CA1091916A - Dielectric compositions of glass and magnesium titanates - Google Patents
Dielectric compositions of glass and magnesium titanatesInfo
- Publication number
- CA1091916A CA1091916A CA274,858A CA274858A CA1091916A CA 1091916 A CA1091916 A CA 1091916A CA 274858 A CA274858 A CA 274858A CA 1091916 A CA1091916 A CA 1091916A
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- Prior art keywords
- mgtio3
- compositions according
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- Prior art date
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Classifications
-
- 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
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0306—Inorganic insulating substrates, e.g. ceramic, glass
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/02—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances
- H01B3/08—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances quartz; glass; glass wool; slag wool; vitreous enamels
- H01B3/085—Particles bound with glass
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/08—Inorganic dielectrics
- H01G4/12—Ceramic dielectrics
- H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
- H01G4/1218—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates
- H01G4/1227—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates based on alkaline earth titanates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/08—Inorganic dielectrics
- H01G4/12—Ceramic dielectrics
- H01G4/129—Ceramic dielectrics containing a glassy phase, e.g. glass ceramic
Abstract
ABSTRACT
Dielectric powder compositions of magnesium titanate plus a glass, useful for forming dielectric layers in multi-layer electrode/dielectric structures on an alumina substrate.
Also, dispersions of such compositions in a vehicle and the resultant multilayer structures.
Dielectric powder compositions of magnesium titanate plus a glass, useful for forming dielectric layers in multi-layer electrode/dielectric structures on an alumina substrate.
Also, dispersions of such compositions in a vehicle and the resultant multilayer structures.
Description
BACKGROUND OF THE INVENTION
~ his invention relates to prlnted circuits, and more partlcularly to compositions ~or producing dlelectric layers ~or use ln such circuits.
It is use~ul ~n fabricatlng printled clrcuits to be able to conserve space by disposing a metallization dlrectly bove other metalllzations. To prlevent shorting and reduce capacitance coupllng, such metalli~ations are separated by dielectric material.
There are ~wo ways to produce such multilayer st,r,uctures. The ~irst consists of printing and firing "crossover" layers between prlnted conductor layers on a ~lngle substrate, to ~orm what is sometimes called a "multilevel" prlnted wiring board. The second method in-volves printing conductor patterns on organic-bonded thin -"tapes" Or particulate alumina, then laminating such pr~nted tapes and firing the resultant lamina~ed structure at high temperature to make a discrete monollthic multilayer structure whlch serves as lts own substrate. The present invention describes the role of certain compositions in rormlng, lnter alia, crossover dielectric layers in the "multilevel" type Or process,,wherein the substrate is a pre~ired alumina ceramlc.
A crossover dielectric composltion is essentially a low dielectric constant insulator capable o~ separating two conductor patterns through several riring steps. High melting, viscous glasses have been used as the dielectric so that the riring of the top conductor line can be carried out at a temperature below that at which so~tening of the dlelectric occurs. Meltlng or sortenlng of the crossover
~ his invention relates to prlnted circuits, and more partlcularly to compositions ~or producing dlelectric layers ~or use ln such circuits.
It is use~ul ~n fabricatlng printled clrcuits to be able to conserve space by disposing a metallization dlrectly bove other metalllzations. To prlevent shorting and reduce capacitance coupllng, such metalli~ations are separated by dielectric material.
There are ~wo ways to produce such multilayer st,r,uctures. The ~irst consists of printing and firing "crossover" layers between prlnted conductor layers on a ~lngle substrate, to ~orm what is sometimes called a "multilevel" prlnted wiring board. The second method in-volves printing conductor patterns on organic-bonded thin -"tapes" Or particulate alumina, then laminating such pr~nted tapes and firing the resultant lamina~ed structure at high temperature to make a discrete monollthic multilayer structure whlch serves as lts own substrate. The present invention describes the role of certain compositions in rormlng, lnter alia, crossover dielectric layers in the "multilevel" type Or process,,wherein the substrate is a pre~ired alumina ceramlc.
A crossover dielectric composltion is essentially a low dielectric constant insulator capable o~ separating two conductor patterns through several riring steps. High melting, viscous glasses have been used as the dielectric so that the riring of the top conductor line can be carried out at a temperature below that at which so~tening of the dlelectric occurs. Meltlng or sortenlng of the crossover
-2-~lel~ctric la accompanied by ~horting of the t~o conductor pattern~ again~t each c: ther wlth ~ub3equent ~ailure o~ the electrical circult. The ma~or requirement Por a cro~soYer dislectric i~ control o~ resoftening or therlaoplasticlty in the top conductor ~iring ~tep, Other pro~perty requlrem~nt~
~r~: ~a) low dielectric congtant to produce lo~ A.C~
capacitance coupli~g bet~een the circults ln~ulated by the cross~er dielectrlc, (b) low electric 103~ (hlgh Q) to avoid dielectrlc h~at~ng, (c) low "plnhollng" tend~ncy a~
a low tendency to avolve gas~e~ in firing, (d) proper gla~s ~o~tening tempera~ure ~o that the initi~l ~iring is adaptabl~
to the screen printing proces~, (e) a high re~lstance to thermal shock crazine, and (~) low ~ensitivity to watsr vapor and subsequent ~purious electrical 1088e~
Al~o required are composi~ion~ for produc~ng d~lectric layers in multilayer capacltor~ printed on an alumina substrate, Such capacitors includc tho~e of Bacher et al. U.S, Patent 3,683,245 and Bergmann U.S. PRtent
~r~: ~a) low dielectric congtant to produce lo~ A.C~
capacitance coupli~g bet~een the circults ln~ulated by the cross~er dielectrlc, (b) low electric 103~ (hlgh Q) to avoid dielectrlc h~at~ng, (c) low "plnhollng" tend~ncy a~
a low tendency to avolve gas~e~ in firing, (d) proper gla~s ~o~tening tempera~ure ~o that the initi~l ~iring is adaptabl~
to the screen printing proces~, (e) a high re~lstance to thermal shock crazine, and (~) low ~ensitivity to watsr vapor and subsequent ~purious electrical 1088e~
Al~o required are composi~ion~ for produc~ng d~lectric layers in multilayer capacltor~ printed on an alumina substrate, Such capacitors includc tho~e of Bacher et al. U.S, Patent 3,683,245 and Bergmann U.S. PRtent
3~679,943.
Among the numerou~ compo~ition~ known ~or produclng dielectric layer~ ln multllayer ~tructure~ are compo~ition~
ba~ed upon gl&~l8e8, su~h as the crystallizable gla~ses of Hoffman U.S. Patent 3,586,522 or AmiLn U.S. Patent 3,785,837;
or uE~on m~x~ure~ oi~ cry~talline materials and gla~e~ ~uch Q8 Amin U.S. P~tent 3,787,219 and ~acher et ~1. U,S. Patent 3,837~869.
Often the alumina substrate on whîch multllayer struc1;ure3 are ~ormed i8 distort~d or bowed by forc2~
exerted by the rired dielectrlc layer(s). There ls a need ror dlelectrlc compos~tions which have thermal expansion characteristics such that bowing is reduced, since other-~i e poor ~ilm adhesion can result.
Reductlon ln alumina substrate bowing caused by many commercially available dielectric compositions ls important, since dlstorted (non~planar~ substrates ~akes allignment difficult in printing subsequent layers on the ~ubstrate. Also9 bowed substrates are more difficult to mount into connector assemblies. Furthermore, the com-pressive forces exerted by the dielectric layer can result in cracklng of the alumina substrate when it undergoes therr.lal cycling, for example~ in dip soldering of the electrodes. The fired dielectric layers must be nonporous, as defined herein, and fireable at temperatures compatible with the firing temperatures of typical electrode composi-tions (e.g., below 975C.). Furthermore, when crystalline fillers are used, the fillers should have dielectric constants which are relatl~ely low.
SUMMARY OF THE INVENTION
I have invented certain compositions useful for printing dielectric layers in multilayer electronic ~tructures. The compositions have a reduced tendency to cause substrate distortion or bowing (i.e., deviation from planarity). The compositions comprise, by weight complementally, ~inely divided powders of (a) 65-90% o~ one or more glasses having a softening point greater than about 700C.
and a thermal expansion coefficient less than that Or alumina, and
Among the numerou~ compo~ition~ known ~or produclng dielectric layer~ ln multllayer ~tructure~ are compo~ition~
ba~ed upon gl&~l8e8, su~h as the crystallizable gla~ses of Hoffman U.S. Patent 3,586,522 or AmiLn U.S. Patent 3,785,837;
or uE~on m~x~ure~ oi~ cry~talline materials and gla~e~ ~uch Q8 Amin U.S. P~tent 3,787,219 and ~acher et ~1. U,S. Patent 3,837~869.
Often the alumina substrate on whîch multllayer struc1;ure3 are ~ormed i8 distort~d or bowed by forc2~
exerted by the rired dielectrlc layer(s). There ls a need ror dlelectrlc compos~tions which have thermal expansion characteristics such that bowing is reduced, since other-~i e poor ~ilm adhesion can result.
Reductlon ln alumina substrate bowing caused by many commercially available dielectric compositions ls important, since dlstorted (non~planar~ substrates ~akes allignment difficult in printing subsequent layers on the ~ubstrate. Also9 bowed substrates are more difficult to mount into connector assemblies. Furthermore, the com-pressive forces exerted by the dielectric layer can result in cracklng of the alumina substrate when it undergoes therr.lal cycling, for example~ in dip soldering of the electrodes. The fired dielectric layers must be nonporous, as defined herein, and fireable at temperatures compatible with the firing temperatures of typical electrode composi-tions (e.g., below 975C.). Furthermore, when crystalline fillers are used, the fillers should have dielectric constants which are relatl~ely low.
SUMMARY OF THE INVENTION
I have invented certain compositions useful for printing dielectric layers in multilayer electronic ~tructures. The compositions have a reduced tendency to cause substrate distortion or bowing (i.e., deviation from planarity). The compositions comprise, by weight complementally, ~inely divided powders of (a) 65-90% o~ one or more glasses having a softening point greater than about 700C.
and a thermal expansion coefficient less than that Or alumina, and
-4-(b) 10-35% crystalline ~lllers which are, based on the total welght of the composition (1) 0-25%, preferably 0-20%, MgTiO3~ and/or (2) 0-35% mixtures of MgO and TiO2.
Where the weight o~ MgT103 in the powder compositions is le~s than 10%, su~ficient crystalline MgO and T102 are pre-sent in such molar proportions that ln the ~ired dielectric lay~r(s) in the multilayer structures there will be at least 10~ crystalline MgTiO3. Furthermore, in the ~irecl dielectrlc layer(s) there is no more than 25%, pre~erab:Ly no,more than 20g~ MgTiO3 present (whether added to the.un-, ~ired powder compositions as preformed MgTiO3 or the resultof reactlon Or MgO and TiO2 during I'iring), but there may be an excess Or MgO or TiO2 up to a total crystalline oxide content o~ 35%.
The powder compositions preferably comprise 86-82%
(a) and 14-18% (b). Preferably the compositions comprise -only preformed MgTiO3 ln component (b).
The compositions may be dispersed in an lnert liquld printing vehicle.
Also part of thls invention are multllayer elec-, tronlc structures such as capacitors and multllevel structures comprising as sequential layers on a substrate a bottom electrode on and adherent to said substrate, a dielectrlc layer over and adherent to at least part of said bottom electrode, and a top electrode over and adherent to at least part of said dielectric layer, whereln said dielectrlc layer consists essentially of, by welght complementally, (a) 65-90% one or more glasses havlng a softening polnt greater than about 700C. and a thermal expanslon coe~ficient less than that of alumina, and (b) 10-35% crystall~ne ~illers whlch are (1) MgT103 and/or (2) mixtures of MgO and TiO2~
provlded that there is 10~25~ pre~erably 10-20%, MgTiO3 in the fired dielectric layer and 0-25% MgO or TiO2.
Such devices include the multilayer capacltors described in ~o the examples below or ln multilevel electronic pat~erns.
The diçlectric layers made using the compositions of this invention minimize alumina substrate bowing during riring, and rurther can produce good electrical properties (e.g., dielectric constant below 10 and Q above about 400).
DETAILED D~SCRIPTIO~
- The compositions of the present invention comprise powders of glass and certain crystalline oxide fillers.
These powders are su~ficiently finely divided to be used ln conventional screen printing operations. Generally, the powders are sufficiently ~inely divided to pass through a 400-mesh screen tU.S. Standard Sieve Scale), and prefera-bly have an average particle size in the range 0.5-15 microns, prererably 1-5 microns, with substantially all particles in the range 1-20 microns. To achleve these sizes, the powders may be ground ln a mill (ball or multidimensional) prlor to use.
The glass and crystalline oxides and their rela-tive proportlons are chosen such that they will cause reduced dlstortlon (bowing) o~ the alumlna substrate upon firlng of the dielectrlc. Some uses can tolerate more bowing than can 1(~9~1L9~L6 others.
The glasses u~ed re substantlally nonconductive and have a softening point (the temperature at which the glass deforms rapldly) greater than abou~ 700C. and have a thermal expansion coefriclent less than that of alumina (70 x 10-7/C.). ~enerally, glasses with less than a total of 30% Bi203 plus PbO are preferred.
~ he glasses in the present lnvention are prepared from suitable batch compositions of oxides (or oxide pre-cursors such as hydroxides and carbonates) by melting any sultable batch composition which yields the desired com--pounds in the desired proportions. The batch composition is first mixed and then melted to yield a substantially homogeneous fluid glass. The temperature maintained during this melting step is not critical, but is usually within the range 1450-1550C. so that the rapid homogenation of the melt can be obtained. After a homogeneous fluid glass is obtained, it ls normally poured lnto water to form a glass frit.
MgTiO3 has a thermal coefficient Or expansion greater than that of alumina. This crystalline oxide, sometlmes referred to as ternary oxide herein, may be pre-~ent in the tunfired) powder compositions of this invention, or alternately may be formed upon firing of the dielectric in the multil~yer conflguration. Thus, the powder composi-tions may contain some or no ternary oxide, but lr less than 10% ternary oxide is present ln the powder composltions;
there will be sufflcient pre~ursor crystalline oxides present (MgO and TiO2) to form at least 10% crystalline MgTiO3 upon firln~. Thus, 1~ 5% M~TiO3 were present in the powder ~LO~i9~1~
composition, there would be suffic~ent precursor oxldes in the powder to ~orm at least 5% more MgTiO3 in the flred dielectric layer.
The powder comprises a ~otal o~ 10-35% MgTiO3 plus MgO and T102. Less than 10% MgTiO3 in the flred dielectric does not provide adequate reductlon in substrate bowing.
More than 35% crystalline oxides in the flred dielectrlc results in porous dielectric layers. Porosity can cause sinking of the conductor layer into and khrough the dielectric, and hence shorting.
When precursor oxides MgO and TiO2 remain in the fired dielectric layerJ the total weight of MgTiO3 and precursor crystalline oxides does not exceed 35%, but at least 10% MgTiO3 is present. Thus the powder compositions comprise, by weight complementally, 10-35% crystalline - oxides and 90-65% glass, preferably 14-18% crystalline oxides and 86-82% glass. The compositions o~ this lnvention are printed as a ~ilm in the conventional manner onto alumina substrates bearing a prefired electrode metalliza-tion. Preferably, screen or stencil printing techniques areemployed. The composition is printed as a finely divided powder in the form o~ a dispersion ln an lnert liquld vehlcle. Any inert liquid may be used as the vehicle, lncluding water or any one of various organlc liquids, with or without thickening and/or stabilizing agents and/or other common additlves. Exemplary of the organic liquids which can be used are the aliphatic alcohols; esters of such alcohols, for example, the acetate and propionates; terpenes such as pine oil, terpineol and the like; solutions of polyisobutyl methacrylate in 2,2,4-trimethyl pentanedlol-1,3-monoisobutyrate; solutions of reslns such as the polymethacrylates o~ lower alcohols, or solu~ions o~ ethyl cellulose, ln solvents such as pine oll and the monobutyl ether of ethylene glycol monoacetate. The vehicle may contaln or be composed o~ volatile liquids to promote ~ast setting a~ter applicatlon to the ~ubstrate.
The ratio of ~ehlcle to inorganic solids may vary considerably and depends upon the manner in which the dis-persion is to be applied and the kind of vehlcle used.
Generally, ~rom 0.4' to 9 parts by weight of ~norganic solids per part by weight of vehicle will be used to produce ~ dis-perslon o~ the desired consistency. Prererably, 2-4 parts of lnorganic solids per part o~ vehicle will be used.
A~ter the compositions of the present invention are printed onto pre~ired ceramic substrates (with ' metallizations thereon), the printed ~ubstrate ls re~ired.
Generally, the dielectric composition is fired in the temperature range 800-975C. to form a continuous dielectric layer. Pre~,erably, the ~iring is conducted at a peak temperature o~ about 900-950C. Peak temperature is held ~or about 10 min. normally, although 5-30 min. may be used by one skilled ln the art. Belt or box furnaces may be used.
Where a belt furnace is used the total ~lring cycle is normally about 40-60 min. ~hese compositions may be rired in air or in nltrogen, but much better results are obtained in air. O~ten a æecond dielectric layer is printed and rired directly over the rlrst to prevent pinholing.
~ lthough the compositlons Or thls invention are designed to be used as dielectric ~ayers in multllayer structures ~ormed on alumina substrates, these compositions ._9_ may be used wlth other substratesg including substra~es hav-ing thermal expansion characterlstics similar to tho~e o~
alum~na. Typical commercially available dlensi~ied (pre~ired) alr~ina s~bstrates comprise above 90% alu~ina; ~or e~ample3 ~merican Lava Corp. ALSIMAG~ 614 contains 96% alumi~a.
me multllayer structures of this in~ention i~-c~ude conductive layers (e.g., c~pacitors) or lines (e~g.
complex circuits with dielectric pads or "crossovers" ak the point of cros~over of the conductor lines). The geometry o~ the multllayer structure i~ not of the presen~ inven-t~on, but will be designed in the con~entional manner by those skilled in the art, according to their requirement~.
~n U.S,. P~tent 3,785,837, di~cusses cro~over dielectrics and Amir~ U.S. Patent 3,787,219 discloses multilayer capaci-tors. S~ructures with a multip~city of layers can be pro-vided with the composition~ of this in~ention~
Example~
In the ~ollowing exa~ple~ presen~ed to illu~trate the in~en~ion~ all parts percen~ages, ratios~ etc. are b~
2Q weight, unless otherwi~e stated. In a number of example~
multilayer capacitors o~ tw~ conductors and an in~ermediate dielectric were prin~ed and ~lred on an alumin~ su~tra~e to de~nonstrate the utility of the presen~ in~en~on. In other examples the dielectric compositlon was prin~ed on an alumina su~str~te and ~ired to illustrate an advantage o~ the p~eæent inventior~, reduced substrate defo~mation or bowing due to the ~red dielectric layer. In every e~le the subst~at~ was a pre~ired (denæi~i~d) 96% alumir~ sub-strate, America}l Lava Co~. ~L~31~G 614.
3Q The glasses used in these exa~les wexe prepared ~ - denotes trade mark as ~ollowæ. A physical mi~ure, in the desired proportic>ns, of' metal oxides, hydroxides and/or carbonates wa~ preps,red and melted at a peak temperature o~ 1450-1~550C. and then quenched by pouring into water. The glas~es wsre then ~nely ground in a conven~o~ liter b~ll nill ~rlth 26 1/~-inch al~nina balls (36 g. glass, 15 ml. water, m~Llled 2 hr.), filtered and dried. ~he powder was æcreened through a 400-mesh screen. Average pa:~lcle size was about 1-5 microns, w:ith substantially all pa:~icles between a~out 10 1-20 micron~.
The cry~alline oxides used, i.e., MgO, TiO2 and MgTiO3, were purchased commerclally, ide~lti~led by X-ray, and reduced in size by mill~ng 100 g. with 100 ml. water ln a multid~mensio.nal mill ~or 2 hr~ The parkicle size o~ the milled oxide w~ in the range of about 1-20 micronsJ average about 1-5 microns.
Dispersions of glass and crystalline oxides accord-ing to this invention were prep~red by mlxing the desired relatlve amounts o~ finely dirided glass and crystallin~
oxid~ (usually in a HOOVER* muller) with a vehlcle o~ suita~
ble consistency and rheology ~or screen print~ng. The solids/Yehlcle ratio Wa5 77/23S that i5 77 parts inorganic solids (glass and cry~talline oxiaes) ~re mixed wlth a vehicle o~ 22.8 parts o~ a mix~ur~ of polymer and sol~ent (20% polyi~obutyl methacrylate in 80~$ o~ a solvent which wa~
2,2,4-trimethyl pen~anediol-1,3~nonoisobutyrate) and 0.2 pa:~s o~ a wetting agen~ (80ya lecithin). In som~ instances up to 2 additional par~s o~ that sol~en~ was add~d to m~di:Ey rheology.
30 ~..~.
The dielectric co~position o~ the preseIlt i~lvention * denotes tr~de mark ~s p~nted and ~ired i~ alr on an alumin~ substr~te to demonstrate the reduction in substrate distortion (bowing) w~th the compo~itions of the present in~ention. The sub~tr~te w~s 2 inches (5.08 ~m.) by 1 inch (2.~4 cm.) by 25 mils (o.64 mm.) thick~ A 200~mesh printing æcreen waæ
masked at the center (a l/l~-inch or o.64 cm. s~uare) ~o that the one entire sur~ace of the substra~e w~uld be ~oYered wlth dielectric compos~tion, exc~pt for th~ central s~u~re. First the thickness (height) o~ that central square ~as measured on each substrate with a Starratt gauge.
Percent bowing equals change in height at the center o~ the substrate divided by the thickness of ~he substrate, each in mils. The gla~ had a the~mal expan~ion coe~icient o~
50 x 10 7foC. The glaæs contained 40% SiO2, 18% BaO, 5 CaO, 6% B203, 10~ A1203, 5% MgO, 8% ZnO, and 8% PbO. A
layer o~ the dielectric co~position of 16 parts MgTiO3 and 84 parts gla~s ~s then printed through that patterned 200-mesh screen on the substrate. The prin~ was dried at 120C.
~or 10 min. and then a secon~ dielectric print was prlnted over the ~irst and dried as be~ore. The printed subst~ate wa~ fired in a box furnace at 950C. for 10 mln.
Two add~tion~l dlelectric layers were printed and dried as before, firing was repeated as be~ore. ~eight a~ the cen~er of the substrats was measured agaln~ The cen~er oi ~he subæt~ate was bow~d slightly neg~tively (abou~ 0.5%) versus the subætrate be~ore any printing or ~$:ring as described herein.
The dielectric layer was found to haYe an ex--cellent appearance and to be non~porous by an ink testV
30 as ~llows . A drop of water soluble ink t S:hea:E :fers SK~UP*
* - denote~ trade mark _ 12 -~ `
deluxe blue No. 2) was placed on the fired dielectric and allowed to stand for about a minute, then washed under running water for about 5 sec. If a stain remains the sample is considered porous.
Comparative Showing A
Example 1 was repeated except that only the glass was used. No ~gTiO3 or any other crystalline ~iller was present. Although the dielectric appearance was again excellent, the substrate was found to have bowed +24.4%.
Com~arative Showing B
Example 1 was repeated except that the inorganic powder contained 26% crystalllne MgO and 74% glass. The amount of bowing was greater than in Example 1, and the dielectric layer was unacceptable due to considerable cracking and surface roughness. This demonstrates the importance of MgTiO3.
Example 2 Example 1 was repeated using a dielectric composi-tion containing less MgTiO3, 10% (plus 90% glass). Substrate bowing was +5.5%, versu$ only about -0.5% in Example 1 uslng 16~ MgTiO3 (the substrate is nearly flat) and ver~u~ -~24.4 bowing in Showing A using 100~ glass. ThuS, 10~ MgTiO3 i8 not preferred.
Example 3 Example 1 was repeated using 84 parts glass and 16 parts crystalline filler of a ljl molar ratio of MgO/TiO2, versus 16 parts preformed MgTiO3 and 84 parts gla~s in Example 1. Substrate bowlng was ~6.2~. Hence preformed MgTi ~ is preferred over MgO/TiO2 mlxtures, although such mlxtures are an improvement over composltions of glass alone (Showing A) and MgO alone (Showing B~.
Examples 4-7 In these examples multilayer capacitors were prepared using the dlelectric compositions o~ thi~ invention.
The glas~ wa~ that of Example 1. The Table sets forth the identity and relative proportions o~ the inorganic solids, from which dispersions were ~ormed as before. The ~ubstrate dimensions were 1 inch (2.54 cm) by 1 inch (2.54 cm) by 25 mils (o.64 mm) thick.
In Examples 4~ 6 and 7, a bottom electrode (a keyhole pattern of a 400 mil circle with electrode tabs extending there~rom) was printed on the substrate with a gold composition through a 325-mesh screen, dried at 125C
~or 10 min. and fired in air at 900C ~or 10 min The gold compo~itlon contalned 80.3 parts ~inely gold and 307 parts finely divided glass binder dispersed in 16 parts vehicle (8% ethyl cellulo~e/94% terpineol). The fired electrode thickness was about 0.7 mils.
In Example 5, the electrode wa~ fired in nitrogen at 900C ~or 10 min. me electrode material comprised a base metal~ copper (80.6 parts finely divided copper and 6.2 parts ~inely divided glass) dlspersed in 13 2 parts vehicle (2.5 part~ ethyl cellulo~e, 48~5 parts dibutyl phthalate, 46.6 parts terpineol and 2.4 parts soya lecithin).
A dielectric layer (a 440 mll circle) was printed over the fired bottom electrode, overlapping the bottom electrode in the area where the top electrode (a keyhole pattern) was intended to be printed. The dielec-tric layer waæ dried at 125C for 10 min. and then a second dielectric layer was printed on the first and dried~ The structllre was ,, --I o ~ ~ o O K ~I rl >~
~ Ir~ N
1)0 O g g 0 e.,,, o o~ ~ 0 f~ ~ O `
0~
~:r :t N ~
;~ C E
~¦ ~ ` '--O N I ~I N 3 ~O
Z
~ N a:~ 0 Il~
m t~ ~ O
~s ~ ~ e I
40~ o bOH l ~ :,.e F~ ~ o o ~ C hO~
h C ~0 l O O ~ :r o :r h I
0~1~ I 0~ ~ O ~0 O llG ~
~0 ~ZC~ J ~n re~ired at 900C for 10 min. The thickness o~ the dielectric layer is set ~orth in the Table.
A ~op ele~rvde (keyhole pat~ern) was pri~ted and dried a~ before o~rer ~he ~red die1ectric la~er using the s~e electrode co~position and ~ring atmosphere as had been used ~or the botto~ electrode in that exa~le, a~d then ~ired at 900C ~or lO min.
Q, a measure o~ loss of power in a re50~1aIlt clr-cuit (~he higher the Q, the lower the power lo~s)~ was determiLned by readirlg c~pacitance (pF) and conductarLce (mh~) from a General R~dio 1682 (l MEIz~ bridge and then using the ~ollo~ing equation 2 ~ Ca~acitance Q=
~.oncLuctance Dissipation factor in decim~ls wa~ determined using a General Radio 1672A (l kHz) bridgeJ and was ~hen converted into percentage.
Dielect~Lc constant 'W~8 dete~Lned ~rom the capacitance, as follows:
K = ~ Qr~
where C is capacitance (pF) t and A are thicknes~ and area of the ~Lelectric~ respectively, in mil~O
IR (lnsulation resistance) was determined at 100 ~ol~s D.C. using a Penn Airborne Products Co. MEGATROMETER*
Model 710.
Breakdo~ voltage (volts hC) w~s determined using an As~ociated Research Inc. HYPOT* Bre~kdown tester.
As indica~ed in the Table9 good electrlcal propextles were o~tained ~L-th each composi~ion.
The bes~ overall per~o~mance w~ observed ~Lth * ~ denotes trade mark _ ~6 -~' i~
a9~
16% preformed MgT103 (0.1% disslpation :Eactor9 low K o~ 7.2, and Q o~ 707 ) .
Where the weight o~ MgT103 in the powder compositions is le~s than 10%, su~ficient crystalline MgO and T102 are pre-sent in such molar proportions that ln the ~ired dielectric lay~r(s) in the multilayer structures there will be at least 10~ crystalline MgTiO3. Furthermore, in the ~irecl dielectrlc layer(s) there is no more than 25%, pre~erab:Ly no,more than 20g~ MgTiO3 present (whether added to the.un-, ~ired powder compositions as preformed MgTiO3 or the resultof reactlon Or MgO and TiO2 during I'iring), but there may be an excess Or MgO or TiO2 up to a total crystalline oxide content o~ 35%.
The powder compositions preferably comprise 86-82%
(a) and 14-18% (b). Preferably the compositions comprise -only preformed MgTiO3 ln component (b).
The compositions may be dispersed in an lnert liquld printing vehicle.
Also part of thls invention are multllayer elec-, tronlc structures such as capacitors and multllevel structures comprising as sequential layers on a substrate a bottom electrode on and adherent to said substrate, a dielectrlc layer over and adherent to at least part of said bottom electrode, and a top electrode over and adherent to at least part of said dielectric layer, whereln said dielectrlc layer consists essentially of, by welght complementally, (a) 65-90% one or more glasses havlng a softening polnt greater than about 700C. and a thermal expanslon coe~ficient less than that of alumina, and (b) 10-35% crystall~ne ~illers whlch are (1) MgT103 and/or (2) mixtures of MgO and TiO2~
provlded that there is 10~25~ pre~erably 10-20%, MgTiO3 in the fired dielectric layer and 0-25% MgO or TiO2.
Such devices include the multilayer capacltors described in ~o the examples below or ln multilevel electronic pat~erns.
The diçlectric layers made using the compositions of this invention minimize alumina substrate bowing during riring, and rurther can produce good electrical properties (e.g., dielectric constant below 10 and Q above about 400).
DETAILED D~SCRIPTIO~
- The compositions of the present invention comprise powders of glass and certain crystalline oxide fillers.
These powders are su~ficiently finely divided to be used ln conventional screen printing operations. Generally, the powders are sufficiently ~inely divided to pass through a 400-mesh screen tU.S. Standard Sieve Scale), and prefera-bly have an average particle size in the range 0.5-15 microns, prererably 1-5 microns, with substantially all particles in the range 1-20 microns. To achleve these sizes, the powders may be ground ln a mill (ball or multidimensional) prlor to use.
The glass and crystalline oxides and their rela-tive proportlons are chosen such that they will cause reduced dlstortlon (bowing) o~ the alumlna substrate upon firlng of the dielectrlc. Some uses can tolerate more bowing than can 1(~9~1L9~L6 others.
The glasses u~ed re substantlally nonconductive and have a softening point (the temperature at which the glass deforms rapldly) greater than abou~ 700C. and have a thermal expansion coefriclent less than that of alumina (70 x 10-7/C.). ~enerally, glasses with less than a total of 30% Bi203 plus PbO are preferred.
~ he glasses in the present lnvention are prepared from suitable batch compositions of oxides (or oxide pre-cursors such as hydroxides and carbonates) by melting any sultable batch composition which yields the desired com--pounds in the desired proportions. The batch composition is first mixed and then melted to yield a substantially homogeneous fluid glass. The temperature maintained during this melting step is not critical, but is usually within the range 1450-1550C. so that the rapid homogenation of the melt can be obtained. After a homogeneous fluid glass is obtained, it ls normally poured lnto water to form a glass frit.
MgTiO3 has a thermal coefficient Or expansion greater than that of alumina. This crystalline oxide, sometlmes referred to as ternary oxide herein, may be pre-~ent in the tunfired) powder compositions of this invention, or alternately may be formed upon firing of the dielectric in the multil~yer conflguration. Thus, the powder composi-tions may contain some or no ternary oxide, but lr less than 10% ternary oxide is present ln the powder composltions;
there will be sufflcient pre~ursor crystalline oxides present (MgO and TiO2) to form at least 10% crystalline MgTiO3 upon firln~. Thus, 1~ 5% M~TiO3 were present in the powder ~LO~i9~1~
composition, there would be suffic~ent precursor oxldes in the powder to ~orm at least 5% more MgTiO3 in the flred dielectric layer.
The powder comprises a ~otal o~ 10-35% MgTiO3 plus MgO and T102. Less than 10% MgTiO3 in the flred dielectric does not provide adequate reductlon in substrate bowing.
More than 35% crystalline oxides in the flred dielectrlc results in porous dielectric layers. Porosity can cause sinking of the conductor layer into and khrough the dielectric, and hence shorting.
When precursor oxides MgO and TiO2 remain in the fired dielectric layerJ the total weight of MgTiO3 and precursor crystalline oxides does not exceed 35%, but at least 10% MgTiO3 is present. Thus the powder compositions comprise, by weight complementally, 10-35% crystalline - oxides and 90-65% glass, preferably 14-18% crystalline oxides and 86-82% glass. The compositions o~ this lnvention are printed as a ~ilm in the conventional manner onto alumina substrates bearing a prefired electrode metalliza-tion. Preferably, screen or stencil printing techniques areemployed. The composition is printed as a finely divided powder in the form o~ a dispersion ln an lnert liquld vehlcle. Any inert liquid may be used as the vehicle, lncluding water or any one of various organlc liquids, with or without thickening and/or stabilizing agents and/or other common additlves. Exemplary of the organic liquids which can be used are the aliphatic alcohols; esters of such alcohols, for example, the acetate and propionates; terpenes such as pine oil, terpineol and the like; solutions of polyisobutyl methacrylate in 2,2,4-trimethyl pentanedlol-1,3-monoisobutyrate; solutions of reslns such as the polymethacrylates o~ lower alcohols, or solu~ions o~ ethyl cellulose, ln solvents such as pine oll and the monobutyl ether of ethylene glycol monoacetate. The vehicle may contaln or be composed o~ volatile liquids to promote ~ast setting a~ter applicatlon to the ~ubstrate.
The ratio of ~ehlcle to inorganic solids may vary considerably and depends upon the manner in which the dis-persion is to be applied and the kind of vehlcle used.
Generally, ~rom 0.4' to 9 parts by weight of ~norganic solids per part by weight of vehicle will be used to produce ~ dis-perslon o~ the desired consistency. Prererably, 2-4 parts of lnorganic solids per part o~ vehicle will be used.
A~ter the compositions of the present invention are printed onto pre~ired ceramic substrates (with ' metallizations thereon), the printed ~ubstrate ls re~ired.
Generally, the dielectric composition is fired in the temperature range 800-975C. to form a continuous dielectric layer. Pre~,erably, the ~iring is conducted at a peak temperature o~ about 900-950C. Peak temperature is held ~or about 10 min. normally, although 5-30 min. may be used by one skilled ln the art. Belt or box furnaces may be used.
Where a belt furnace is used the total ~lring cycle is normally about 40-60 min. ~hese compositions may be rired in air or in nltrogen, but much better results are obtained in air. O~ten a æecond dielectric layer is printed and rired directly over the rlrst to prevent pinholing.
~ lthough the compositlons Or thls invention are designed to be used as dielectric ~ayers in multllayer structures ~ormed on alumina substrates, these compositions ._9_ may be used wlth other substratesg including substra~es hav-ing thermal expansion characterlstics similar to tho~e o~
alum~na. Typical commercially available dlensi~ied (pre~ired) alr~ina s~bstrates comprise above 90% alu~ina; ~or e~ample3 ~merican Lava Corp. ALSIMAG~ 614 contains 96% alumi~a.
me multllayer structures of this in~ention i~-c~ude conductive layers (e.g., c~pacitors) or lines (e~g.
complex circuits with dielectric pads or "crossovers" ak the point of cros~over of the conductor lines). The geometry o~ the multllayer structure i~ not of the presen~ inven-t~on, but will be designed in the con~entional manner by those skilled in the art, according to their requirement~.
~n U.S,. P~tent 3,785,837, di~cusses cro~over dielectrics and Amir~ U.S. Patent 3,787,219 discloses multilayer capaci-tors. S~ructures with a multip~city of layers can be pro-vided with the composition~ of this in~ention~
Example~
In the ~ollowing exa~ple~ presen~ed to illu~trate the in~en~ion~ all parts percen~ages, ratios~ etc. are b~
2Q weight, unless otherwi~e stated. In a number of example~
multilayer capacitors o~ tw~ conductors and an in~ermediate dielectric were prin~ed and ~lred on an alumin~ su~tra~e to de~nonstrate the utility of the presen~ in~en~on. In other examples the dielectric compositlon was prin~ed on an alumina su~str~te and ~ired to illustrate an advantage o~ the p~eæent inventior~, reduced substrate defo~mation or bowing due to the ~red dielectric layer. In every e~le the subst~at~ was a pre~ired (denæi~i~d) 96% alumir~ sub-strate, America}l Lava Co~. ~L~31~G 614.
3Q The glasses used in these exa~les wexe prepared ~ - denotes trade mark as ~ollowæ. A physical mi~ure, in the desired proportic>ns, of' metal oxides, hydroxides and/or carbonates wa~ preps,red and melted at a peak temperature o~ 1450-1~550C. and then quenched by pouring into water. The glas~es wsre then ~nely ground in a conven~o~ liter b~ll nill ~rlth 26 1/~-inch al~nina balls (36 g. glass, 15 ml. water, m~Llled 2 hr.), filtered and dried. ~he powder was æcreened through a 400-mesh screen. Average pa:~lcle size was about 1-5 microns, w:ith substantially all pa:~icles between a~out 10 1-20 micron~.
The cry~alline oxides used, i.e., MgO, TiO2 and MgTiO3, were purchased commerclally, ide~lti~led by X-ray, and reduced in size by mill~ng 100 g. with 100 ml. water ln a multid~mensio.nal mill ~or 2 hr~ The parkicle size o~ the milled oxide w~ in the range of about 1-20 micronsJ average about 1-5 microns.
Dispersions of glass and crystalline oxides accord-ing to this invention were prep~red by mlxing the desired relatlve amounts o~ finely dirided glass and crystallin~
oxid~ (usually in a HOOVER* muller) with a vehlcle o~ suita~
ble consistency and rheology ~or screen print~ng. The solids/Yehlcle ratio Wa5 77/23S that i5 77 parts inorganic solids (glass and cry~talline oxiaes) ~re mixed wlth a vehicle o~ 22.8 parts o~ a mix~ur~ of polymer and sol~ent (20% polyi~obutyl methacrylate in 80~$ o~ a solvent which wa~
2,2,4-trimethyl pen~anediol-1,3~nonoisobutyrate) and 0.2 pa:~s o~ a wetting agen~ (80ya lecithin). In som~ instances up to 2 additional par~s o~ that sol~en~ was add~d to m~di:Ey rheology.
30 ~..~.
The dielectric co~position o~ the preseIlt i~lvention * denotes tr~de mark ~s p~nted and ~ired i~ alr on an alumin~ substr~te to demonstrate the reduction in substrate distortion (bowing) w~th the compo~itions of the present in~ention. The sub~tr~te w~s 2 inches (5.08 ~m.) by 1 inch (2.~4 cm.) by 25 mils (o.64 mm.) thick~ A 200~mesh printing æcreen waæ
masked at the center (a l/l~-inch or o.64 cm. s~uare) ~o that the one entire sur~ace of the substra~e w~uld be ~oYered wlth dielectric compos~tion, exc~pt for th~ central s~u~re. First the thickness (height) o~ that central square ~as measured on each substrate with a Starratt gauge.
Percent bowing equals change in height at the center o~ the substrate divided by the thickness of ~he substrate, each in mils. The gla~ had a the~mal expan~ion coe~icient o~
50 x 10 7foC. The glaæs contained 40% SiO2, 18% BaO, 5 CaO, 6% B203, 10~ A1203, 5% MgO, 8% ZnO, and 8% PbO. A
layer o~ the dielectric co~position of 16 parts MgTiO3 and 84 parts gla~s ~s then printed through that patterned 200-mesh screen on the substrate. The prin~ was dried at 120C.
~or 10 min. and then a secon~ dielectric print was prlnted over the ~irst and dried as be~ore. The printed subst~ate wa~ fired in a box furnace at 950C. for 10 mln.
Two add~tion~l dlelectric layers were printed and dried as before, firing was repeated as be~ore. ~eight a~ the cen~er of the substrats was measured agaln~ The cen~er oi ~he subæt~ate was bow~d slightly neg~tively (abou~ 0.5%) versus the subætrate be~ore any printing or ~$:ring as described herein.
The dielectric layer was found to haYe an ex--cellent appearance and to be non~porous by an ink testV
30 as ~llows . A drop of water soluble ink t S:hea:E :fers SK~UP*
* - denote~ trade mark _ 12 -~ `
deluxe blue No. 2) was placed on the fired dielectric and allowed to stand for about a minute, then washed under running water for about 5 sec. If a stain remains the sample is considered porous.
Comparative Showing A
Example 1 was repeated except that only the glass was used. No ~gTiO3 or any other crystalline ~iller was present. Although the dielectric appearance was again excellent, the substrate was found to have bowed +24.4%.
Com~arative Showing B
Example 1 was repeated except that the inorganic powder contained 26% crystalllne MgO and 74% glass. The amount of bowing was greater than in Example 1, and the dielectric layer was unacceptable due to considerable cracking and surface roughness. This demonstrates the importance of MgTiO3.
Example 2 Example 1 was repeated using a dielectric composi-tion containing less MgTiO3, 10% (plus 90% glass). Substrate bowing was +5.5%, versu$ only about -0.5% in Example 1 uslng 16~ MgTiO3 (the substrate is nearly flat) and ver~u~ -~24.4 bowing in Showing A using 100~ glass. ThuS, 10~ MgTiO3 i8 not preferred.
Example 3 Example 1 was repeated using 84 parts glass and 16 parts crystalline filler of a ljl molar ratio of MgO/TiO2, versus 16 parts preformed MgTiO3 and 84 parts gla~s in Example 1. Substrate bowlng was ~6.2~. Hence preformed MgTi ~ is preferred over MgO/TiO2 mlxtures, although such mlxtures are an improvement over composltions of glass alone (Showing A) and MgO alone (Showing B~.
Examples 4-7 In these examples multilayer capacitors were prepared using the dlelectric compositions o~ thi~ invention.
The glas~ wa~ that of Example 1. The Table sets forth the identity and relative proportions o~ the inorganic solids, from which dispersions were ~ormed as before. The ~ubstrate dimensions were 1 inch (2.54 cm) by 1 inch (2.54 cm) by 25 mils (o.64 mm) thick.
In Examples 4~ 6 and 7, a bottom electrode (a keyhole pattern of a 400 mil circle with electrode tabs extending there~rom) was printed on the substrate with a gold composition through a 325-mesh screen, dried at 125C
~or 10 min. and fired in air at 900C ~or 10 min The gold compo~itlon contalned 80.3 parts ~inely gold and 307 parts finely divided glass binder dispersed in 16 parts vehicle (8% ethyl cellulo~e/94% terpineol). The fired electrode thickness was about 0.7 mils.
In Example 5, the electrode wa~ fired in nitrogen at 900C ~or 10 min. me electrode material comprised a base metal~ copper (80.6 parts finely divided copper and 6.2 parts ~inely divided glass) dlspersed in 13 2 parts vehicle (2.5 part~ ethyl cellulo~e, 48~5 parts dibutyl phthalate, 46.6 parts terpineol and 2.4 parts soya lecithin).
A dielectric layer (a 440 mll circle) was printed over the fired bottom electrode, overlapping the bottom electrode in the area where the top electrode (a keyhole pattern) was intended to be printed. The dielec-tric layer waæ dried at 125C for 10 min. and then a second dielectric layer was printed on the first and dried~ The structllre was ,, --I o ~ ~ o O K ~I rl >~
~ Ir~ N
1)0 O g g 0 e.,,, o o~ ~ 0 f~ ~ O `
0~
~:r :t N ~
;~ C E
~¦ ~ ` '--O N I ~I N 3 ~O
Z
~ N a:~ 0 Il~
m t~ ~ O
~s ~ ~ e I
40~ o bOH l ~ :,.e F~ ~ o o ~ C hO~
h C ~0 l O O ~ :r o :r h I
0~1~ I 0~ ~ O ~0 O llG ~
~0 ~ZC~ J ~n re~ired at 900C for 10 min. The thickness o~ the dielectric layer is set ~orth in the Table.
A ~op ele~rvde (keyhole pat~ern) was pri~ted and dried a~ before o~rer ~he ~red die1ectric la~er using the s~e electrode co~position and ~ring atmosphere as had been used ~or the botto~ electrode in that exa~le, a~d then ~ired at 900C ~or lO min.
Q, a measure o~ loss of power in a re50~1aIlt clr-cuit (~he higher the Q, the lower the power lo~s)~ was determiLned by readirlg c~pacitance (pF) and conductarLce (mh~) from a General R~dio 1682 (l MEIz~ bridge and then using the ~ollo~ing equation 2 ~ Ca~acitance Q=
~.oncLuctance Dissipation factor in decim~ls wa~ determined using a General Radio 1672A (l kHz) bridgeJ and was ~hen converted into percentage.
Dielect~Lc constant 'W~8 dete~Lned ~rom the capacitance, as follows:
K = ~ Qr~
where C is capacitance (pF) t and A are thicknes~ and area of the ~Lelectric~ respectively, in mil~O
IR (lnsulation resistance) was determined at 100 ~ol~s D.C. using a Penn Airborne Products Co. MEGATROMETER*
Model 710.
Breakdo~ voltage (volts hC) w~s determined using an As~ociated Research Inc. HYPOT* Bre~kdown tester.
As indica~ed in the Table9 good electrlcal propextles were o~tained ~L-th each composi~ion.
The bes~ overall per~o~mance w~ observed ~Lth * ~ denotes trade mark _ ~6 -~' i~
a9~
16% preformed MgT103 (0.1% disslpation :Eactor9 low K o~ 7.2, and Q o~ 707 ) .
Claims (23)
1. Compositions of finely divided inorganic powders useful for forming dielectric layers in multi-layer electronic structures of conductive and dielectric layers on an alumina substrate, the compositions comprising, by weight complementally, (a) 65-90% of one or more glasses having a softening point greater than 700°C. and a thermal expansion coefficient less than that of alumina, and (b) 10-35% of crystalline fillers which are, based on the total weight of the composition, (1) 0-25% MgTiO3 and/or (2) 0-35% mixtures of precursor crystalline oxides MgO and TiO2 capable of forming MgTiO3 provided that where the weights of MgTiO3 in these compositions is less than 10%, the relative proportions of precursor crystal-line oxides (2) are such that in the fired dielectric layer(s) in the aforesaid multi-layer electronic structure(s) there will be a total of at least 10% MgTiO3, and further provided that the relative proportions of precursor crystalline oxides are such that in the fired dielectric layers there will be no more than 25% MgTiO3.
2. Compositions according to claim 1 of 86-82% (a) and 14-18% (b).
3. Compositions according to claim l wherein component (b) (1) comprises 0-20% MgTiO3.
4. Compositions according to claim l wherein component (b) is MgTiO3.
5. Compositions according to claim 2 wherein component (b) is MgTiO3.
6. Compositions according to claim 3 wherein component (b) is MgTiO3.
7. Compositions according to claim 1 wherein component (a) is Ti-free.
8. Compositions according to claim 2 wherein component (a) is Ti-free.
9. Compositions according to claim 3 wherein component (a) is Ti-free.
10. Compositions according to claim 4 wherein component (a) is Ti-free.
11. Compositions according to claim 1 dispersed in an inert liquid vehicle.
12. Compositions according to claim 2 dispersed in an inert liquid vehicle.
13. Compositions according to claim 3 dispersed in an inert liquid vehicle.
14. Compositions according to claim 4 dispersed in an inert liquid vehicle.
15. Compositions according to claim 5 dispersed in an inert liquid vehicle.
16. Compositions according to claim 6 dispersed in an inert liquid vehicle.
17. In multilayer electronic structures comprising as sequential layers on a substrate a bottom electrode on and adherent to said substrate, a dielectric layer over and adherent to at least part of said bottom electrode, and a top electrode over and adherent to at least part of said dielectric layer, improved multilayer structures wherein said dielectric layer comprises by weight complementally, (a) 65-90% glass having a softening point greater than 700°C. and a thermal expansion coefficient less than that of alumina, and (b) 10-35% of crystalline fillers which are, based on the total weight of the dielectric layer, (1) 10-25% MgTi03 and (2) 0-25% MgO or Ti02.
18. Structures according to claim 17 wherein component (b) (1) is 10-20% MgTiO3.
19. Structures according to claim 17 wherein the dielectric layer comprises 86-82% (a) and 14-18% (b).
20. Structures according to claim 18 wherein the dielectric layer comprises 86-82% (a) and 14-18% (b).
21. Structures according to claim 17 wherein component (b) is MgTiO3.
22. Structures according to claim 18 wherein component (b) is MgTiO3.
23. Structures according to claim 17 wherein component (a) is Ti-free.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/672,031 US4071881A (en) | 1976-03-30 | 1976-03-30 | Dielectric compositions of magnesium titanate and devices thereof |
| US672,031 | 1984-11-16 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1091916A true CA1091916A (en) | 1980-12-23 |
Family
ID=24696861
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA274,858A Expired CA1091916A (en) | 1976-03-30 | 1977-03-28 | Dielectric compositions of glass and magnesium titanates |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US4071881A (en) |
| JP (1) | JPS5851362B2 (en) |
| CA (1) | CA1091916A (en) |
| DE (1) | DE2714196C3 (en) |
| FR (1) | FR2346824A1 (en) |
| GB (1) | GB1576892A (en) |
| IT (1) | IT1085530B (en) |
Families Citing this family (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4308570A (en) * | 1980-02-25 | 1981-12-29 | Sprague Electric Company | High Q monolithic capacitor with glass-magnesium titanate body |
| US4506026A (en) * | 1982-12-22 | 1985-03-19 | Tam Ceramics, Inc. | Low firing ceramic dielectric for temperature compensating capacitors |
| FR2568722B1 (en) * | 1984-08-03 | 1987-10-23 | Thomson Csf | DIELECTRIC CERAMIC SUBSTRATE AND PROCESS FOR OBTAINING |
| JPS61107050U (en) * | 1984-12-19 | 1986-07-07 | ||
| EP0234338A1 (en) * | 1986-02-13 | 1987-09-02 | W.C. Heraeus GmbH | Thick-film multilayer dielectric composition for firing in air and nitrogen |
| US4980246A (en) * | 1987-05-15 | 1990-12-25 | Alpha Industries | Dense ceramic alloys and process of making same |
| US5024980A (en) * | 1987-05-15 | 1991-06-18 | Alpha Industries | Ceramic dielectric alloy |
| US4942146A (en) * | 1987-05-15 | 1990-07-17 | Alpha Industries | Dense ceramic alloys and process of making same |
| GB2209521A (en) * | 1987-09-09 | 1989-05-17 | Era Patents Ltd | Green tape |
| US4853827A (en) * | 1988-08-01 | 1989-08-01 | Rogers Corporation | High dielectric multilayer capacitor |
| GB2234855A (en) * | 1988-12-29 | 1991-02-13 | Rogers Corp | High dielectric multilayer capacitor |
| JP2711618B2 (en) * | 1992-06-30 | 1998-02-10 | ティーディーケイ株式会社 | Dielectric composition, multilayer wiring board and multilayer ceramic capacitor |
| JP2001072434A (en) * | 1999-06-30 | 2001-03-21 | Sumitomo Chem Co Ltd | Inorganic filler for compounding of glass paste |
| EP1065693A3 (en) * | 1999-06-30 | 2001-03-21 | Sumitomo Chemical Company, Limited | Glass paste |
| US6368514B1 (en) | 1999-09-01 | 2002-04-09 | Luminous Intent, Inc. | Method and apparatus for batch processed capacitors using masking techniques |
| JP2001302280A (en) | 2000-04-19 | 2001-10-31 | Sumitomo Chem Co Ltd | Inorganic powder for compounding glass paste and glass paste using the same |
| TW200732270A (en) * | 2006-02-17 | 2007-09-01 | Delta Electronics Inc | Dielectric glass-ceramic composition, dielectric glass-ceramic substrate and manufacturing method thereof |
| JP2007319202A (en) * | 2006-05-30 | 2007-12-13 | Sadao Tsukamoto | Cutter knife stored by one action and preventing excess protrusion of blade |
| JP5982243B2 (en) * | 2012-03-30 | 2016-08-31 | 積水化学工業株式会社 | Titanium oxide paste |
| US10113073B2 (en) * | 2015-04-07 | 2018-10-30 | GM Global Technology Operations LLC | Dielectric thick film ink |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2691088A (en) * | 1949-11-28 | 1954-10-05 | Ungewiss Alfred | Ohmic resistance |
| US3267342A (en) * | 1965-05-18 | 1966-08-16 | Corning Glass Works | Electrical capacitor |
| US3470002A (en) * | 1967-01-30 | 1969-09-30 | Bell Telephone Labor Inc | Glaze for high density alumina |
| JPS4870855A (en) * | 1971-12-29 | 1973-09-26 | ||
| US3787219A (en) * | 1972-09-22 | 1974-01-22 | Du Pont | CaTiO{11 -CRYSTALLIZABLE GLASS DIELECTRIC COMPOSITIONS |
| JPS5110844B2 (en) * | 1973-04-24 | 1976-04-07 | ||
| US3940255A (en) * | 1974-08-05 | 1976-02-24 | Ferro Corporation | Process for making cordierite glass-ceramic having nucleating agent and increased percent cordierite crystallinity |
| US3996502A (en) * | 1975-06-02 | 1976-12-07 | Zenith Radio Corporation | Thick film capacitors |
-
1976
- 1976-03-30 US US05/672,031 patent/US4071881A/en not_active Expired - Lifetime
-
1977
- 1977-03-28 CA CA274,858A patent/CA1091916A/en not_active Expired
- 1977-03-29 FR FR7709348A patent/FR2346824A1/en active Granted
- 1977-03-29 GB GB13201/77A patent/GB1576892A/en not_active Expired
- 1977-03-29 IT IT21843/77A patent/IT1085530B/en active
- 1977-03-30 JP JP52036929A patent/JPS5851362B2/en not_active Expired
- 1977-03-30 DE DE2714196A patent/DE2714196C3/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| DE2714196C3 (en) | 1980-07-03 |
| JPS52125799A (en) | 1977-10-21 |
| US4071881A (en) | 1978-01-31 |
| GB1576892A (en) | 1980-10-15 |
| JPS5851362B2 (en) | 1983-11-16 |
| FR2346824A1 (en) | 1977-10-28 |
| IT1085530B (en) | 1985-05-28 |
| DE2714196B2 (en) | 1979-10-25 |
| FR2346824B1 (en) | 1981-04-30 |
| DE2714196A1 (en) | 1977-10-06 |
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| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |