CA1122789A - Glass-ceramic structures and sintered multilayer substrates thereof with circuit patterns of gold, silver or copper - Google Patents
Glass-ceramic structures and sintered multilayer substrates thereof with circuit patterns of gold, silver or copperInfo
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- CA1122789A CA1122789A CA377,129A CA377129A CA1122789A CA 1122789 A CA1122789 A CA 1122789A CA 377129 A CA377129 A CA 377129A CA 1122789 A CA1122789 A CA 1122789A
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Abstract
GLASS-CERAMIC STRUCTURES AND SINTERED
MULTILAYER SUBSTRATES THEREOF WITH CIRCUIT
PATTERNS OF GOLD, SILVER OR COPPER
Abstract of the Disclosure Sintered glass-ceramic substrates containing multi-level, interconnected thick-film circuit patterns of highly conductive metals such as gold, silver or copper are provided which can be fired in air (for gold and silver) or in neutral atmospheres (for copper) at tem-peratures below the melting points of these metals. This has been made possible by the discovery that finely divided powders of certain glasses described herein sinter to essentially zero porosity at temperatures below 1000°C
while simultaneously maturing to glass-ceramics of low dielectric constant, high flexural strength and low thermal expansivity.
MULTILAYER SUBSTRATES THEREOF WITH CIRCUIT
PATTERNS OF GOLD, SILVER OR COPPER
Abstract of the Disclosure Sintered glass-ceramic substrates containing multi-level, interconnected thick-film circuit patterns of highly conductive metals such as gold, silver or copper are provided which can be fired in air (for gold and silver) or in neutral atmospheres (for copper) at tem-peratures below the melting points of these metals. This has been made possible by the discovery that finely divided powders of certain glasses described herein sinter to essentially zero porosity at temperatures below 1000°C
while simultaneously maturing to glass-ceramics of low dielectric constant, high flexural strength and low thermal expansivity.
Description
17 Field of the Invention 18 This invention relates to glass-ceramic structures 19 and, more particularly, to thick or thin film or hybrid, 'inter-connected multilayer substrates made of sintered 21 glass-ceramic insulator and conducting patterns made of 22 thick film gold, silver or copper (for electronic devices).
23 Also, this invention relates to the process and materials 24 for producing such substrates starting with certain glass powders and conductor "inks" or "pastes" containing finelY
26 divided powders of gold, silver or copper by the so-called ~7 "laminatod yroen slleet" tecllnitlue at firing teml~eratllrt3s.
Z~ not excoedilly tlle meltin-J ~vints vf tllc onductor metal 29 employed. The substrates may,be designed with termination . , .. .. ~. ... .. . . . . .. . .
llZZ789 1 pads for attaching semiconductor chips, connector leads,
23 Also, this invention relates to the process and materials 24 for producing such substrates starting with certain glass powders and conductor "inks" or "pastes" containing finelY
26 divided powders of gold, silver or copper by the so-called ~7 "laminatod yroen slleet" tecllnitlue at firing teml~eratllrt3s.
Z~ not excoedilly tlle meltin-J ~vints vf tllc onductor metal 29 employed. The substrates may,be designed with termination . , .. .. ~. ... .. . . . . .. . .
llZZ789 1 pads for attaching semiconductor chips, connector leads,
2 capa~ltor~, r~ tors, cover~i, o~c. t~ c~ln~ec~lol)H
3 ~otweon huriod con~]~lc~or 1MY~:rl l:L~ CI~ VI~I LIIrC)~
4 the so-called "vias" formed by metal-paste-filled holes in the individual layers formed prior to lamination which 6 upon sintering will become dcnsely sintercd mctQl intor-7 connections.
8 escription of the Prior Art 9 The "laminated green sheet" process for fabri-cating multilayer substrates of alumina, mullite and other 11 refractory ceramics are adequately described in prior art 12 (such as U. S. Patent 3,423,517 and 3,723,176). While the 13 procedures of this invention are similar to those described 14 in the above patents, important changes are incorporated ther~in to allow for the use of glass powders of this 16 invention.
17 Alumina (A12O3), because of its excellent insul-18 ating properties, thermal conductivity, stability and 19 strength is generally the material of choice for substrate fabrication. However, for certain high performance 21 applications the relatively high dielectric constant, 22 hereinafter designated by the letter "K", of alumina 23 (K A12O3 ~ 10) entails significant signal propogation de-24 lays and noise. In addition, the high maturing temperatures of commercial aluminas (~1600C) restrict the choice of 26 co sinterable conducting metallurgies to refractory metals 27 such a~ tungsten, molybdenum, platinum, palladium or com-28 binations of these with each other or with certain other ~Z2789 1 metals and precludes the sole use of good electrical 2 conductors such as gold, silver, or copper because these 3 latter will be molten much before the sintering temperature 4 of alumina is reached. A further disadvantage of alumina is its relatively high thermal expansion coefficient 6 ( ~ 65-70 x 10 7/oC) compared to that of silicon semi-7 conductor chips (~ 35 x 10 7/oC) which may, in certain 8 cases, result in some design and reliability concerns.
9 Glass Ceramics -Stookey, in his basic patent U. S. 2,920,971 on 11 glass-ceramics, has described in detail the theoretical 12 concepts and production techniques for such products. In 13 brief, glass-ceramics are obtained through the controlled, 14 in-situ, crystallization of a glass body of proper composi-tion brought about by a two-step heat treatment procedure.
16 The glass composition generally includes substances called 17 nucleating agents examples of which are TiO2, ZrO2, P2O5, 18 SnO2 and certain colloidal metal particles. The resultant 19 body is composed of a multitude of fine grained crystals of substantially uniform size homogeneously dispersed in a 21 glassy matrix, the crystal phase constituting the major 22 portion of the body. The high degree of crystallinity, 23 their very small dimensions and the absence of porosity 24 make these glass-ceramics generally superior in strength to the precursor glasses and other properties such as 26 thermal expansivity, chemical durability etc. closely 27 resemble those of the crystalline phase formed.
~12~78g 1 The glass-ceramic bod.ies made in accordance 2 with the above or similar methods wherein a glass article 3 shaped by conventional glass making techniques such as 4 drawing, pressing, blowing etc. of hot, plastic glass mass followed by conversion to the glass-ceramic state by 6 suitable heat treatments will be, hereinafter, referred 7 to as "bulk-crystallized" or simply as "bulk" glass-8 ceramics to distinguish them from $he sintered glass-g ceramics of this invention.
There have been references to sinterable glas~-11 ceramics in prior art but these are not suitable for the 12 present application for one reason or another. For example, 13 U. S. Patent 3,825,468 refers to sintered glass-ceramic 14 bodies which are porous in the interior and non-porous in the exterior surfaces. Such bodies would have low rupture 16 strengths due mainly to the internal porosity r with typical 17 flexural strengths of less than 10,000 psi. Furthermore, 18 the final sintering temperatures for these glass-ceramics 19 would be well in excess of 1000C and hence above the melting points of gold, silver and copper. Another example is U. S.
21 Patent 3,450,546 which describes non-porous, transparent, 22 sintered glass-ceramics produced by sintering in vacuum at 23 temperatures above 1200C. Helgesson (see "Science of 24 Ceramics", pp. 347-361, published by the British Ceramic Z5 Society, 1976) describes the sintering of a glass powder 26 of composition 53 wt.% SiO2, 26 wt.% A12O3 and 21 wt.% MgO.
27 ~hey could obtain dense, corderite glass-ceramics at a 28 sintering temperature of about 950C provided the glass ~lZ~789 1 powder was given a prior chemical treatment in an alkali 2 solution. In the absence of this treatment, they found 3 that it was not possible to sinter,the glass powder due 4 to premature surface crystallization.
Numerous glass compositions allow sintering to 6 dense bodies at temperatures below 1000C but are unsuit-7 able for the purposes of this invention owing to the fact 8 the relatively high fluidity (viscosity of 105 to 108 poises) g at the sintering temperature would result in excessive move-ment of the buried conductor patterns and otherwise prevent 11 the attainment of the rigid tolerances for dimensions and 12 distortion that have to be met. The rupture strengths of 13 glasses, typically about 10,000 psi, are also much lower 14 than desired for this application. The glasses of the compositions described herein undergo crystallization 16 during the sintering heat treatment forming pervasive 17 rigid networks of micron-sized crystallites which drastically 18 reduces the overall fluidity of the body thereby enabling 19 greater dimensional and distortional control. This very crystallization of refractory phases in the glass during 21 sintering however, can militate against the realization of 22 dense sintering. In the two types of glass-ceramics des-23 cribed in this invention, certain principles, described 24 hereinafter, have been discovered that enable one to over-25` come this difficulty.
llZZ789 1 Summary of the Invention 2 Accordingly, the primary object of this invention 3 is to provide glass-ceramic bodies, having low dielectric 4 constants and other useful properties for substrate applica-tions, which can be easily obtained by the sintering of 6 certain glass powders and concurrent conversion into glass-7 ceramics at lower temperatures than similar materials known 8 from prior art.
9 Another object is to provide materials of lower dielectric constant than prior inorganic materials used in 11 multilayer substrate applications.
12 A further object is to provide new glass-ceramic 13 compositions suitable for the production of such bodies 14 which are characterized as essentially non-porous and which possess microstructures consisting of networks of fine 16 crystallites with the residual glass and secondary crystal-17 lites occupying the interstitial spaces of such networks.
18 This unique microstructure imparts to these glass-ceramics 19 rupture strengths substantially higher than in sintered glass-ceramics known from prior art.
21 Another object is to provide multilayer glass-22 ceramic substrates which are compatible with thick film 23 circuitry of gold, silver or copper and co-fireable there-24 with.
Another object is to provide multilayer substrates 26 having thermal expansion coefficients closely matched to 27 that of silicon semiconductor chips.
llZZ7~39 Yet another objective is to provide a method for fabricating multilayer substrates of glass-ceramics with conductor patterns of gold, silver or copper.
To these and other ends, the invention embodies ~mon~ its ~eatures a method of making the body by the said method, new compositi~ns for making the body by the said method, an article comprising the body and a method of making the article, hereinafter referred to as a "multi-layer glass-ceramic substrate".
n Hore particularly, there is provided:
A non-porous glass ceramic article comprising: ~
a microstructure of a pérvasive continuous network of 2 to 5~m crystallite selected from the group consisting of ~-spodumene and alphacordierite with the interstices of said networ~ occupied by residual glass having dispersed therein discrete secondary 1 to 2~m crystallite of lithium metasilicate associated with said B-spodumene network and clinoen-statite associated with said alphacordierite network.
There is also provided:
A glass ceramic article substantially non-porous throughout the volume thereof comprising:
a microstructure o. a pervasive continuous connected network of 2 to 5~m crystallites selected Srom the sroup consisting of A) ~-spodumene with the interstices of said network thereof occupied by residual glass having dispersed the-ein discrete secondary 1 to 2~m crystallites of lithium metasilicate znd B) ~lpha-cordierite with tne interstices thereo' occupied by residual glcss having dispersed therein secondary 1 to 2~m crystallites of clinoes-tatite; and an electrical conductor pattern embedded in said article having ter~inal portions terminating at at least one surface or said ar. cle ror electric~l conr.ection thereto.
llZZ789 There is also provided:
A ceramic article substantially non-porous through-out the volume thereof comprising:
a microstructure of a pervasive continuous connected network of 2 to 5~m crystallites selected from the group consist-ing of A) ~-spodumene with the interstices of said network t~e_e-of occupied by residual glass having dispersed therein discrete secondary 1 to 2~m cr~stallites of lithi~m metasilicate and B) alphacordierite with the interstices of said networ~ thereof occupied by residual glass having dispersed therein seconda~
1 to 2~m crystallites of clinoenstatite; and at least two spaced and interconnected levels of electrical conductor patterns embedded in said article and having termi~al portions extending to at least one surface of said article for electrical connection to an external electri_al cir-cuit.
There is also provided:
A method of making a glass ceramic article compriiing forming a glass from a batch selected from 20 the group consisting of, by weight A. SiO2 65 to 75% LiO23.5 to 11%
A123 1 h2O3O to 2.5 MgO 0 to 2% P2O50 to 2.5 Zn2 to 2% F0 to 3%, from 0 to 2% of at least o~ne oxide selected from the group consisting of CaO and BaO, and from 1.0 to 3.5% of at least one oxide selected from the group consisting of Na2O and ~2' and B. S~O2 48 to 55~ ~25 to 3 A12O3 18 to 25% TiO2 to 2.5 MgO 18 to 25% SnO2 0 to 2.5~
ZnO 0 to 2~ ZrO2 0 to 2.5%, pulverizing said glass to particle sizes of about 2 to a~out 7~m;
- -7a-11'~2789 ~ haping said glass particles into a desired configuration;
heating said shaped particles to a temperature in the range of about 870 to about 1000C at a rate not exceeding 2C~minute;
sintering said shaped particles at said temperature for times in the range of 1 to 5 hours to coalesce and crystallize said particles; and cooling said sintered particles at a rate not exceeding 4C per minute to a temperature of at least about 400C.
rief Description of the Drawings FIGURE 1 shows typical dilatometric shrinkage curves of B-spodumene glass ceramics of this invention.
FIGURE 2 is a photomicrograph of a sintered B-spodumene glass ceramic of this invention, by scanning electron microscope (SEM) 1000X.
FIGURE 3 shows typical dilatometric shrinkage curve~ for cordl~ri~n y].nn~l-ce~n~ .cn Or ~ i.nvnnl~ol~.
FIGURE 4 is a typical photomicrograph of a sintered ~-cordierite glass-ceramic of this invention (SEM 2000X).
Description of the rreferred r~mbodiments or ~ wo ~yl)c~ o~ ~Jl~U9-C~ U o~
invention, one has ~-spodumene, Li2O.A12O3.45iO2 as the principal crystalline phase while the other has cordierite, 2MgO.2A12O3.5SiO2, as the main crystalline phase. The common feat~re of these sintered glass-ceramics, apart from their excellent sinterabili~ty below 1000C, is a microstructure that can be described as composed of networks -7b-.. . .. .. .. . ...
Z78g 1 that are highly crystalline, the interstices of which 2 are occupied by small amounts of the residual glass and 3 some discrete secondary crystallites. Such microstructures 4 differ from those observed in "bulk" glass-ceramics in that in the latter the glassy phase forms the matrix or the 6 network with discrete crystallites dispersed in it. We 7 believe that the unique microstructures observed in the 8 glass-ceramics of this inven ion give rise to their high 9 flexural strengths.
~he general composi~ion range of the glass-11 ceramics applicable for this invention are given in Table I.
~12Z789 1TA~LE I
2COMPOSITION RANGES (WEIG}IT PERCENTAGES) 3 ~-Spodumene Type Cordierite Type 4 sio2 65 to 75 48 to 55 A12O3 12 to 17 18 to 23 6 . MgO 0 to 2 18 to 25 7 CaO } 0 to 2 -8 BaO ~alone or combined) 9 ZnO 0 to 2 ^ 0 to 2 10 Li2o 3.5 to 11 0 to 1 11 Na2O¦ l.0 to 3.5 ~ -12 K2O J (alone or combined) 13 B2O3 0 to 2.5 0 to 3 14 P2O5 0 to 2.5 0 to 3 15 Tio2 0 to 3 0 to 2.5~
16 SnO2 0 to 2.5 ~Total not to 17 zro2 0 to 2.5J exceed 5.0 18 F 0 to 3 19 The ranges of constituents of the above glass-ceramics that will yield satisfactory materials are determined by several 21 factors. Important among these are:
22 a) The requirement for the glass cerami~~ to 23 sinter to zero apparent porosity at tempexatures 24 below 1000C, and preferably in the vicinity of 950C.
b) The requirement for the thermal expansion 26 coefficient, measured in the temperagure range of 27 20 - 300C, of the glass-ceramic to be in the range 28 of 20 to 40 x 10 7/oC and preferably to be close to 29 30 x 10 7/oC.
- l~ZZ789 1 Sinterable ~-Spodumene Glass-Ceramics ~2 SiO2 and A1203 contents greater than the upper 3 limits given in Table I would not allow satisfactory sinter-4 ing to be achieved. Also, the Li2o content should not fall below seven percent except when either B203 and F act as 6 fluxes and therefore facilitate sintering; they have the 7 added advantage of assisting melting and refining of the 8 glasses. The sodium and potassium oxides are essential 9 constituents since they promote the formation of binary lithium silicates, particularly the metasilicate as a 11 minor crystalline phase which, as discussed below, plays a 12 major role in the sintering process.
13 The SiO2 and A1~03 contents must also fall within 14 the specified ranges to ensure the development of the desired volume fraction of ~-spodumene to enable the correct thermal 16 expansion coefficient to be attained as well as to ensure 17 high strength. The P205 and TiO2 are desirably included to 18 promote internal nucleation of the glass grains; inclusion 19 of ZrO2 also assists internal nucleation.
ll;~Z789 1 Specific Compositions 2 Examples of specific compositions are given in 3 Table II as follows:
8 escription of the Prior Art 9 The "laminated green sheet" process for fabri-cating multilayer substrates of alumina, mullite and other 11 refractory ceramics are adequately described in prior art 12 (such as U. S. Patent 3,423,517 and 3,723,176). While the 13 procedures of this invention are similar to those described 14 in the above patents, important changes are incorporated ther~in to allow for the use of glass powders of this 16 invention.
17 Alumina (A12O3), because of its excellent insul-18 ating properties, thermal conductivity, stability and 19 strength is generally the material of choice for substrate fabrication. However, for certain high performance 21 applications the relatively high dielectric constant, 22 hereinafter designated by the letter "K", of alumina 23 (K A12O3 ~ 10) entails significant signal propogation de-24 lays and noise. In addition, the high maturing temperatures of commercial aluminas (~1600C) restrict the choice of 26 co sinterable conducting metallurgies to refractory metals 27 such a~ tungsten, molybdenum, platinum, palladium or com-28 binations of these with each other or with certain other ~Z2789 1 metals and precludes the sole use of good electrical 2 conductors such as gold, silver, or copper because these 3 latter will be molten much before the sintering temperature 4 of alumina is reached. A further disadvantage of alumina is its relatively high thermal expansion coefficient 6 ( ~ 65-70 x 10 7/oC) compared to that of silicon semi-7 conductor chips (~ 35 x 10 7/oC) which may, in certain 8 cases, result in some design and reliability concerns.
9 Glass Ceramics -Stookey, in his basic patent U. S. 2,920,971 on 11 glass-ceramics, has described in detail the theoretical 12 concepts and production techniques for such products. In 13 brief, glass-ceramics are obtained through the controlled, 14 in-situ, crystallization of a glass body of proper composi-tion brought about by a two-step heat treatment procedure.
16 The glass composition generally includes substances called 17 nucleating agents examples of which are TiO2, ZrO2, P2O5, 18 SnO2 and certain colloidal metal particles. The resultant 19 body is composed of a multitude of fine grained crystals of substantially uniform size homogeneously dispersed in a 21 glassy matrix, the crystal phase constituting the major 22 portion of the body. The high degree of crystallinity, 23 their very small dimensions and the absence of porosity 24 make these glass-ceramics generally superior in strength to the precursor glasses and other properties such as 26 thermal expansivity, chemical durability etc. closely 27 resemble those of the crystalline phase formed.
~12~78g 1 The glass-ceramic bod.ies made in accordance 2 with the above or similar methods wherein a glass article 3 shaped by conventional glass making techniques such as 4 drawing, pressing, blowing etc. of hot, plastic glass mass followed by conversion to the glass-ceramic state by 6 suitable heat treatments will be, hereinafter, referred 7 to as "bulk-crystallized" or simply as "bulk" glass-8 ceramics to distinguish them from $he sintered glass-g ceramics of this invention.
There have been references to sinterable glas~-11 ceramics in prior art but these are not suitable for the 12 present application for one reason or another. For example, 13 U. S. Patent 3,825,468 refers to sintered glass-ceramic 14 bodies which are porous in the interior and non-porous in the exterior surfaces. Such bodies would have low rupture 16 strengths due mainly to the internal porosity r with typical 17 flexural strengths of less than 10,000 psi. Furthermore, 18 the final sintering temperatures for these glass-ceramics 19 would be well in excess of 1000C and hence above the melting points of gold, silver and copper. Another example is U. S.
21 Patent 3,450,546 which describes non-porous, transparent, 22 sintered glass-ceramics produced by sintering in vacuum at 23 temperatures above 1200C. Helgesson (see "Science of 24 Ceramics", pp. 347-361, published by the British Ceramic Z5 Society, 1976) describes the sintering of a glass powder 26 of composition 53 wt.% SiO2, 26 wt.% A12O3 and 21 wt.% MgO.
27 ~hey could obtain dense, corderite glass-ceramics at a 28 sintering temperature of about 950C provided the glass ~lZ~789 1 powder was given a prior chemical treatment in an alkali 2 solution. In the absence of this treatment, they found 3 that it was not possible to sinter,the glass powder due 4 to premature surface crystallization.
Numerous glass compositions allow sintering to 6 dense bodies at temperatures below 1000C but are unsuit-7 able for the purposes of this invention owing to the fact 8 the relatively high fluidity (viscosity of 105 to 108 poises) g at the sintering temperature would result in excessive move-ment of the buried conductor patterns and otherwise prevent 11 the attainment of the rigid tolerances for dimensions and 12 distortion that have to be met. The rupture strengths of 13 glasses, typically about 10,000 psi, are also much lower 14 than desired for this application. The glasses of the compositions described herein undergo crystallization 16 during the sintering heat treatment forming pervasive 17 rigid networks of micron-sized crystallites which drastically 18 reduces the overall fluidity of the body thereby enabling 19 greater dimensional and distortional control. This very crystallization of refractory phases in the glass during 21 sintering however, can militate against the realization of 22 dense sintering. In the two types of glass-ceramics des-23 cribed in this invention, certain principles, described 24 hereinafter, have been discovered that enable one to over-25` come this difficulty.
llZZ789 1 Summary of the Invention 2 Accordingly, the primary object of this invention 3 is to provide glass-ceramic bodies, having low dielectric 4 constants and other useful properties for substrate applica-tions, which can be easily obtained by the sintering of 6 certain glass powders and concurrent conversion into glass-7 ceramics at lower temperatures than similar materials known 8 from prior art.
9 Another object is to provide materials of lower dielectric constant than prior inorganic materials used in 11 multilayer substrate applications.
12 A further object is to provide new glass-ceramic 13 compositions suitable for the production of such bodies 14 which are characterized as essentially non-porous and which possess microstructures consisting of networks of fine 16 crystallites with the residual glass and secondary crystal-17 lites occupying the interstitial spaces of such networks.
18 This unique microstructure imparts to these glass-ceramics 19 rupture strengths substantially higher than in sintered glass-ceramics known from prior art.
21 Another object is to provide multilayer glass-22 ceramic substrates which are compatible with thick film 23 circuitry of gold, silver or copper and co-fireable there-24 with.
Another object is to provide multilayer substrates 26 having thermal expansion coefficients closely matched to 27 that of silicon semiconductor chips.
llZZ7~39 Yet another objective is to provide a method for fabricating multilayer substrates of glass-ceramics with conductor patterns of gold, silver or copper.
To these and other ends, the invention embodies ~mon~ its ~eatures a method of making the body by the said method, new compositi~ns for making the body by the said method, an article comprising the body and a method of making the article, hereinafter referred to as a "multi-layer glass-ceramic substrate".
n Hore particularly, there is provided:
A non-porous glass ceramic article comprising: ~
a microstructure of a pérvasive continuous network of 2 to 5~m crystallite selected from the group consisting of ~-spodumene and alphacordierite with the interstices of said networ~ occupied by residual glass having dispersed therein discrete secondary 1 to 2~m crystallite of lithium metasilicate associated with said B-spodumene network and clinoen-statite associated with said alphacordierite network.
There is also provided:
A glass ceramic article substantially non-porous throughout the volume thereof comprising:
a microstructure o. a pervasive continuous connected network of 2 to 5~m crystallites selected Srom the sroup consisting of A) ~-spodumene with the interstices of said network thereof occupied by residual glass having dispersed the-ein discrete secondary 1 to 2~m crystallites of lithium metasilicate znd B) ~lpha-cordierite with tne interstices thereo' occupied by residual glcss having dispersed therein secondary 1 to 2~m crystallites of clinoes-tatite; and an electrical conductor pattern embedded in said article having ter~inal portions terminating at at least one surface or said ar. cle ror electric~l conr.ection thereto.
llZZ789 There is also provided:
A ceramic article substantially non-porous through-out the volume thereof comprising:
a microstructure of a pervasive continuous connected network of 2 to 5~m crystallites selected from the group consist-ing of A) ~-spodumene with the interstices of said network t~e_e-of occupied by residual glass having dispersed therein discrete secondary 1 to 2~m cr~stallites of lithi~m metasilicate and B) alphacordierite with the interstices of said networ~ thereof occupied by residual glass having dispersed therein seconda~
1 to 2~m crystallites of clinoenstatite; and at least two spaced and interconnected levels of electrical conductor patterns embedded in said article and having termi~al portions extending to at least one surface of said article for electrical connection to an external electri_al cir-cuit.
There is also provided:
A method of making a glass ceramic article compriiing forming a glass from a batch selected from 20 the group consisting of, by weight A. SiO2 65 to 75% LiO23.5 to 11%
A123 1 h2O3O to 2.5 MgO 0 to 2% P2O50 to 2.5 Zn2 to 2% F0 to 3%, from 0 to 2% of at least o~ne oxide selected from the group consisting of CaO and BaO, and from 1.0 to 3.5% of at least one oxide selected from the group consisting of Na2O and ~2' and B. S~O2 48 to 55~ ~25 to 3 A12O3 18 to 25% TiO2 to 2.5 MgO 18 to 25% SnO2 0 to 2.5~
ZnO 0 to 2~ ZrO2 0 to 2.5%, pulverizing said glass to particle sizes of about 2 to a~out 7~m;
- -7a-11'~2789 ~ haping said glass particles into a desired configuration;
heating said shaped particles to a temperature in the range of about 870 to about 1000C at a rate not exceeding 2C~minute;
sintering said shaped particles at said temperature for times in the range of 1 to 5 hours to coalesce and crystallize said particles; and cooling said sintered particles at a rate not exceeding 4C per minute to a temperature of at least about 400C.
rief Description of the Drawings FIGURE 1 shows typical dilatometric shrinkage curves of B-spodumene glass ceramics of this invention.
FIGURE 2 is a photomicrograph of a sintered B-spodumene glass ceramic of this invention, by scanning electron microscope (SEM) 1000X.
FIGURE 3 shows typical dilatometric shrinkage curve~ for cordl~ri~n y].nn~l-ce~n~ .cn Or ~ i.nvnnl~ol~.
FIGURE 4 is a typical photomicrograph of a sintered ~-cordierite glass-ceramic of this invention (SEM 2000X).
Description of the rreferred r~mbodiments or ~ wo ~yl)c~ o~ ~Jl~U9-C~ U o~
invention, one has ~-spodumene, Li2O.A12O3.45iO2 as the principal crystalline phase while the other has cordierite, 2MgO.2A12O3.5SiO2, as the main crystalline phase. The common feat~re of these sintered glass-ceramics, apart from their excellent sinterabili~ty below 1000C, is a microstructure that can be described as composed of networks -7b-.. . .. .. .. . ...
Z78g 1 that are highly crystalline, the interstices of which 2 are occupied by small amounts of the residual glass and 3 some discrete secondary crystallites. Such microstructures 4 differ from those observed in "bulk" glass-ceramics in that in the latter the glassy phase forms the matrix or the 6 network with discrete crystallites dispersed in it. We 7 believe that the unique microstructures observed in the 8 glass-ceramics of this inven ion give rise to their high 9 flexural strengths.
~he general composi~ion range of the glass-11 ceramics applicable for this invention are given in Table I.
~12Z789 1TA~LE I
2COMPOSITION RANGES (WEIG}IT PERCENTAGES) 3 ~-Spodumene Type Cordierite Type 4 sio2 65 to 75 48 to 55 A12O3 12 to 17 18 to 23 6 . MgO 0 to 2 18 to 25 7 CaO } 0 to 2 -8 BaO ~alone or combined) 9 ZnO 0 to 2 ^ 0 to 2 10 Li2o 3.5 to 11 0 to 1 11 Na2O¦ l.0 to 3.5 ~ -12 K2O J (alone or combined) 13 B2O3 0 to 2.5 0 to 3 14 P2O5 0 to 2.5 0 to 3 15 Tio2 0 to 3 0 to 2.5~
16 SnO2 0 to 2.5 ~Total not to 17 zro2 0 to 2.5J exceed 5.0 18 F 0 to 3 19 The ranges of constituents of the above glass-ceramics that will yield satisfactory materials are determined by several 21 factors. Important among these are:
22 a) The requirement for the glass cerami~~ to 23 sinter to zero apparent porosity at tempexatures 24 below 1000C, and preferably in the vicinity of 950C.
b) The requirement for the thermal expansion 26 coefficient, measured in the temperagure range of 27 20 - 300C, of the glass-ceramic to be in the range 28 of 20 to 40 x 10 7/oC and preferably to be close to 29 30 x 10 7/oC.
- l~ZZ789 1 Sinterable ~-Spodumene Glass-Ceramics ~2 SiO2 and A1203 contents greater than the upper 3 limits given in Table I would not allow satisfactory sinter-4 ing to be achieved. Also, the Li2o content should not fall below seven percent except when either B203 and F act as 6 fluxes and therefore facilitate sintering; they have the 7 added advantage of assisting melting and refining of the 8 glasses. The sodium and potassium oxides are essential 9 constituents since they promote the formation of binary lithium silicates, particularly the metasilicate as a 11 minor crystalline phase which, as discussed below, plays a 12 major role in the sintering process.
13 The SiO2 and A1~03 contents must also fall within 14 the specified ranges to ensure the development of the desired volume fraction of ~-spodumene to enable the correct thermal 16 expansion coefficient to be attained as well as to ensure 17 high strength. The P205 and TiO2 are desirably included to 18 promote internal nucleation of the glass grains; inclusion 19 of ZrO2 also assists internal nucleation.
ll;~Z789 1 Specific Compositions 2 Examples of specific compositions are given in 3 Table II as follows:
5 COMPOSITIONS OF ~-SPODUMENE GLASS-CERAMICS
6 Glass No. 1 2 3 4 5 6 7
7 SiO2 71.5 74.9 71.0 71.5 71.5 71.0 67.8
8 A123 15.0 7.5 ,13.0 13.0 13.0 15.0 16.0
9 MgO ~ - - 1.5 CaO
11 BaO - 2.0 2.0 12 ZnO - 2.1 2.5 2.0 2.0 2.0 13 Li2o 10.0 8.8 8.0 10.0 8.0 8.0 4.2 14 Na2O - - - - - - 0.9 15 K2O 2.0 3.1 2.0 2.0 2.0 2.0 16 B O - - _ _ 2.0 0-5 1.8 17 P2O5 1.5 1.6 1.5 1.5 1.5 1.5 18 2 ~ - - _ _ 2.5 19 F ~ 0.8 20 ~ Sintering 21 Temp.(C) 925 850 990 900 855 * 910 22 Thermal 23 Exp.Coeff.
24 (C lxl07) 32 83 60 43 29 _ 20 25 Modulus of 26 Rupture 27 (psi) 30,000 67,000 10,400 63,400 30,000 - 25,200 28 K 6.5 - 6.5 6.3 6.4 - 5.0 29 (permittivity) * did not sinter satisfactorily at temperatures below 1000C
7~g I These glasses were melted at temperatures close 2 to 1500C from mixtures of suitable raw materials until 3 free from unreacted material and gas bubbles. The molten 4 glass was quenched by pouring it into col~ water to produce "cullet" suitable for further grinding. The "cullet" was 6 ground to average particle sizes ranging from 3-7 ~m and 7 mixed with suitable organic binders and solvents to obtain 8 a castable slip or slurry from which thin sheets were cast 9 using conventional doctor blading techniques. The bodies were prepared by laminating a desired number of these 11 sheets in a laminating press at moderate temperatures and 12 pressures (e.g. 100C and 3000 psi) to obtain a monolithic 13 "green" body. Specimens for the measurement of rupture 14 strength, thermal expansion coefficient and dielectric constant measurements were formed as above and fired in air 16 using programmed furnaces. Prior experimentation had showed 17 that the heating rate should be low, not greater than 2C/
18 minute; faster heating rates resulted in incomplete binder 19 burnout. It is also believed that the use of a relatively slow heating rate is advantageous in allowing surface and 21 internal nucleation processes to be completed in a controlled 22 manner.
23 The modulus of rupture of the sintered glass-24 ceramics was measured in a 3-point bending mode on bar specimens and in general the mean of ten (10) déterminations 26` was calculated. Thermal expansion coefficients were measured 27 in the range from room temperature to 300C using two-point Z78g il metl-od. Dielectrio col~tan~ were d~ m~rle~ a~ a ~re-2 ~uency of 1 Mll~ at 25C.
3 Typical values of thesc pro~)crties are quoted in 4 Table II. In general, the sintering temperatures given are those yielding optimum results but it should be understood 6 that for each material, a sintering range exists usually 7 extending 20C above and below the optimum temperature.
8 The optimum holding time at the sintering temp~rature was 9 two hour~, though times ranging from one to five hours also give satisfactory results.
11 Of the compositions given in Table II, glasses 12 #1, #4, #5, and #7 yielded glass-ceramics having properties 13 suitable for the present multilayer substrate application.
14 Compositions #3 and #6 failed to sinter satisfactorily below 1000C and composition #2, while it yielded a high 16 strength material, resulted in a glass-ceramic of thermal 17 expansion coefficient outside the desired rang~.
18 X-ray diffraction analysis showed that glass 19 ceramics ~1, #4 and #5 contained ~-spodumene as the major phase and a lithium meta and disilicates as minor phases.
21 Composition #2 contained only a very small amount of ~-22 spodumene plus a major amount of an unidentified crystal 23 phase~ Composition #3 contained ~-spodumene as the major 24 phase along with minor amounts of lithium metasilicate and dlsillcate.
26 On thi6 basis, it is believed that ~-spodumene 27 should be present a6 a major phase to enable the desired 28 thermal expansion coefficient to be obtained but that binary .
;Z789 1 lithium ~illcat~s must also b~ pr-~s~llt A~ mi.l10~ PhA~
1)r~ 0 n1I~ rI n~J D~ I L1OI~ 1HLI-3 ceramics at tempor~turcs bolow 1000C.
~ Dl~AI:onlo~ric ~Illrilll~tl~lf~ oElF~ lln ~ oll S laminates as a function temperature illustrate very well 6 the differences between those materials containing lithium 7 metasilicate as a minor phase and those that do not contain 8 this phase. Curve A, FIG~RE 1, is typical of the former 9 type (e.g. composition #1) and Curve B, FIGURE 1 of the latter type of material ~e.g~. glasses #2 and #6). For the 11 satisfactory material (Curve A) densification commences at 12 a temperature of about 580C. At this stage, the material 13 is still uncrystallized glass. At a temperature of about 14 610C, however, further densification is arrested owing to the onset of crystallization. A second densification stage 16 commences at about 910C and this proceeds until the glass-17 ceramic becomes non-porous. For the unsatisfactory ma~erials 18 (Curve B), the second densification stage is absent at 19 temperatures below 1000C.
Differential thermal analysis, x-ray diffraction 21 analysis and electron microscopic studies have indicated that 22 the commencement of the second stage of the sintering process 23 corresponds to the liquidus temperature of lithium meta-24 silicate phase. Some of the metasilicate recrystallizes on cooling the glass-ceramic.
26 It is believed that the satisfactory sintering of 27 these ~-spodumene glass-ceramics involves the following 28 steps. Initial sintering of the glass powder by viscous 29 flow and diffusion processes, possibly also assisted by ~lZZ7139 1 glass-in-glass phase separation, occurs between 580-600C.
~2 As a result of surface nucleation processes, the individual 3 glass grains become covered with a layer of lithium meta-4 silicate. Internal nucleation within the glass grains follows causing the precipitation of ~-spodumene crystals, whose 6 maximum size will be set by the particle diameter. Further 7 sintering then requires the partial or complete melting of 8 the metasilicate phase which brings about (i) consolidation 9 of the ~-spodumene grains by capillary forces and (ii) neck or bridge formation between~the ~-spodumene particles 11 promoted by the reaction of the molten metasilicate with 12 the alumina and silica of the residual glass to form further 13 quantities of ~-spodumene. At temperatures above the 14 recommended sintering range, the metasilicate appears to flux the B-spodumene destroying the inter-particle bridges.
16 The reaction of the lithium metasilicate with residual glass 17 to form B-spodumene in certain Li2O - A12O3 - SiO2 systems 18 has also been alluded to by Stookey in U. S. Patent 2,971,853.
19 The microstructure of the glass-ceramics obtained from such a sintering mechanism consists of cosintered 21 B-sPodumene crystals forming rigid skeletal structures with 22 the residual glass occupying the interstitial regions in such 23 a ~tructure. FIGURE 2 is an example of such a microstructure 24 which more resembles those of conventional ceramics obtained by sintering ceramic powders, such as alumina with minor 26 glass additions than those of "bulk" glass-ceramics. The 27 absence of a continuous glassy matrix or network is believed 28 to be the principal factor governing the high flexural 29 strengths of the present materials.
~lZZ78g 1 It is to be understood that as used herein and ~2 in the claims, the term "B-sPodumene glass" is defined as 3 and restxicted to (1) a precursor for ~-spodumene glass 4 ceramic and (2) formed from a batch consisting of, by 5 weight:
6 SiO265 to 75% Lio2 3 5 to 11%
7 A12O312 to 17~ B2O3 0 to 2.5%
8 MgO 0 to 2~ P2O5 0 to 2.5~
9 ZnO 0 to 2~ F 0 to 3%, and also from 0 to 2% of at least one oxide selected from the 11 group consisting of CaO and BaO, and from 1.0 to 3.5~ of at 12 least one oxide selected from the group consisting of Na2O
13 and K2O.
14 Conversely, as used herein and in the claims, the term "B-spodumene glass ceramic" is defined as and restricted 16 to a glass ceramic structure coalesced and crystallized from 17 "B-spodumene glasses" into an article having a microstructure 18 of a pervasive continuous network of 2 to 5 ~m crystallites of 19 B-spodumene with the interstices of said network occupied by residual glass having dispersed therein discrete secondary 21 1 to 2 ~m crystallites of lithium metasilicate.
22 Sinterable Cordierite Glass-Ceramics _ 23 The overall composition ranges of the cordierite 24 glass-ceramics of this invention is given in Table I and specific examples are listed in Table III.
I` ocOo n o u~ o #
~ ~ o ~ 789 o u) , ~D
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~I NNu~ a~~ O
o O O U) O IJ') N ~D
O
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o O
O
~~') ~N ~I N 1~ 1~ 0 1 _1 NN
o ~c In ~~I N N ~ O 0~ U~
o O lc O
r~
NN N I ~1 1_I I I a~ N u~
Ln o O
o l_ U~ ~ ~1 N N ~1 1 _I I I I I a~ N ~7 C~) ~ r-l N N 11 H U~
~ O O
r :l .
~ ,~ o 1-~ 1 U~ r N
H U~ O N N ~ N ~1 1 0 _i I I I a~ ~ co H ~n R. ~1 ~ N U') ~ ~ ~i O ~
~ ~ U~
P~, tl ~I N N U~
~_1 .,~
O N N ~D O O ~c ~ _i O t~l I ~ I I I I ~ ~1 N U'l _I N N Ul O
o O
`J N _I I I II I ~5) u~ N
N N It~
O
'' O U~
In ` ~ :C
~r ,1 ~ ~ o t~ O ~ X
U
Z ~ ~ ~ O O
),~ _ ~ Ul X
U~ O N U~ O ~1 ~ N N ~ ~
~1 0 N 0 0 N 0 0~ 0~ 0 0~ ~ a) .C X O o O ~ P~ h m ~ u -- :~ o~
,--1 N ~ N N
ll'ZZ~89 1 The composition limits are set on the one hand by the need 2 to ensure that cordierite appears as the major crystalline 3 phase in order to achieve desired thermal expanSiQn co-4 efficients and on the other to facilitate sintering below 1000C. Reduction of MgO and ~12O3 contents below the 6 specified limits is not permissible for this reason. Ex-7 cessively high A12O3 and SiO2 contents would result in 8 materials not capable of sintering below 1000C. MgO
9 contents higher than the specified maximum could result in the formation of magnesium silicates in significant 11 amounts causing the thermal expansion coefficients to be 12 higher than desired.
13 The minor constituents are included to perform 14 important functions. ~he P2O5, ZrO2, TiO2 and SnO2 are added to promote nucleation and to regulate the micro-16 structural development. The Li2o and B2O3 are included as 17 sintering aids; they also serve to regulate the nature of 18 the crystalline phase formed~ Cordierite can appear in 19 either the ~ or ~ form. Sometimes, mixtures of the two appear in the same glass-ceramic. As will become clear in 21 what follows, it has been discovered that in order to 22 produce glass-ceramics having stable thermal expansion 23 coefficients in the desired range as well as lower dielectric 24 constants, it is necessary to develop the cordierite phase predominantly in the ~ form.
2~ The method of glass preparation, grinding and 27 green hody preparation are similar to that given for the llZ~789 1 ~-spodumene compositions. The average particle size for 2 the glass powder should be in the range of 2 to 7 ~m for 3 good sintering and strength.
4 Table III gives the optimum sintering temperatures S for the cordierite ceramics. It has also been discovered, 6 however, that satisfactory materials can be produced at 7 sintering temperatures spanning 80~100C covered by the 8 exothermic peak in the thermograms of the corresponding 9 glasses. For example, composition #10 can be satisfactorily sintered at temperatures within the range of 870C to 950C
11 and the variation of the thermal expansion coefficient for 12 materials sintered within this range is only - l x 107/C.
13 The crystalline phases developed in the dif~erent 14 glass-ceramics are influenced by the minor constituents and in some cases by the sinterinq temperatures employed.
16 Composition #8 forms ~-cordierite as a major phase, 17 together with minor amounts of ~-cordierite. Composition 18 #9 contains ~-cordierite as the only crystalline phase.
19 The formation of ~-cordierite confers to the glass-ceramic a somewhat higher thermal expansion coefficient as well as 21 an apparent higher dielectric constants. It is evident 22 that the minor constituent Li2o catalyses the formation 23 of ~-form of cordierite. Composition #10 contains only 24 -cordierite due, it is believed, to the presence of boric oxide in the glass composition. Composition #ll 26 contains ~-cordierite as the major phase along with 27 some -cordierite. Although the thermal expansion coefficient 28 of this material for the sintering temperature of 925C falls FI9-77-046 -l9-.
~lZZ78g 1 within the desired range of 20 to 50 x 107/C, we have noted 2 that the thermal expansion coefficient is dependent on the 3 sintering temperature employed. Material sintered at 970C
4 has an expansion coefficient of 36.4 x 107/C and that sintered at 990C has the value of 40 x 107/C. The enhanced 6 strength for composition #11 is thought to result from im-7 proved crystal nucleation promoted by the inclusion of ZrO2.
8 This nucleant, however, a~so promotes the formation of the 9 ~-cordierite phase if its concentration is above a critical limit. Composition #12, con~aining lower concentrations of 11 B2O3 and ZrO2 compared to composition #11, develops -cor-12 dierite as the major crystal phase together with clinoenstatite 13 as a minor phase. The thermal expansion coefficient of this 14 material is stable over a wide sintering temperature range.
For sintering temperatures between 915C and 970C, the 16 expansion coefficient only varied for 23 x 107/C to 24 x 107/C.
17 The high strength of composition #12 is attributed on the basis 18 of microscopic and x-ray diffraction studies to a high volume 19 fraction of the crystalline phase which occurs as a crystal-line network having a very small domain size. The formation 21 of clinoenstatite minor phase in the residual glass during 22 sintering i8 also likely to have contributed to the high 23 flexural strength of this material.
24 Investigation has shown that the sintering process for the cordierite glass-ceramics is fundamentally different 26 from that for the ~-spodumene glass-ceramics. FIGURE 3 27 shows typical shrinkage curves for a material that sinters l~Z2789 1 to zero porosity below 1000C (Curve A, e.g. composition #10, 2 Table III) and for a material that does not undergo complete 3 densification below 1000C (Curve B, e.g. composition #8).
4 It will be seen that unlike the ~-spodumene glass-ceramics, the cordierite materials undergo sintering in a single stage.
6 For materials that are sinterable below 1000C, we believe 7 that the densification involves predominantly glass-to-glass 8 coalescence. For example; composition #10 can be sintered 9 to negligible porosity at a temperature of 850C but examina-tion of the material fired to this temperature shows very 11 little crystallinity in it.
12 Based on optical and electron microscopic observa-13 tions and on x-ray diffraction results, it is believed that 14 the sintering process for these materials is as follows:
After the burn-out of the organic binders, there is no 16 further dimensional change until glass particles begin to 17 coalesce by viscous and diffusional mechanisms, perhaps 18 also assisted by the glass-in-glass phase separation observed 19 in this temperature range. Soon thereafter, an interconnect-ing network of crystallites appears roughly delineating the 21 prior glass particle boundaries, this leading us to believe 22 that surface nucleation must have occurred on the individual 23 glass grains prior to their coalescence. The formation of 24 these highly crystalline networks acts to arrest the excessive deformation by viscous flow of the body. Internal nucleation 26 and crystallization within the glassy domains occurs at a 27 slightly higher temperature, this being promoted by the 28 added nucleants such as P2O5, ZrO2, Tio2 and ZnO. This l'~'h~7f~
.
1 mechanism is well illustrated in an experiment in which 2 a bundle of fibers glass #10 of each of about 0.2mm 3 diameter was subjected to the same thermal cycle as was 4 used for sintering. The glass fibers sintered together at their points of contact but each fiber had developed 6 a highly crystalline skin to a depth of about 1-2~m. The 7 interiors of the fibers remained largely glassy. The 8 ~unction of additives suc~ as Li2o and B2O3 may well be 9 to delay the onset of crystallization thereby allowing sintering within desired temperature range.
11 It is believed that the critical factors that 12 enable the distortion-free sintering to near theoretical 13 densities of these glass-ceramics are the following:
14 (i) the absence a well-defined nucleation hold on the way to the sintering temperature which prevents internal 16 nucleation and of crystallization prior to the completion 17 of glass-to-glass sintering, (ii) the relative ease of 18 surface nucleation compared to bulk nucleation in these 19 glasses, such nucleation occurring despite the factor (i) above prior to glass-to-glass sintering, (iii) a clear 2t separation between the surface nucleation and crystal-22 lization temperatures allowing the glass densification to 23 take place to completion at temperatures in between, (iv) 24 the onset of surface crystallization following soon after the completion of densification providing a crystallized 26 network that prevents further viscous deformation.
27 The sintered glass-ceramics can be said to have 28 a two-level microstructure, a cellular network of crystals ~lZZ789 l ~n tho oc~lo oC l~ prl~ Jlnnn l)nr~cl~ rll~l~n 2 (2-5~m), forming the first level within which are formed 3 discretc crystals o~ sub-micron ~o 1-2l~n~ size di~pcrRed 4 in the residual glassy phase. A typical microstructure is shown in FIGURE 4. This unique dual microstructure 6 is believed responsible for the high flexural strength of 7 these sintered glass-ceramics. Furthermore, by minor 8 additions of Li2o or B2O3, it is possible to control the 9 form of cordierite that is formed and thus to control the thermal expansion coefficient and dielectric constant 11 within certain limits.
12 The glass-ceramic of the ~-spodumene type as well 13 as of the cordierite type described above can be used for 14 other applications besides the multilayer substrates. Such applications could be based on one or more of their proper-16 ties such as their easy sinterability, Iow thermal expansion 17 coefficients, low dielectric constant and high flexural 18 strength. While some of these compositions cannot be bulk 19 crystallized, others such as composition #1 of Table II can be used in this condition.
21 Also, it is to be understood that as used herein 22 and in the claims the term "alpha-cordierite glass" is de-23 fined as and limited to (l) a precursor for "alpha-cordierite 24 glass ceramics", and (2) formed from a bath consisting of, 25 by weight 26 SiO248 to 55% P2O5 0 to 3~
27 Al2O318 to 25% Tio2 to 2.5%
28 MgO18 to 25% SnO2 0 to 2.5~
29 ZnO0 to 2% Zr2 to 2.5%
1 Conversely, as used herein and in the claims, the term 2 "alpha-cordierite glass ceramic" is defined as and limited 3 to a glass ceramic structure coalesced and crys~allized from 4 "alpha-cordierite glasses" to an article having a micro-structure of a pervasive network of 2 to 5~m crystallites 6 of alpha-cordierite and clinoenstatite with the interstices 7 of the network occupied by residual glass having dispersed 8 therein discrete secondar~ 1 to 2~m crystallites of 9 clinoenstatite and additional cordierite phase.
Multilayer Substrate Fabrica~ion 11 The glasses of the ~-spodumene type and the 12 cordierite type described previously can be used to fabricate 13 multilayer glass-ceramic substrates containing co-sintered 14 conductor patterns of gold, silver or copper. The substrate fabrication involves the following steps:
16 Step 1: The cullet of the chosen glass is ground 17 to average particle sizes in the range of 2 to 7~m. The 18 grinding can be done in two stages -- a preliminary dry or 19 wet grinding to -- 400 mesh particle size followed by further grinding with suitable organic binders and solvents until 21 the average particle size is reduced to lie between 2 to 22 7~m and a castable slurry or slip is obtained. A single 23 stage prolonged grinding of cullet in the medium of the 24 binder and solvent until the desired particle size is obtalned can also be used. In the latter case, a filtering 26 step may be needed to remove oversized particles. ~y way 27 of example, a suitable binder is poly-vinyl butaryl resin 28 with a plasticizer such as dioctophthalate or dibutyl : !
1 phthalate. Other suitable polymers are polyvinyl formal, 2 polyvinyl chloride, polyvinyl acetate or certain acrylic 3 resins. The purposes of adding an easily evaporable 4 solvent such as methanol is (i) to initially dissolve the binder so as to enable it to coat the individual glass 6 particles, and (ii) to adjust the rheology of the slip or 7 slurry for good castability.
8 Step 2: The slip or slurry prepared as in Step 1 9 is cast, in accordance with conventional techniques, into thin green sheets preferably by a doctor-blading technique.
11 Step 3: The cast sheets are blanked to the re-12 quired dimensions in a blanking tool and via holes are 13 punched in them in the required configuration.
14 Step 4: Metallizing paste of gold, silver or copper is extruded into the via ho~es in the individual 16 sheets by screen printing method.
17 Step 5: The required conductor patterns are 18 screen printed on to the individual green sheets of Step 4.
19 Step 6: A plurality of sheets prepared as in Step 5 are laminated together in registry in a laminating 21 press.
22 The temperature and pressure employed for 23 lamination should be such as to cause (i) the individual 24 green sheets to bond to each other to yield a monolithic green substrate, (ii) to cause the green ceramic to 26 sufficiently flow and enclose the conductor patterns.
27 Step 7: Firing the ceramic to the sintering 28 temperature to accomplish binder removal, sintering of the ~ . . ~ . .
7~
-'1 glass particles and their concurrent conversion to glass-2 ceramics by crystallization, and the sintering of the 3 metal particles in the conductor patterns to dense metal 4 lines and vias. The particular glass-ceramic composition chosen should be one that has an optimum sintering tempera-6 ture-between 50-150C below the melting point of the con-7 ductor metal employed.
8 During'the firing cycle, the organic 9 binders begin to come off at 300C and the binder removal is essentially complete before appreciable glass-to-glass 11 sintering has occurred. The sintering proceeds according 12 to the mechanisms previously outlined and results in the 13 conversion of glass to glass ceramic state in which the 14 crystalline phases formed occupy greater than 80% of the body by volume. The holding time at the sintering tempera-16 ture can vary from 1 to 5 hours. The body is then cooled 17 at a controlled rate not to exceed 4C/minute to at least 18 about 400C after which faster cooling rates may be used.
19 The critical factors governing the fabrication of a multilayer substrate to close dimensional 21 and distortional tolerances are the following;
22 (i) Complete and controlled removal of organic 23 binders during the firing cycle prior to appreciable glass-24 to-glass coalescence. A slow heating rate of 1C to 2C is essential for ensuring a controlled binder removal rate.
2~ (ii) The crystallization of glass during the 27 sintering process which arrests the tendency of the glass 28 to deform by viscous flow.
~Z~789 1 (iii) The matching of the shrinkages of the 2 conductor pattern and the glass-ceramic. Shrinkage of ~3 the metal paste is governed by factors such as average 4 particle size and size distribution, particle loading in the paste and the lamination pressure. The firing 6 shrinkage of the glass-ceramic can also be manipulated 7 within certain limits by varying the binder-to-glass xatio 8 in the green sheets and the lamination pressure.
9 It is noted that despite the large disparity in the thermal expansion coefficients of gold, silver and 11 copper, on the one hand, and,the glass-ceramics of this 12 invention, on the other, structural integrity of ~he 13 substrate is preserved because of (i) the high degree of 14 ductility of these metals and (ii) good bonding between the metal and the glass-ceramic. The latter could be en-16 hanced by the additions of suitable glass frits or other 17 bonding aids to the metallizing paste.
18 When using copper as the metallizing paste, the 19 firing of the substrate has to be done in non-oxidizing atmospheres. For this reason, organic binders employed 21 for green sheet fabrication should be capable of being 22 evaporated off in such atmospheres at reasonable tempera-23 tures.
24 While the invention has been particularly shown and described with reference to the preferred embodiments 26 thereof, it will be understood by those skilled in the art 2~ that the foregoins and other change6 in form and detail may 28 be made therein without departing from the spirit and scope 29 of the invention.
11 BaO - 2.0 2.0 12 ZnO - 2.1 2.5 2.0 2.0 2.0 13 Li2o 10.0 8.8 8.0 10.0 8.0 8.0 4.2 14 Na2O - - - - - - 0.9 15 K2O 2.0 3.1 2.0 2.0 2.0 2.0 16 B O - - _ _ 2.0 0-5 1.8 17 P2O5 1.5 1.6 1.5 1.5 1.5 1.5 18 2 ~ - - _ _ 2.5 19 F ~ 0.8 20 ~ Sintering 21 Temp.(C) 925 850 990 900 855 * 910 22 Thermal 23 Exp.Coeff.
24 (C lxl07) 32 83 60 43 29 _ 20 25 Modulus of 26 Rupture 27 (psi) 30,000 67,000 10,400 63,400 30,000 - 25,200 28 K 6.5 - 6.5 6.3 6.4 - 5.0 29 (permittivity) * did not sinter satisfactorily at temperatures below 1000C
7~g I These glasses were melted at temperatures close 2 to 1500C from mixtures of suitable raw materials until 3 free from unreacted material and gas bubbles. The molten 4 glass was quenched by pouring it into col~ water to produce "cullet" suitable for further grinding. The "cullet" was 6 ground to average particle sizes ranging from 3-7 ~m and 7 mixed with suitable organic binders and solvents to obtain 8 a castable slip or slurry from which thin sheets were cast 9 using conventional doctor blading techniques. The bodies were prepared by laminating a desired number of these 11 sheets in a laminating press at moderate temperatures and 12 pressures (e.g. 100C and 3000 psi) to obtain a monolithic 13 "green" body. Specimens for the measurement of rupture 14 strength, thermal expansion coefficient and dielectric constant measurements were formed as above and fired in air 16 using programmed furnaces. Prior experimentation had showed 17 that the heating rate should be low, not greater than 2C/
18 minute; faster heating rates resulted in incomplete binder 19 burnout. It is also believed that the use of a relatively slow heating rate is advantageous in allowing surface and 21 internal nucleation processes to be completed in a controlled 22 manner.
23 The modulus of rupture of the sintered glass-24 ceramics was measured in a 3-point bending mode on bar specimens and in general the mean of ten (10) déterminations 26` was calculated. Thermal expansion coefficients were measured 27 in the range from room temperature to 300C using two-point Z78g il metl-od. Dielectrio col~tan~ were d~ m~rle~ a~ a ~re-2 ~uency of 1 Mll~ at 25C.
3 Typical values of thesc pro~)crties are quoted in 4 Table II. In general, the sintering temperatures given are those yielding optimum results but it should be understood 6 that for each material, a sintering range exists usually 7 extending 20C above and below the optimum temperature.
8 The optimum holding time at the sintering temp~rature was 9 two hour~, though times ranging from one to five hours also give satisfactory results.
11 Of the compositions given in Table II, glasses 12 #1, #4, #5, and #7 yielded glass-ceramics having properties 13 suitable for the present multilayer substrate application.
14 Compositions #3 and #6 failed to sinter satisfactorily below 1000C and composition #2, while it yielded a high 16 strength material, resulted in a glass-ceramic of thermal 17 expansion coefficient outside the desired rang~.
18 X-ray diffraction analysis showed that glass 19 ceramics ~1, #4 and #5 contained ~-spodumene as the major phase and a lithium meta and disilicates as minor phases.
21 Composition #2 contained only a very small amount of ~-22 spodumene plus a major amount of an unidentified crystal 23 phase~ Composition #3 contained ~-spodumene as the major 24 phase along with minor amounts of lithium metasilicate and dlsillcate.
26 On thi6 basis, it is believed that ~-spodumene 27 should be present a6 a major phase to enable the desired 28 thermal expansion coefficient to be obtained but that binary .
;Z789 1 lithium ~illcat~s must also b~ pr-~s~llt A~ mi.l10~ PhA~
1)r~ 0 n1I~ rI n~J D~ I L1OI~ 1HLI-3 ceramics at tempor~turcs bolow 1000C.
~ Dl~AI:onlo~ric ~Illrilll~tl~lf~ oElF~ lln ~ oll S laminates as a function temperature illustrate very well 6 the differences between those materials containing lithium 7 metasilicate as a minor phase and those that do not contain 8 this phase. Curve A, FIG~RE 1, is typical of the former 9 type (e.g. composition #1) and Curve B, FIGURE 1 of the latter type of material ~e.g~. glasses #2 and #6). For the 11 satisfactory material (Curve A) densification commences at 12 a temperature of about 580C. At this stage, the material 13 is still uncrystallized glass. At a temperature of about 14 610C, however, further densification is arrested owing to the onset of crystallization. A second densification stage 16 commences at about 910C and this proceeds until the glass-17 ceramic becomes non-porous. For the unsatisfactory ma~erials 18 (Curve B), the second densification stage is absent at 19 temperatures below 1000C.
Differential thermal analysis, x-ray diffraction 21 analysis and electron microscopic studies have indicated that 22 the commencement of the second stage of the sintering process 23 corresponds to the liquidus temperature of lithium meta-24 silicate phase. Some of the metasilicate recrystallizes on cooling the glass-ceramic.
26 It is believed that the satisfactory sintering of 27 these ~-spodumene glass-ceramics involves the following 28 steps. Initial sintering of the glass powder by viscous 29 flow and diffusion processes, possibly also assisted by ~lZZ7139 1 glass-in-glass phase separation, occurs between 580-600C.
~2 As a result of surface nucleation processes, the individual 3 glass grains become covered with a layer of lithium meta-4 silicate. Internal nucleation within the glass grains follows causing the precipitation of ~-spodumene crystals, whose 6 maximum size will be set by the particle diameter. Further 7 sintering then requires the partial or complete melting of 8 the metasilicate phase which brings about (i) consolidation 9 of the ~-spodumene grains by capillary forces and (ii) neck or bridge formation between~the ~-spodumene particles 11 promoted by the reaction of the molten metasilicate with 12 the alumina and silica of the residual glass to form further 13 quantities of ~-spodumene. At temperatures above the 14 recommended sintering range, the metasilicate appears to flux the B-spodumene destroying the inter-particle bridges.
16 The reaction of the lithium metasilicate with residual glass 17 to form B-spodumene in certain Li2O - A12O3 - SiO2 systems 18 has also been alluded to by Stookey in U. S. Patent 2,971,853.
19 The microstructure of the glass-ceramics obtained from such a sintering mechanism consists of cosintered 21 B-sPodumene crystals forming rigid skeletal structures with 22 the residual glass occupying the interstitial regions in such 23 a ~tructure. FIGURE 2 is an example of such a microstructure 24 which more resembles those of conventional ceramics obtained by sintering ceramic powders, such as alumina with minor 26 glass additions than those of "bulk" glass-ceramics. The 27 absence of a continuous glassy matrix or network is believed 28 to be the principal factor governing the high flexural 29 strengths of the present materials.
~lZZ78g 1 It is to be understood that as used herein and ~2 in the claims, the term "B-sPodumene glass" is defined as 3 and restxicted to (1) a precursor for ~-spodumene glass 4 ceramic and (2) formed from a batch consisting of, by 5 weight:
6 SiO265 to 75% Lio2 3 5 to 11%
7 A12O312 to 17~ B2O3 0 to 2.5%
8 MgO 0 to 2~ P2O5 0 to 2.5~
9 ZnO 0 to 2~ F 0 to 3%, and also from 0 to 2% of at least one oxide selected from the 11 group consisting of CaO and BaO, and from 1.0 to 3.5~ of at 12 least one oxide selected from the group consisting of Na2O
13 and K2O.
14 Conversely, as used herein and in the claims, the term "B-spodumene glass ceramic" is defined as and restricted 16 to a glass ceramic structure coalesced and crystallized from 17 "B-spodumene glasses" into an article having a microstructure 18 of a pervasive continuous network of 2 to 5 ~m crystallites of 19 B-spodumene with the interstices of said network occupied by residual glass having dispersed therein discrete secondary 21 1 to 2 ~m crystallites of lithium metasilicate.
22 Sinterable Cordierite Glass-Ceramics _ 23 The overall composition ranges of the cordierite 24 glass-ceramics of this invention is given in Table I and specific examples are listed in Table III.
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~ ~ U~
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o O
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N N It~
O
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U
Z ~ ~ ~ O O
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~1 0 N 0 0 N 0 0~ 0~ 0 0~ ~ a) .C X O o O ~ P~ h m ~ u -- :~ o~
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ll'ZZ~89 1 The composition limits are set on the one hand by the need 2 to ensure that cordierite appears as the major crystalline 3 phase in order to achieve desired thermal expanSiQn co-4 efficients and on the other to facilitate sintering below 1000C. Reduction of MgO and ~12O3 contents below the 6 specified limits is not permissible for this reason. Ex-7 cessively high A12O3 and SiO2 contents would result in 8 materials not capable of sintering below 1000C. MgO
9 contents higher than the specified maximum could result in the formation of magnesium silicates in significant 11 amounts causing the thermal expansion coefficients to be 12 higher than desired.
13 The minor constituents are included to perform 14 important functions. ~he P2O5, ZrO2, TiO2 and SnO2 are added to promote nucleation and to regulate the micro-16 structural development. The Li2o and B2O3 are included as 17 sintering aids; they also serve to regulate the nature of 18 the crystalline phase formed~ Cordierite can appear in 19 either the ~ or ~ form. Sometimes, mixtures of the two appear in the same glass-ceramic. As will become clear in 21 what follows, it has been discovered that in order to 22 produce glass-ceramics having stable thermal expansion 23 coefficients in the desired range as well as lower dielectric 24 constants, it is necessary to develop the cordierite phase predominantly in the ~ form.
2~ The method of glass preparation, grinding and 27 green hody preparation are similar to that given for the llZ~789 1 ~-spodumene compositions. The average particle size for 2 the glass powder should be in the range of 2 to 7 ~m for 3 good sintering and strength.
4 Table III gives the optimum sintering temperatures S for the cordierite ceramics. It has also been discovered, 6 however, that satisfactory materials can be produced at 7 sintering temperatures spanning 80~100C covered by the 8 exothermic peak in the thermograms of the corresponding 9 glasses. For example, composition #10 can be satisfactorily sintered at temperatures within the range of 870C to 950C
11 and the variation of the thermal expansion coefficient for 12 materials sintered within this range is only - l x 107/C.
13 The crystalline phases developed in the dif~erent 14 glass-ceramics are influenced by the minor constituents and in some cases by the sinterinq temperatures employed.
16 Composition #8 forms ~-cordierite as a major phase, 17 together with minor amounts of ~-cordierite. Composition 18 #9 contains ~-cordierite as the only crystalline phase.
19 The formation of ~-cordierite confers to the glass-ceramic a somewhat higher thermal expansion coefficient as well as 21 an apparent higher dielectric constants. It is evident 22 that the minor constituent Li2o catalyses the formation 23 of ~-form of cordierite. Composition #10 contains only 24 -cordierite due, it is believed, to the presence of boric oxide in the glass composition. Composition #ll 26 contains ~-cordierite as the major phase along with 27 some -cordierite. Although the thermal expansion coefficient 28 of this material for the sintering temperature of 925C falls FI9-77-046 -l9-.
~lZZ78g 1 within the desired range of 20 to 50 x 107/C, we have noted 2 that the thermal expansion coefficient is dependent on the 3 sintering temperature employed. Material sintered at 970C
4 has an expansion coefficient of 36.4 x 107/C and that sintered at 990C has the value of 40 x 107/C. The enhanced 6 strength for composition #11 is thought to result from im-7 proved crystal nucleation promoted by the inclusion of ZrO2.
8 This nucleant, however, a~so promotes the formation of the 9 ~-cordierite phase if its concentration is above a critical limit. Composition #12, con~aining lower concentrations of 11 B2O3 and ZrO2 compared to composition #11, develops -cor-12 dierite as the major crystal phase together with clinoenstatite 13 as a minor phase. The thermal expansion coefficient of this 14 material is stable over a wide sintering temperature range.
For sintering temperatures between 915C and 970C, the 16 expansion coefficient only varied for 23 x 107/C to 24 x 107/C.
17 The high strength of composition #12 is attributed on the basis 18 of microscopic and x-ray diffraction studies to a high volume 19 fraction of the crystalline phase which occurs as a crystal-line network having a very small domain size. The formation 21 of clinoenstatite minor phase in the residual glass during 22 sintering i8 also likely to have contributed to the high 23 flexural strength of this material.
24 Investigation has shown that the sintering process for the cordierite glass-ceramics is fundamentally different 26 from that for the ~-spodumene glass-ceramics. FIGURE 3 27 shows typical shrinkage curves for a material that sinters l~Z2789 1 to zero porosity below 1000C (Curve A, e.g. composition #10, 2 Table III) and for a material that does not undergo complete 3 densification below 1000C (Curve B, e.g. composition #8).
4 It will be seen that unlike the ~-spodumene glass-ceramics, the cordierite materials undergo sintering in a single stage.
6 For materials that are sinterable below 1000C, we believe 7 that the densification involves predominantly glass-to-glass 8 coalescence. For example; composition #10 can be sintered 9 to negligible porosity at a temperature of 850C but examina-tion of the material fired to this temperature shows very 11 little crystallinity in it.
12 Based on optical and electron microscopic observa-13 tions and on x-ray diffraction results, it is believed that 14 the sintering process for these materials is as follows:
After the burn-out of the organic binders, there is no 16 further dimensional change until glass particles begin to 17 coalesce by viscous and diffusional mechanisms, perhaps 18 also assisted by the glass-in-glass phase separation observed 19 in this temperature range. Soon thereafter, an interconnect-ing network of crystallites appears roughly delineating the 21 prior glass particle boundaries, this leading us to believe 22 that surface nucleation must have occurred on the individual 23 glass grains prior to their coalescence. The formation of 24 these highly crystalline networks acts to arrest the excessive deformation by viscous flow of the body. Internal nucleation 26 and crystallization within the glassy domains occurs at a 27 slightly higher temperature, this being promoted by the 28 added nucleants such as P2O5, ZrO2, Tio2 and ZnO. This l'~'h~7f~
.
1 mechanism is well illustrated in an experiment in which 2 a bundle of fibers glass #10 of each of about 0.2mm 3 diameter was subjected to the same thermal cycle as was 4 used for sintering. The glass fibers sintered together at their points of contact but each fiber had developed 6 a highly crystalline skin to a depth of about 1-2~m. The 7 interiors of the fibers remained largely glassy. The 8 ~unction of additives suc~ as Li2o and B2O3 may well be 9 to delay the onset of crystallization thereby allowing sintering within desired temperature range.
11 It is believed that the critical factors that 12 enable the distortion-free sintering to near theoretical 13 densities of these glass-ceramics are the following:
14 (i) the absence a well-defined nucleation hold on the way to the sintering temperature which prevents internal 16 nucleation and of crystallization prior to the completion 17 of glass-to-glass sintering, (ii) the relative ease of 18 surface nucleation compared to bulk nucleation in these 19 glasses, such nucleation occurring despite the factor (i) above prior to glass-to-glass sintering, (iii) a clear 2t separation between the surface nucleation and crystal-22 lization temperatures allowing the glass densification to 23 take place to completion at temperatures in between, (iv) 24 the onset of surface crystallization following soon after the completion of densification providing a crystallized 26 network that prevents further viscous deformation.
27 The sintered glass-ceramics can be said to have 28 a two-level microstructure, a cellular network of crystals ~lZZ789 l ~n tho oc~lo oC l~ prl~ Jlnnn l)nr~cl~ rll~l~n 2 (2-5~m), forming the first level within which are formed 3 discretc crystals o~ sub-micron ~o 1-2l~n~ size di~pcrRed 4 in the residual glassy phase. A typical microstructure is shown in FIGURE 4. This unique dual microstructure 6 is believed responsible for the high flexural strength of 7 these sintered glass-ceramics. Furthermore, by minor 8 additions of Li2o or B2O3, it is possible to control the 9 form of cordierite that is formed and thus to control the thermal expansion coefficient and dielectric constant 11 within certain limits.
12 The glass-ceramic of the ~-spodumene type as well 13 as of the cordierite type described above can be used for 14 other applications besides the multilayer substrates. Such applications could be based on one or more of their proper-16 ties such as their easy sinterability, Iow thermal expansion 17 coefficients, low dielectric constant and high flexural 18 strength. While some of these compositions cannot be bulk 19 crystallized, others such as composition #1 of Table II can be used in this condition.
21 Also, it is to be understood that as used herein 22 and in the claims the term "alpha-cordierite glass" is de-23 fined as and limited to (l) a precursor for "alpha-cordierite 24 glass ceramics", and (2) formed from a bath consisting of, 25 by weight 26 SiO248 to 55% P2O5 0 to 3~
27 Al2O318 to 25% Tio2 to 2.5%
28 MgO18 to 25% SnO2 0 to 2.5~
29 ZnO0 to 2% Zr2 to 2.5%
1 Conversely, as used herein and in the claims, the term 2 "alpha-cordierite glass ceramic" is defined as and limited 3 to a glass ceramic structure coalesced and crys~allized from 4 "alpha-cordierite glasses" to an article having a micro-structure of a pervasive network of 2 to 5~m crystallites 6 of alpha-cordierite and clinoenstatite with the interstices 7 of the network occupied by residual glass having dispersed 8 therein discrete secondar~ 1 to 2~m crystallites of 9 clinoenstatite and additional cordierite phase.
Multilayer Substrate Fabrica~ion 11 The glasses of the ~-spodumene type and the 12 cordierite type described previously can be used to fabricate 13 multilayer glass-ceramic substrates containing co-sintered 14 conductor patterns of gold, silver or copper. The substrate fabrication involves the following steps:
16 Step 1: The cullet of the chosen glass is ground 17 to average particle sizes in the range of 2 to 7~m. The 18 grinding can be done in two stages -- a preliminary dry or 19 wet grinding to -- 400 mesh particle size followed by further grinding with suitable organic binders and solvents until 21 the average particle size is reduced to lie between 2 to 22 7~m and a castable slurry or slip is obtained. A single 23 stage prolonged grinding of cullet in the medium of the 24 binder and solvent until the desired particle size is obtalned can also be used. In the latter case, a filtering 26 step may be needed to remove oversized particles. ~y way 27 of example, a suitable binder is poly-vinyl butaryl resin 28 with a plasticizer such as dioctophthalate or dibutyl : !
1 phthalate. Other suitable polymers are polyvinyl formal, 2 polyvinyl chloride, polyvinyl acetate or certain acrylic 3 resins. The purposes of adding an easily evaporable 4 solvent such as methanol is (i) to initially dissolve the binder so as to enable it to coat the individual glass 6 particles, and (ii) to adjust the rheology of the slip or 7 slurry for good castability.
8 Step 2: The slip or slurry prepared as in Step 1 9 is cast, in accordance with conventional techniques, into thin green sheets preferably by a doctor-blading technique.
11 Step 3: The cast sheets are blanked to the re-12 quired dimensions in a blanking tool and via holes are 13 punched in them in the required configuration.
14 Step 4: Metallizing paste of gold, silver or copper is extruded into the via ho~es in the individual 16 sheets by screen printing method.
17 Step 5: The required conductor patterns are 18 screen printed on to the individual green sheets of Step 4.
19 Step 6: A plurality of sheets prepared as in Step 5 are laminated together in registry in a laminating 21 press.
22 The temperature and pressure employed for 23 lamination should be such as to cause (i) the individual 24 green sheets to bond to each other to yield a monolithic green substrate, (ii) to cause the green ceramic to 26 sufficiently flow and enclose the conductor patterns.
27 Step 7: Firing the ceramic to the sintering 28 temperature to accomplish binder removal, sintering of the ~ . . ~ . .
7~
-'1 glass particles and their concurrent conversion to glass-2 ceramics by crystallization, and the sintering of the 3 metal particles in the conductor patterns to dense metal 4 lines and vias. The particular glass-ceramic composition chosen should be one that has an optimum sintering tempera-6 ture-between 50-150C below the melting point of the con-7 ductor metal employed.
8 During'the firing cycle, the organic 9 binders begin to come off at 300C and the binder removal is essentially complete before appreciable glass-to-glass 11 sintering has occurred. The sintering proceeds according 12 to the mechanisms previously outlined and results in the 13 conversion of glass to glass ceramic state in which the 14 crystalline phases formed occupy greater than 80% of the body by volume. The holding time at the sintering tempera-16 ture can vary from 1 to 5 hours. The body is then cooled 17 at a controlled rate not to exceed 4C/minute to at least 18 about 400C after which faster cooling rates may be used.
19 The critical factors governing the fabrication of a multilayer substrate to close dimensional 21 and distortional tolerances are the following;
22 (i) Complete and controlled removal of organic 23 binders during the firing cycle prior to appreciable glass-24 to-glass coalescence. A slow heating rate of 1C to 2C is essential for ensuring a controlled binder removal rate.
2~ (ii) The crystallization of glass during the 27 sintering process which arrests the tendency of the glass 28 to deform by viscous flow.
~Z~789 1 (iii) The matching of the shrinkages of the 2 conductor pattern and the glass-ceramic. Shrinkage of ~3 the metal paste is governed by factors such as average 4 particle size and size distribution, particle loading in the paste and the lamination pressure. The firing 6 shrinkage of the glass-ceramic can also be manipulated 7 within certain limits by varying the binder-to-glass xatio 8 in the green sheets and the lamination pressure.
9 It is noted that despite the large disparity in the thermal expansion coefficients of gold, silver and 11 copper, on the one hand, and,the glass-ceramics of this 12 invention, on the other, structural integrity of ~he 13 substrate is preserved because of (i) the high degree of 14 ductility of these metals and (ii) good bonding between the metal and the glass-ceramic. The latter could be en-16 hanced by the additions of suitable glass frits or other 17 bonding aids to the metallizing paste.
18 When using copper as the metallizing paste, the 19 firing of the substrate has to be done in non-oxidizing atmospheres. For this reason, organic binders employed 21 for green sheet fabrication should be capable of being 22 evaporated off in such atmospheres at reasonable tempera-23 tures.
24 While the invention has been particularly shown and described with reference to the preferred embodiments 26 thereof, it will be understood by those skilled in the art 2~ that the foregoins and other change6 in form and detail may 28 be made therein without departing from the spirit and scope 29 of the invention.
Claims (5)
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A method of forming a glass ceramic composite structure comprising forming at least one green sheet comprised of a thermoplastic organic binder having dispersed therein 2 to 7µm sized particles of glass selected from the group con-sisting of .beta.-spodumene and alphacordierite glasses, forming on a surface of a first said green sheet a pattern of an electrical conductor forming composition;
superimposing a second said sheet on said surface of said first sheet to sandwich said pattern therebetween;
laminating said superimposed sheets together;
heating said laminate to a temperature in the range of about 870°C to about 1000°C at a rate not exceed-ing 2°C per minute;
firing said laminate at said temperature to a) decompose and eliminate said binder, and b) to coalesce and crystallize the said glass of said laminate into a glass ceramic structure having said electrical conductor pattern extending within the interior thereof.
superimposing a second said sheet on said surface of said first sheet to sandwich said pattern therebetween;
laminating said superimposed sheets together;
heating said laminate to a temperature in the range of about 870°C to about 1000°C at a rate not exceed-ing 2°C per minute;
firing said laminate at said temperature to a) decompose and eliminate said binder, and b) to coalesce and crystallize the said glass of said laminate into a glass ceramic structure having said electrical conductor pattern extending within the interior thereof.
2. The method of Claim 1 wherein said conductor pattern is a metallic composition of copper, silver, gold and alloys thereof.
3. The method of Claim 1 including providing means for extending said pattern to at least one surface of said fired laminate.
4. The method of Claim 3 wherein said conductor pattern is a metallic composition of copper, silver, gold and alloys thereof.
5. The method of Claim 3 including mounting an integrated circuit semiconductor chip on said surface in electrical connection to a portion of said pattern extension.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA377,129A CA1122789A (en) | 1978-02-06 | 1981-05-07 | Glass-ceramic structures and sintered multilayer substrates thereof with circuit patterns of gold, silver or copper |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/875,703 US4301324A (en) | 1978-02-06 | 1978-02-06 | Glass-ceramic structures and sintered multilayer substrates thereof with circuit patterns of gold, silver or copper |
| US875,703 | 1978-02-06 | ||
| CA314,417A CA1109664A (en) | 1978-02-06 | 1978-10-26 | Glass-ceramic structures and sintered multilayer substrates thereof with circuit patterns of gold, silver or copper |
| CA377,129A CA1122789A (en) | 1978-02-06 | 1981-05-07 | Glass-ceramic structures and sintered multilayer substrates thereof with circuit patterns of gold, silver or copper |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1122789A true CA1122789A (en) | 1982-05-04 |
Family
ID=27165941
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA377,129A Expired CA1122789A (en) | 1978-02-06 | 1981-05-07 | Glass-ceramic structures and sintered multilayer substrates thereof with circuit patterns of gold, silver or copper |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1122789A (en) |
-
1981
- 1981-05-07 CA CA377,129A patent/CA1122789A/en not_active Expired
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