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United States Patent
Ollivier et a].

(10) Patent N0.:
(45) Date of Patent:
4,381,945 A 4,654,095 A 4,663,240 A
4,940,849 A

US 7,326,367 B2
*Feb. 5, 2008


5/1983 Nair et a1. 3/1987 Steinberg 5/1987 Hajdu et a1~
7/1990 Morris et a1.


Inventors: Patricia J. Ollivier, Raleigh, NC (US);

i *

"""""""" " 361604

Kenneth Warren Hang, Hillsborough,
NC (Us)

5’02l’293 A , ,
5,162,062 A *

@1991 H0 e a' uang et a1.
11/1992 Carroll 6161. .............. .. 148/24

(73) Assignee: E.I. du Pont de Nemours and
Company, Wilmington, DE (US)
(*) Notice: Subject to any disclaimer, the term of this patent is extended or adjusted under 35
U_S_C_ 154(1)) by 0 days_

5,225,287 A

5,175,031 A

12/1992 0 h ki

7/1993 pecrrgcet 31‘
1/1995 Carroll et a1. 8/1995 Hormadaly et a1.
5/1996 LaBranche et a1. ....... .. 252/514
2/1998 Shaikh et a1. ............. .. 428/323

5,250,394 A
5,254,191 A

10/1993 Wei et a1.
10/1993 Mikeska et a1.

5,378,408 A 5,439,852 A
5,518,663 A *
5,714,246 A *

This patent is subject to a terminal disClaimer

5,744,232 A
5,753,571 A
2003/0096692 A1
2004/0155227 A1*

4/1998 Balley et al'
5/1998 Donohue et a1.
5/2003 Wang et a1.
8/2004 1/2006 Bechtloif et a1. ......... .. 252/500


Appl' NO" 11/398’141

2005/0104032 A1*
2006/0001009 A1*

5/2005 (3110 et a1. .............. .. 252/181.1
Garreau-Iles et a1. ..... .. 252/500



APr- 5’ 2006
P _

2006/0083906 A1*
t_ D t
a a



P bl_

2006/0128549 A1*

6/2006 Hormadaly ................ .. 501/45

ma ion

Us 2007/0295939 A1

Dec. 27, 2007

0 045 482 A 2/1982

Related US. Application Data
. . . .


0 718 855 A
1 534 053 A


(60) 52031850511211 app11cat10n No. 60/674,434, ?led on Apr.
51 Int. Cl.


08050806 A * 2/l996

* cited by examiner

( ) H01B 1/00
H01B 1/12

252/500; 428/209; 428/208;

Prir'nary ExamineriMark Kopec
Asszslanl ExammeriKhanh T. Nguyen

US. Cl. .................... ..

428/323; 252/514; 252/519, 148/23; 148/24;
58 F, M f Cl
501/45; 501/47; 501/48; 501/26; 361/304

. . . .

. .





5 01 /2 6

Th1s mventlon 15 related to th1ck ?lm conductor compos1

( )


0 sgjcagsogis if“; 8
1. t.
’ ?l f ’ ’

23 209f
1;‘ 8/ 2 4_ 3 6’1 B 04’ h hit
15 Dry‘

tions comprising electrically conductive gold powder, one or
more glass frit or ceramic oxide compositions and an organic vehicle. It is further directed to the composition’s uses for
LTCC (loW temperature co-?red ceramic) tape, for fabrica

1 t

ee app lea Ion

e or Comp 6 e Seam


References Cited
4,215,170 A 7/1980 Oliva

tion of multilayer electronic circuits and in high frequency

microelectronic applications.
10 Claims, N0 Drawings

to meet tional phase that imparts appropriate electrically functional properties to the composition.367 B2 1 THICK FILM CONDUCTOR PASTE COMPOSITIONS FOR LTCC TAPE IN MICROWAVE APPLICATIONS FIELD OF THE INVENTION 2 SUMMARY OF THE INVENTION The invention is directed to a thick ?lm composition comprising: (a) an electrically conductive gold poWder. co?ring and ?exible design capabilities. cadmium free thick ?lm conductor. the composition(s) of the present invention are useful in the formation of microWave circuit components including. transition metal oxides. BACKGROUND OF THE INVENTION An interconnect circuit board of an LTCC design is a physical realiZation of electronic circuits or subsystems made from a number of extremely small circuit elements that are electrically and mechanically interconnected. “organic mediums” or “organic vehicles” are terms used to describe the polymer or resin meet Wire bonding requirements. and (f) co?ring the assemblage of compact package and electrically connected to each other and/ or to common connections extending from the package. such as telecommunications. The present inventors provided such a lead free and cadmium free conductor that simultaneously main Which forms the composition. (2) transition metal oxides. a thick ?lm composition comprises a func sitions used in high frequency applications have been knoWn to require a “double print” (i. (c) printing of any of several thick ?lm func tional compositions over the surface of the via ?lled green tape layers of step (b)iincluding. and transmission lines. including desired resistivity.US 7. The components 45 microWave applications Wherein the compositions minimiZe lead and cadmium content in the circuits to meet environ mental concerns. activate the inorganic binder phase and to impart the electrically functional properties. over the outermost surface microelectronic applications. Additionally. 25 Complex electronic circuits generally require that the circuit be constructed of several layers of conductors sepa DETAILED DESCRIPTION OF INVENTION rated by insulating dielectric layers. The composition is ?red to burn out the organic phase. dispersed in an organic medium. (d) printing at least one patterned layer of any thick ?lm composition.e. Still further. (3) precursors to transition metal oxides. Electrically Functional PoWderiElectrically Conductive Gold PoWder Generally. auto present invention is useful in high frequency applications 35 motive or military applications including radar. more than one application of the conductor composition on the substrate) to meet the desired properties of the system. Inorganic Components The inorganic components of the present invention com metalliZation compatible With LTCC that display very loW microWave insertion losses commensurate With those of thin prise (l) electrically conductive metal poWders and (2) 50 ?lm gold. and mixtures thereof. The functional phase com 60 satisfactory Wire bond acceptance and adhesion properties. Wire bondability. manufacturers are noW seeking thick ?lm conductor compositions for use in high frequency position(s) of the present invention are electrically conduc tive metal poWders and one or more inorganic binders selected from (1) glass frits. The invention is further directed to a method of forming tape and for fabrication of multilayer electronic circuits. are discussed herein beloW. It is further directed to the compositions use in high frequency a multilayer circuit comprising: (a) forming a patterned array of vias in a plurality of layers of green tape. Many prop er‘ties are required of the conductors used in the fabrication such as transmit/receive modules and radar applications. including. Wirebond connection. U. solderability. Furthermore. . “Organics”. LTCC tape has been used in prior art high frequency microWave applications. feedthroughs (via or EM coupled). for its mul tilayer. (b) one or more glass frit or ceramic oxide compositions Wherein said glass frit and oxides do not contain lead or This invention is related to thick ?lm conductor compo sitions for use on LTCC (loW temperature co-?red ceramic) cadmium. The electrical performance of the metalliZation is attained by using a spherical metal particle shape and uniform particle siZe distribution in the thick ?lm paste. No. but not limited to: antenna. baluns. called vias. Furthermore.744.232 to Bailey discloses a thick ?lm I. and (4) mixtures thereof. adhesion. couplers. The conductive layers are interconnected betWeen levels by electrically conductive pathWays. migration resistance. the printed parts are dried to remove volatile solvents. (b) ?lling the vias in the green tape layer(s) of step (a) With a thick ?lm composition. Additional optional inorganic phases may be added to the composition as necessary to meet the desired properties of the particular application. It is especially dif?cult to maintain the desired thick ?lm prises electrically functional poWders dispersed in an organic medium that acts as a carrier for the functional phase conductor properties While minimiZing or eliminating lead and cadmium. solder leach resistance. some prior art thick ?lm conductor compo inorganic binders selected from one or more glass frits.326. and long term stability. precursors to transition metal oxides. 65 tains the desired thick ?lm conductor properties and requires only one application of the thick ?lm on the substrate to Prior to ?ring.. The main components of the thick ?lm conductor com 40 of multilayer circuits for microWave applications. (e) laminating the printed green tape layers of step (d) and any blank layers deemed 20 necessary to form an assemblage comprising a plurality of un?red functional and non-functional layers separated by un?red green tape. through a dielectric layer. ?lters. I/O’s. It is frequently desirable to combine these diverse electronic components in an arrangement so that they can be physically isolated and mounted adjacent to one another in a single of the green tape layers of step (c). the present invention. in particular. Bailey does not disclose the use of a lead free. the alumina substrates by alloWing vertical integration. 55 A. the use of the present invention. but not limited to. step (e). but not limited to. “MicroWave applications” are de?ned herein as 30 LoW Temperature Co?red Ceramic (LTCC) multilayer struc ture alloWs a circuit to be more compact than traditional applications Which require a frequency in the range of 300 MHZ to 300 GHZ (3><l0A8 to 3><l0All HZ). Pat. Use of a The composition(s) and multilayer circuit(s) of the present invention are particularly useful in microWave appli cations. beam former. 5. and (c) an organic vehicle.S.

0-10 Na2O.38 5.92 3.55 1. rhodium. The gold poWder of the present invention is present in the amount of 50-95 Weight percent total thick ?lm composition. For example. It is knoWn that mixtures of high and loW melting frits can be used to control the sintering characteristics of the conductive particles. . Some other lead-free and cadmium-free glass frits useful in the present invention include alkali borosilicate-based and bismuth borosilicate-based frits. These precursors can be in the form of organometallic compounds.94 6.84 7.20 43. some glass compositions useful in the present invention are represented by the folloWing composition. The melt is then quenched by cooling the melt. The electrically functional poWders in the present thick ?lm composition are conductive gold poWder(s).06 16. Other transition metal oxides may also be employed as all or part of the inorganic binder.17 8. The inorganic binders of the present invention are selected from one or more of (1) lead free and cadmium free 40 glass frits. cobalt.15 7. As is Well knoWn in the art.6 40.82 1.32 3. thermal expansion. in one embodiment.-l500o C.90 34. 3-20 A1203. 50 It is preferred that the inorganic binder is a glass frit having a softening point of betWeen about 350 and 800° C. 0-2 BaO. the folloWing oxides and their precursors are useful in the present invention: TiO2. in order that the compositions can be ?red at the desired Transition metal oxides can also be formed in situ through the addition of precursor compounds. the metal oxides present in the thick ?lm composition could be directly in the form of an oxide or converted from metal-containing compounds 60 present invention.47 2. preferably from about 1 to about 4 um. Inorganic Binders Traditionally. Other transition metal oxides and their precursors are also useful in softening temperatures obtained by the ?ber elongation method ofASTM C338-57. the glass frit of the preceding composition is present in the thick ?lm composition in the range of 0-3. ruthenium. For example. copper oxide may be present or elemental copper. For example. alloys.13 15. components are given in Weight percent total glass compo sition. the oxide 65 the present invention. 0-4 Li2O. the term “softening point” refers to under ?ring conditions.5 3. 0-3 ZrO3. cosmetic and performance requirements.53 40. manganese and iron are useful in the present invention.45 5 19. as Well as other oxides. These additives improve adhesion as measured by Wire bonding or soldering. The electrically conductive gold poW ders of the present invention have a typical siZe of D5O less than about 10 microns. As used herein. Co3O4. H3BO3 for B2O3) in the desired proportions and heating the mixture to form a melt.96 15. copper.82 5.326.33 36. Particle siZe reduction can then be teristics.47 5. usually 1200o C.47 0.42 19.59 0. 30 composition.90 1.) to effect proper sintering. Sb2O3. As noted above.20 2. nickel. organo coppers.33 application method. particularly 8500 C. Metal poWders may be coated With surfactants Well knoWn in the art. yet gaseous evolution has ceased. SnO2. typically by pouring onto a cold belt or into cold running Water. mixtures of gold With small amounts of other metal poWders (for example up to 3 Weight percent based on total thick ?lm composition of silver).0 pm.20 2.5 to about 6. by mixing the desired com ponents (or precursors thereof. l-44 SiO2.88 1. or compounds of several elements.53 7. The peak temperature is generally in the range ll00° C. or crystalliza tion products from a frit Which form copper oxide. RuO2..95 15. carbonates. as Well as solvents 4 TABLE 1 Glass Compositions (in Weight percent total glass composition) A B c D E F G and small amounts of additional organic components.367 B2 3 components of a thick ?lm composition. 5-16 NaF.39 2.40 8.20 3. particularly a LTCC substrate. Oxides or oxide precursors of Zinc.18 13.70 15.84 19.9 Z102 Z110 B30 17. While simultaneously meeting Wettability. titanium. based on Weight percent total glass composi tion: 5-20 B203. metals in addition to the gold poWder may be added to the thick ?lm composition to meet the 20 desired properties of the conductor application.40 1.92 2. such as surfactants. and mixtures of gold poWders.2 19.02 5.27 10. 0-19 ZnO. Reactions betWeen oxides.19 16.14 8. typically in the range of 0-3 Weight percent total ?lm composition. MnOx. frits and any precursor materials that occur upon ?ring can form either glasses or 55 temperatures (typically 750-9000 C. As noted above.. heating is conducted to a peak temperature and for a time such that the melt becomes from glass compositions to meet current toxicity and envi ronmental regulations may limit the types of binder that can be used to achieve the desired softening and How charac entirely liquid. CuOx.54 1. e.2 9. In one embodiment.67 18. One or more different glass frit compositions may be used in the oxides Which aid binding of the functional metal layer to the substrate. Some embodiments comprise small amounts 25 As represented in Table 1.93 40.-l400o C.52 1.04 0.6 1. Wetting and adhesion to the substrate. The elec trically functional poWders may comprise elemental gold.11 9. B.01 16.. conductive compositions have been based on lead or cadmium containing frits. and 0-11 ZnF2. Fe2O3. 0-9 CaO. typically (although not limited to) have an average particle siZe from about 0. In one embodiment. The elimination of lead The glass binders (glass frits) are prepared by conven tional glass-making techniques.US 7. silver (Ag) is used in amounts of less than 2 Weight percent based on total thick ?lm composition. (2) transition metal oxides. The particle diameter and shape of the metal poWder is not particularly important as long as it is appropriate to the B203 $102 A1203 N320 Li2O P205 NaF CaO 6. Examples of some useful glass compositions (composi tions A to G) are given in Table 1 below.07 znr2 10.71 11. or frits.09 14. The particle siZe of the frits and oxides is not narroWly critical and materials useful in the present invention Will accomplished by milling as desired. ZrO2. (3) precursors to transition metal oxides. the thick ?lm composition of the present invention comprises copper oxide or a precursor of copper oxide. 2-41 P205. and (4) mixtures thereof.g.0 Weight percent total thick of Ag.92 12.

resistive. and thus densify the entire assembly. For example. “Firing” causes the inorganic components in the layers. No. No.US 7. the copper oxide is present in the amount of about 0. precursors of transition metal oxide and mixtures thereof are present in the total thick ?lm composition in up to 3 Weight percent. Various combinations of these and other solvents are formulated to obtain the viscosity and 45 isostatic pressing die is typically used to ensure precise alignment betWeen layers.254. a sharply focused laser can be used to volatiliZe thick ?lm composition. hoWever. glued or soldered to the surface of ?red parts. the term “?ring” means heating the assembly in an oxidiZing atmosphere. C. to a temperature.1 to 1. the conductor com position of the present invention may be used on one or more properties to the composition. military or automotive applications (such as auto The conductor composition of the present invention may be used in conjunction With uncured ceramic material. Organic Medium The inorganic components are typically dispersed into an organic medium by mechanical mixing to form viscous layer(s) to form resistive or capacitive circuit elements. transition metal oxide. transmit receive modules. radar. such as surfac 30 of the inner layers of the circuit.0 Wt. appropriate viscosity and thixotropy for screen print 25 ing. In addition. butyl carbitol. 095 to Steinberg and Us. any suitable method may be utiliZed. Wood rosin. resistors and/or capacitors. the conductor composition of the present invention is not used as a via ?ll composition. Typically. of other suitable conductor compositions. Usually. the dispersion Will contain 50-95 Wt % of inorganic components and 5-50 Wt % 50 furnace With a programmed heating cycle. such as Green TapeTM LoW Temperature Co?red Ceramic (LTCC). This is typically done by mechanical punch tive traces. the methods disclosed in Us. any suitable application tech nique may be employed. capacitive or dielectric functionality. resistors. thus forming reaction metal conductor layer to the via-?ll composition is usually applied by standard screen printing techniques.0 Weight percent of the total thick ?lm composition. Pat. Other examples of polymers include ethylhydroxyethyl cel lulose. The conductor composition of the present invention may be printed on the outermost layers of the circuit. and good ?ring and burn out properties.654. resistive. via holes are formed in the TapeTM. their precursors or mixtures thereof are present in the range of 0-3 Weight percent total 6 ing. A sheet of Green TapeTM is blanked With registration holes in each corner to a siZe someWhat larger than the actual dimensions of the circuit. Conductors.or beta terpineol or mixtures thereof With other solvents such as 40 Wire-bonded component. to react or sinter. mixtures of ethyl cellulose and phenolic resins. The most Widely used solvents found in thick ?lm compositions are ester alcohols and terpenes such as alpha. thus forming a ?red article. including: stable dispersion of solids. %. of organic medium (vehicle) in order to obtain good coating. For example. capacitors and any other components are typically formed by conventional screen printing tech 20 compositions called “pastes” having suitable consistency and rheology for printing. It is understood by those skilled in the art that the circuit may comprise “blank layers” or layers of dielectric or insulating material on Which no functional conductive. The rheological properties of the medium must be such that they lend good application niques. In one embodiment. Thus. The most frequently used polymer for this purpose is ethyl cellulose. 5. dibutylphthalate. and for a time suf?cient to volatiliZe (burn-out) the organic material in the layers of the assemblage and alloW reaction and sintering of the inorganic components of both the tape and conductors. . This conductive total thick ?lm composition. polymethacrylates of loWer alcohols. acceptable un?red “green” strength.191 to Mikeska may be utiliZed.2-0. Pat. The assemblies are trimmed to an appropriate siZe either after lamination or after ?ring. a small amount of additives. and monobutyl ether of ethylene glycol monoacetate can also be used. The organic medium is typically a solution of polymer(s) in solvent(s). conductive vias. Additionally. butyl carbitol acetate. antennas etc). a typical Green TapeTM layer may have contain one or more conduc Green TapeTM. The interconnections betWeen layers are formed by ?lling the vias With a thick ?lm conductive composition (via-?ll composition). In the case of a 35 tants. or a combination thereof. to form a multilayer electronic circuit. as Well. either before or after lamination. In a further embodiment. appropriate Wetta bility of the substrate and the paste solids. resistor inks or high dielectric constant inks can be printed on selected reacting With the glass and substrate or the paste (thick products in situ that bind the substrates. the conductor composition of the present invention is particularly useful as it has superior Wire-bondability properties over prior art compositions. may be a part of the organic medium.6 Weight percent of the and form via holes in the Green TapeTM. These tracks can be of the present invention. hexylene glycol and high boiling alcohols and alcohol esters. and it can vary. hoWever.367 B2 5 The transition metal oxides. The term “functional layer” refers to the printed Green 65 circuits. Components are typically Wire-bonded. The outermost layers of the circuit are used to attach compo nents. copper oxide is present in the total composition in less than 2. A con?ned uniaxial or kerosene. Each layer of circuitry is typically completed by screen printing conductor tracks. the individual layers are collated and laminated.326. The tape may be either constrained or free sintered during the ?ring process. Oxides aid adhesion by ceramic components of the ?lm). 4. APPLICATION 55 As used herein. This ?red article may be a multilayered circuit used in telecommuni cations. A Wide variety of inert liquids can be used as organic medium. as Well as others knoWn to those skilled in the art. Green TapeTM is typically used as a dielectric or insulating material for multilayer electronic 60 motive position sensors. a good drying rate. or capacitive layers are deposited. To electrically connect various layers of the multilayer circuit. In a further embodiment. Additionally. Firing is typically carried out in a conveyor belt furnace or in a box volatility requirements desired. the copper oxide is present in the range of about 0. The ratio of organic medium in the thick ?lm composition to the inorganic components in the dispersion is dependent on the method of applying the paste and the kind of organic medium used. as indicated above. Also. After each layer of the circuit is completed. such as air. a thick ?lm conductive composition different to that disclosed herein is typically utiliZed as a via-?ll composition. Which has conductive. volatile liquids for promoting rapid hardening after application on the substrate can be included in the vehicle. In the case of this invention. The glass frit. and various other paste components.

2-41 P205.5 0.2 40 2. The composition of claim 1 further comprising silver poWder in the range of 0-3 Weight percent based on total 83. 3-20 A1203.7 41.100 pulls 0. 5-16 NaF.substrate separation under the heel Optimally. categoriZed in six Ways: 35 What is claimed is: 1.9 0. 6. the paste Was formulated to the proper solids and Rhodium complex Organic** Cosmetic Fired Appearance Re?re Appearance 1 mil Au .2 1 0. resis Mean Std Dev 0.8 viscosity levels through the addition of solvent or resin NG OK OK OK OK OK NT OK NT OK NT OK containing organic vehicle. All ingredients Were thoroughly mixed in a mixer on a three roll mill or both in order to achieve appropriate dispersion. Any separation of the metal from the substrate (type 0.5 1.9 83 83 84 Ag Frit* CuOx 1 0. dibutylphthalate. 3 or 4 bond failures are observed. The composition of claim 1 Wherein said transition metal oxide is present in the range of 0. 45 frit.5 or 6 failure modes Were observed. .3 1 0. based on total thick ?lm composition. electrical contact. Test Procedures used in Examples 20 bonds 2 mil Au.4 14.0 0. The thick ?lm pastes of Examples A-G Were formed A CdO Bi203 0 0 D B 0 0 C 0.metal separation at the heel Metal .6 0 0 0 0 *The frit used in Examples A.75 0 0 0 0 300 um bonding ?ngers and larger bonding pads. 1-44 SiO2. dielthyl Observations Were made regarding both the strength of the bond and the failure mode of the pull. The solids level Was also chosen for good screen printability.4 13.1 2.0 0.75 pulls Mean Std Dev 42.6 2 mil Au. This Was done to observe any tendency for metalli pulls 25 Mean Std Dev 43. A thick ?lm conductive composition for use in micro Wave applications comprising: @kIl-BUJHO Ingredients (Wt %) Au Metal . 4. 5. and F is represented by Frit G in Table 1.2-0. These patterned parts Were co?red and bonded using 25 and 50 um gold Wire using a Hughes 2460 or K&S 4124 bonder respectively. etc).326. In the examples cited here. 0-4 Li2O.5.5 0.9 1. 7.1.1 thick ?lm composition.0 Weight percent based on total thick the bonding. E.1.5.8 0. 30 ** The organic vehicle for this composition included ethyl cellulose.7 43.6 tivity. 3. B. The composition of claim 1 Wherein said glass frit has a softening point in the range of 350 to 8000 C.6 0 0 13. 0-2 BaO. During testing.367 B2 7 EXAMPLES 8 TABLE 2-continued The invention Will noW be described in further detail With practical examples (Examples A-G).5 0.5.US 7. and c) organic medium Wherein said inorganic binders are lead free and cadmium free.0 2. Viscosity Was chosen (here 150-500 PaS) to be able to print conductor lines using standard screen printing equipment and techniques. The composition of claim 1 Wherein said composition is compatible With loW temperature co-?red ceramic tape. 0-9 CaO. approximately 1920 bonds Were formed and 75-100 Were pulled for adhesion values. 2. Once the metals and oxides Were suitably dis persed.9 1. The composition of claim 1 comprising said glass frit in the range of 0 to 2.5 14. Any separation of the bond from the metalliZation indicated an issue With bondability or bond acceptance.6 Misses/1920 13.1 NT Wirebonding: Parts Were patterned in a manner Which provided 150 and 0.1 42. 55 ?lm composition.6 Weight percent total thick ?lm composition. The composition of claim 1 Wherein said gold poWder is present in the range of 60-90 Weight percent based on total TABLE 2 D A B C Double print E F 60 thick ?lm composition.6) indicated an adhesion issue. as Well as for optimal functional performance (adhesion. lecithin and a phenolic resin dispersed in a mixture of texanol.1 42 1.7 2. bonds Were placed at the center of the bond ?nger as Well as close to the edge of the bond ?nger. 0-10 Na2O.9 83.3 1.3 0.metal separation at the ball a) gold poWder.1 1 1 0. dimethylphthalate.9 42. Good bond acceptance Was de?ned as no misses or other errors during binder is present in an amount of up to 3 Weight percent.8 0.9 0 0 12. Failure modes Were eneglycol dibutylether. 0-19 ZnO. Bonds Were pulled using a Dage Series 4000 bond tester.7 0 0 13.4 13.3 13.6 0 0 12. selected from the group consisting of 5-20 B2O3.4 2. edge .7 0.6 0 0 13. Examples A-F indicate that no type 0. b) one or more inorganic binders selected from (1) glass 40 Break at top of ball Wire break Break at bond heel Bond .1. 0-3 ZrO3.1 0.5 1 Double print E 0 0 F 0 0 according to the following methodology. soya Zation lifting during either bonding or bond pull testing. only type 2.substrate separation under the ball Bond .8 42. 8.2 0.9 43. In these examples. glycol ether and pine oil. the thick ?lm paste components and their percentages are listed in Table 2. and 0-11 ZnF2 (2) transition metal oxides and (3) precursors of transition metal oxides.9 0. center bond .8 0. and (4) mixtures thereof.1. The composition of claim 1 Wherein said inorganic 50 Another test of the bond acceptance included bonding multiple 25 um Wires to the metalliZation.7 0.

compris ing a multilayer circuit comprising the following steps: a) forming a patterned array of Vias in a plurality of layers of green tape. Wirebond connec of step (b). beam former. tion. and high frequency transmit/receive modules or radar. baluns.US 7. l/O’s. .326. and transmission lines. EM coupled feedthroughs. ?lters. Via surface of some or all of the Via-?lled green tape layers 10 feedthroughs. The method of using of claim 9 to form microWaVe circuit components selected from the group consisting of: c) printing pattered thick ?lm functional layers over a antenna. couplers. (e) 10. d) laminating the printed green tape layers of step (c) to form an assemblage comprising a plurality of un?red interconnected functional layers separated by un?red green tape.367 B2 9 9. A method of using the composition of claim 1 to form 10 e) printing at least one patterned layer of the thick ?lm composition of claim 1 over the assemblage of step (d). f) co?ring the assemblage and patterned layer(s) of step b) ?lling the Vias in the green tape layer(s) of step (a) With a thick ?lm composition.