an oxide ceramic.
24. The ceramic composite as in claim 5 wherein the subs trate portion is a nitride ceramic.
25. The ceramic composite as in claim 5 wherein the sub strate portion is an oxide ceramic.
26. The ceramic composite as in claim 5 wherein the substrate portion is a carbide ceramic.
27. The ceramic composite as in claim 5 wherein the substrate portion is a carbon based ceramic.
28. The ceramic composite as in claim 21 wherein the metal is stainless steel.
29. The ceramic composite as in claim 15 wherein said ceramic contains Ti╬╕2-
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