CN1159134A - Thick film compositions for via fill and capture pad applications - Google Patents
Thick film compositions for via fill and capture pad applications Download PDFInfo
- Publication number
- CN1159134A CN1159134A CN96121923A CN96121923A CN1159134A CN 1159134 A CN1159134 A CN 1159134A CN 96121923 A CN96121923 A CN 96121923A CN 96121923 A CN96121923 A CN 96121923A CN 1159134 A CN1159134 A CN 1159134A
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- Prior art keywords
- paste
- inorganic bond
- conductor
- filler
- thick film
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02697—Forming conducting materials on a substrate
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- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Physics & Mathematics (AREA)
- Power Engineering (AREA)
- Conductive Materials (AREA)
- Parts Printed On Printed Circuit Boards (AREA)
- Electrodes Of Semiconductors (AREA)
- Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
- Production Of Multi-Layered Print Wiring Board (AREA)
Abstract
The invention relates to a method of filling conductive passage and a method that transitional compounds are used to form conductive trapping fillings between electrical functional layers of different metals for electrical insulation layer separation.
Description
The application is that the part of the U.S sequence number 08/368927 (EL-0360-B) of 1995.1.5. application continues, the 08/368927th, the continuation of the U.S sequence number 08/233485 (EL-0360-A) of 1994.4.26 application, and 08/233485 be the continuation of the U.S sequence number 07/956273 (EL-0360) of 1992.10.5 application.
The present invention relates to thick film combination, particularly a kind of thick film paste composite, by utilize in the multilayer electronic component interior access with capture filler and be connected different metal it is useful.
The current densities that increases has stimulated the development of ceramic multilayer circuit.For adapting to this needs, developed two class technology: sunken cord and (2) screen printing multiple layer inner connection on the single ceramic substrate (1).
Sunken cord to connect in the pottery and comprise three main combination block: insulating barrier, as aluminium oxide and the aluminium oxide that combines with the glass cordierite; The spray metal, as Mo and the W that under high temperature reduction atmosphere, handles, or noble metal of under air or inert atmosphere, handling at low temperatures and alloy thereof; With path filler and capture the filler conductor, as noble metal and composition thereof and its alloy, so that connect conductive tracks in the adjacent layer.This paper on the whole, with the path filler with capture the filler conductor and be called " transition combination thing ".
Insulating barrier is the most frequent to be made by unprocessed band, this band be dispersed in the unsintered insulation in the SOLID ORGANIC polymeric matrix inorganic adhesive material wear into fine grain film, above-mentioned polymer is easy to volatilization when the baking insulating material.But this layer also can be by making the thick film muddle of insulation to substrate.It is to be dispersed in the finely disintegrated solid insulation that contains in the organic media that is dissolved in the polymeric binder in the solvent and the dispersion of inorganic bond that this thick film is stuck with paste.
Multilayer circuit is by providing hole (path) in insulation on the belt, and web plate type metal track is filled this path with conductor paste again and made on this belt; The undressed band plate that will have some figures of filling vias then is stacked together, and lamination also toasts under suitable temperature, so that the organic material that is contained in conduction and the insulating barrier volatilizees, this conducting metal of sintering also makes the insulating material densification.According to the material that in any particular system, adopts, can low temperature (800-1000 ℃) or at high temperature (1300-1600 ℃) with its baking, sunkening cord with formation connects in the pottery.
Stick with paste the multiple layer inner connection that forms screen printing by screen printing insulator, conductor and bonding conductor on ceramic substrate (the path filler in equaling to sunken cord) and connect, so that build up coherent layer.Usually print each layer respectively, print each element (insulator and conductor) of this layer sometimes, and dry and baking.Repeat this technology then, to form sandwich construction.Which floor this technology is limited to, but known in the prior art sunkening cord (band) structure is above 60 layers.
For example, for lead connection, reliability with reduce cost that silver conductor prepares circuit and the metal spraying that has on top layer is useful with burying.This structure with conductor of the Ag that imbeds and top layer gold need or be captured the filler paste composite by means of thick film path inserts outer field Au is electrically connected with the Ag that imbeds.
Using Ag, Au or Ag/Pd to stick with paste makes Au and Ag be connected with several shortcomings.For example, Ag is diffused among the Au easily, has polluted the Au conductor like this, and reduces reliability owing to increasing Ag in the danger that top layer moves.The counterdiffusion mutually of Ag and Au particularly in the temperature range (700-950 ℃) of its sintering, causes the Kirkendall hole also finally to cause opening circuit.
So, to be badly in need of very much the path filler or to capture filler (transition) composition, it can connect different metal (Ag, Ag Pd and Au or Ag) and the obstacle of a kind of metal diffusing to another kind of metal is provided.Except its obstacle, these compositions also have the mechanics requirement of low resistance and compatible sandwich construction.
The present invention relates to use path fill composition of the present invention to make sandwich construction, sequential steps is as follows: fill via hole in the insulating barrier of separating the different metal electric functional layer with a kind of composition by screen printing, above-mentioned composition comprises that weight with total inoganic solids is benchmark, 75-100% wears into fine grain Ru, Os, Ir and Rh, 25-0% wears into fine grain inorganic bond, and the both is dispersed in the liquid organic medium; Toast via hole then, so that this liquid medium volatilizees the particle (if any) of reburn knot conducting metal particles and inorganic bond in from then on sticking with paste through filling.
In addition, the present invention relates between the electric functional layer of the different metal that is insulated layer separation, form the method for capturing filler of conduction, it comprises sequential steps: by screen printing filler is captured in the printing on the insulating barrier of separating electric functional layer of transition combination thing, above-mentioned transition combination thing comprises, with the inoganic solids gross weight is benchmark, and 75-100% wears into fine grain Ru, Os, Ir and Rh and composition thereof and alloy.25-0% wears into fine grain inorganic bond, and the both is dispersed in the liquid organic medium; The via hole of baking through filling, make this liquid organic medium from then on stick with paste in volatilization, knot conducting metal particles and inorganic binder particle (if any) reburn.
A kind of logical method of multiple layer inner connection of making comprises using and captures the filler configuration, whereby by with transition conductor with silver and the horizontal bridge joint of gold.In this case, this transition conductor overlapped on the silver conductor of imbedding and to be directly connected to the method printing of golden path.Owing to laterally separate (mil promptly 〉=4) and the suitable transition material of use fully between golden path and the silver conductor, circuit can bear and many times toast again and do not have an electric reliability accident relevant with the Kirkendall cavitation process.Do not have this horizontal separation, integrity problem may take place, this be since Ag near Au, with the possibility of adding that is not adequately protected of the transition conductor that causes with the relevant shortcoming of printing.
Making another method that multiple layer inner connection connects comprises: separating different metal, adopting in the insulating barrier as the electric functional layer of Ag and Au to form via hole.Fill this path with transition conductor composition of the present invention, to make it to have and capture the same function of filler.
In above-mentioned technology, transition conductor composition of the present invention is used by web plate or mould printing usually.Therefore, but the form that said composition will be the thick film of screen printing sticks with paste.
Under the situation of path filler, it is inserted the method printing transition conductor of the path of separating the silver conductor imbed and metallic conductor.This transition conductor composition can use inorganic bond and wear into fine grain metal, this metal can not with the Ag alloying, promptly do not form the solid solution with Ag, it is scattered in the liquid organic medium.For the suitable metal of this purpose is Os, Ru, Ir, Rh and composition thereof and alloy.In these metals, preferred Ru.But this metallic particles partial oxidation, preferably its surface area is 0.1-5m
2/ g.The accurate ratio of inorganic material (metal and adhesive) and liquid organic medium depends on the rheology in the paste.But this paste contains 75-100% (weight) metal and inorganic binder particle usually, and they are scattered in the liquid organic medium of 0-25%, and still, the weight of preferable alloy is 85-99% (weight), and preferred medium is 1-15%.As long as the rheology of sticking with paste is fit to used printing equipment, the ratio of medium and inorganic material is undemanding.When baking during said composition, the volatilization and from stick with paste fully of this organic media with conducting metal particles and frit-sintered.
Inorganic bond of the present invention or glass system must seal, to avoid by surface migration between porous glass material.Preferably, this glass system comprises ZnO in prescription, because known ZnO avoids surface migration.
The conductivity that improves glass under baking temperature can promote the migration of dissociated ion, moves in the glass ceramic material as silver.In addition, discover that this " battery effect " in the conductor insulation circuit is the real performance of migration.The known alkali metal oxide that mixes glass is as PbO, CdO and Bi
2O
3Form thing with low temperature glass, as B
2O
3, GeO
2, V
2O
5All can improve the DC conductivity of glass.So the glass system that uses among the present invention should avoid improving DC conductivity.In addition, near the electrical potential difference that causes being produced by the different metal conductor conductor filler causes that the glass system of foaming does not conform with glass of the present invention and selects, above-mentioned different metal conductor is separated by the electrolyte that the glass of molten state constitutes, this electrolyte has low-resistivity under fusion temperature, thereby allow big electric current, promote that ion moves by insulating material.So the preferred glass system of the present invention is a glass known in the present technology, they are crystallizable, and produce the residual glass of infusibility especially and keep high resistivity in melt temperature.
The main purpose of organic media is the carrier as the finely disintegrated solid in the dispersive composition, and the form of dispersion is that it can easily be coated onto on pottery or other substrate.Therefore, this organic media must at first be can be with solid dispersed to wherein organic media with enough degrees of stability.The second, the rheological characteristic of this organic media must be to make dispersion that good coating be arranged.
Most of thick film combinations are coated onto on the substrate by screen printing.So they must have suitable viscosity, so that it easily passes through screen cloth.In addition, they should be thixotropings, in order to pass through it to be fixed fast the resolution that obtains thus behind the screen cloth.And rheological characteristic is the first important performance, preferably this organic media is prepared to such an extent that make this solid and substrate have suitable wettability, and good rate of drying is enough to stand rough machined dry film intensity, the baking of becoming reconciled.The satisfactory appearance of the composition that toasted also is important.
According to all these standards, there is multiple liquid to can be used as organic media.The organic media that is used for most of thick film combinations generally is the resin solution that is dissolved in solvent, and this solvent usually also contains thixotropic agent and wetting agent, and said solvent seethes with excitement between 130-350 ℃ of scope usually.
The example of suitable solvent comprises kerosene, solvent naphtha, dibutyl phthalate, butyl must pure and acetic acid esters, hexylene glycol and high-boiling point alcohol and alcohol ester.Prepare viscosity and the volatility of various combinations to obtain to wish of these and other solvent.
The most normal use and preferred resin be ethyl cellulose.But resin also can use as the mixture of ethylhydroxyethylcellulose, wood rosin, ethyl cellulose and phenolic resins, the polymethacrylates and the ethylene glycol acetate-butyl ether of lower alcohol.
The carrier that preferred thick film applies is based on weight ratio about 1: 8 ethyl cellulose and β-terpinol.This paste is suitable to be prepared with three-roll mill.The preferred viscosity of these compositions is about 100-200Pa.S., and this records with 10rpm with the 5# axle on Brookfield HBT viscosimeter.The amount of the carrier that is used is determined by the dispensing viscosity of final hope.
Normally used thixotropic agent is castor oil and the derivative and the ethyl cellulose of hydrogenation.Certainly, always do not need to add thixotropic agent, because thinning relevant with the shear in any suspension, the inherent characteristic of this flux resin only suits in this.Suitable wetting agent comprises phosphate and soybean lecithin.
This paste should prepare with three-roll mill.When room temperature is measured with the shear rate low, that neutralization is high with the Brookfield viscosimeter, the viscosity of this paste is generally 0.1-300Pa.S.The amount of the organic media that is adopted (carrier) and type are mainly determined by the dispensing viscosity and the print thickness of final hope.
Sandwich type element can be in non-reduced atmosphere, as toasting in air or the nitrogen, and uses reducing atmosphere, is unnecessary as hydrogen.The special benefits of the present composition is exactly that its baking can be in air and need not baking atmosphere is regulated especially.
When making the sandwich type element of bridge joint, paste into conducting layer figure by the screen printing thick film conductor.This class is stuck with paste and is comprised the low-alloy of wearing into fine grain silver or silver that is dispersed in the liquid organic medium.This paste can contain a spot of inorganic bond, and this inorganic bond is no more than this conduction usually and sticks with paste about 20% of solids content (weight).Preferred at least 0.5% (weight) inorganic bond that uses is to obtain sufficient technique effect.The solidification point of this inorganic bond is lower than the sintering temperature of silver.Have thick film when sticking with paste the multilayer module of conductive layer in baking, volatilize during fully from then on organic media is stuck with paste, and with the metallic particles sintering of silver.As truly using inorganic bond, it also is sintered.Be noted that above-mentioned path filled compositions is suitable for too when forming conductive layer according to the invention.
The particle size of solid itself is undemanding in the transition combination thing, as long as particle is not quite to influencing sintering nocuously, or excessive for screen printing, or not little of causing that difficult treatment gets final product.So the particle size range of the solid that uses among the present invention is preferably in the 0.5-10 micrometer range between the 0.1-20 micron.Form that the insulating barrier that uses in the multilayer can thick film be stuck with paste is coated with or is coated with the form of undressed (not baking) band.
Under the situation that insulative thick film is stuck with paste, the screen printing isolating separator layer.Under the situation of the undressed band of the insulation that can toast altogether, two layers or multilayer band is overlapped together, so that form bottom substrate.Under the situation of being with the undressed band of insulation of pressing substrate (TOS), one or more layers band is laminated on the bottom substrate.The thick film of insulation is stuck with paste and is comprised the fine grain solid insulation of wearing into that is dispersed in the liquid organic medium, and the undressed band that insulate comprises the fine grain solid insulation of wearing in the solid matrix that is dispersed in organic polymer.In both cases, when this layer of baking, dispersion medium volatilizees fully, and makes solid insulation by densification.
When using undressed band to make insulating barrier, whether this band contains inorganic bond, depends on the baking temperature of this system.For example, need the (if there is) inorganic bond hardly at the undressed band of aluminium oxide of high temperature (1300-1600 ℃) baking, this is because enough closely knit probably during baking.Therefore, will contain 0-10% (volume) inorganic bond thing at the undressed band of the aluminium oxide of high-temperature baking.On the other hand, need at the undressed band of the filling aluminium oxide of low temperature (800-1000 ℃) baking a large amount of (volume) at the sintered inorganic bond of this low baking temperature.Under latter event, this band that is toasted is the glass glue matrix that has wherein disperseed the sintering of alumina particle basically.So the undressed band of the filling aluminium oxide that will toast at low temperatures or the undressed band of filling any pottery can contain the inorganic bond (is benchmark with total inoganic solids) greater than 50% (volume).Both can be at undressed band, the thick film of conductive layer is stuck with paste or the chemical composition of the (if there is) inorganic bond that can use in the transition combination thing, is unrestricted with regard to the aspect that obtains advantage of the present invention.
Discuss the present invention in more detail by the embodiment that provides.But scope of the present invention is subjected to the restriction of these embodiment never in any form.Embodiment 1
Preparation is stuck with paste as the thick film of bridging forehearth filler in the LTCC circuit.The composition that this path filler is stuck with paste is as follows:
In paste total weight % in paste inorganic matter weight % frit * 12.87 14.06Ru 78.67 85.94 medium * * 5.07-Duoeen 1.67-hexanol 0.05-
100.00 100.00* frit weight %SiO
233.6Al
2O
38.6ZrO
23.4ZnO 20.3BaO 21.5SrO 12.4** medium 62% (weight) Texanol31% (weight) dibutyl phthalate 7% (weight) ethyl cellulose
This paste is as connecting the path filler of multilayer in the preparation in the following manner:
1. (Wilmington is DE) to form insulating barrier for Dupont 951AT Green Tape, E.I.du pont de Nemours and Company to use the commercially available undressed band of filling alumina glass;
2. use (cofirable) that can toast altogether golden thick film to stick with paste to form the external conductor figure of this multilayer.
3. use silver thick film to stick with paste to form the inner conductor figure of this multilayer; With
4. use above-mentioned path filler to stick with paste the via hole that connects this silver and golden conductive pattern to fill.
5. the plate that filling vias is set makes to have the top layer of the assembly of 7 additional undressed belts, above-mentioned belt is laminated and in 875 ℃ of bakings altogether.
Measure the resistance of baking element, and measure after toasting 5 times again in baking back altogether or at 850 ℃ and not open circuit.Carry out X-ray energy dispersion analysis (EDAX) for being sprayed directly on to this transition by the surperficial golden sprayed coating on the filler.Baking back EDAX mensuration Ag/Au peak area ratio is 0.008 altogether, and is 0.017 after toasting for 5 times again, and this has proved has blocked the diffusion of silver by the bridging forehearth filler effectively.Embodiment 2
The preparation thick film is stuck with paste to get over as the mistake in the LTCC circuit and is captured filler.This composition of capturing the filler paste is as follows:
Inorganic matter weight % frit * 12.42 14.05Ru 75.99 85.95 medium * * 6.31-soybean lecithin 1.13-dibutyl phthalate 2.33-Texanol 1.69 during total weight % sticks with paste in the paste-
100.00 100.00* frit weight %SiO
233.6Al
2O
38.6ZrO
23.4ZnO 20.3BaO 21.5SrO 12.4** medium 62% (weight) Texanol31% (weight) dibutyl phthalate 7% (weight) ethyl cellulose
This thick film is stuck with paste as by as shown in the formula the filler of capturing that connects multilayer in the preparation:
1 uses Dupont 951AT Green Tape to form insulating barrier;
2 use the golden thick film that can toast altogether to stick with paste, and with the external conductor figure of formation multilayer, and use golden path filler with the path in the top layer of filling multilayer.
3 use silver thick film to stick with paste to form the inner conductor figure of multilayer; With
4 use this to capture filler sticks with paste to form with outside silver-colored conductive pattern separation and to be communicated with golden path captured inside filler in the belt of top.
The 5 superimposed access panels of filling as the gold of top layer that contain have that transition captures that the assembly of the inner panel of filler and silver conductor and additional undressed belt forms 8 layers structure and 875 ℃ of bakings altogether.
Mensuration is through the resistance of element of baking, altogether the baking back or 850 ℃ 10 times again the baking back measure and do not open circuit.Embodiment 3
Prepare path filler thick film paste composite by following composition:
Inorganic matter weight % frit 22.9 28.6 (F3876) Ru 57.1 71.4 medium 10.2-surfactants 2.9-solvent 6.9 during total weight % sticks with paste in the paste-
100.00 100.00
This thick film is stuck with paste as the path filler that connects multilayer in preparing as follows:
1 fires the insulating thick film layer on alumina substrate
2 fire silver conductor on insulating barrier.
3 fire the insulating thick film layer of band path on whole silver conductor layer.This insulating barrier is made of printing, drying, the baking procedure opened in twice minute.
4 are printed onto in the path baking then by screen printing with the path fill composition.Carry out this step with two kinds of diverse ways:
Each insulating barrier that (A) will toast is filled with thick film combination, baking then, and the result causes twice printing and the baking of the combination of this paste;
(B) only once fill the double insulating layer path, thereby cause the one-step print thing and the baking of the composition of this paste.
5 fire thick film gold conductor at the top of insulating barrier.This gold overlaps and stops on the path packing material.By the element electric continuity that silver-path filler-Jin circuit test is made by this way, begin not find to open circuit, and after following situation, test:
-1x, 3x, 5x, 10x toast 10 and 15 mil paths again.
-1000 thermal cycles (50 ℃-+150 ℃)
Near do not see golden bonding filler this path filler golden lead bonding force descends.
Claims (8)
- The method of the conductive path between 1 one kinds of electric functional layers of filling the different metal that electric insulation layer separates, it comprises that sequential steps is:(1) uses the transition combination thing, by the via hole in this insulating barrier of this electric functional layer of screen printing filling separation, it is benchmark that above-mentioned composition comprises with total inoganic solids weight, what contain 75-100% wears into fine grain Ru and composition thereof and alloy, 25-0% wears into fine grain inorganic bond, and the two all is dispersed in the liquid organic medium; With(2) baking through filling via hole so that this liquid organic medium from then on stick with paste in volatilization, the particle (if any) of this conducting metal particles of sintering and inorganic bond then.
- 2 one kinds form the method that conduction is captured filler, comprise sequential steps between the electric functional layer of the different metal that electric insulation layer is separated:(1) captures filler with transition combination thing screen printing on the metallic conductor that is embedded in, the 75-100% that it is benchmark that above-mentioned composition comprises with total inoganic solids weight wears into fine grain Ru and composition thereof and alloy, 25-0% wears into fine grain inorganic bond, and the both is dispersed in the liquid organic medium;(2) fill the via hole that connects the different metal conductor; With(3) toast so that this liquid organic medium volatilizees in from then on sticking with paste, then this conducting metal particles of sintering and sintering inorganic binder particle (if there is).
- 3 claims 1 or 2 composition, the softening point that it contains 0.5-20% are 400-1000 ℃ inorganic bond.
- 4 claims 1 or 2 method, wherein this insulating barrier is formed by the undressed band of the filling pottery that does not contain inorganic bond, and this transition combination thing does not contain inorganic bond, and baking is being carried out under non-reduced atmosphere under 1300-1600 ℃.
- The method of 5 claims 4 is wherein toasted and is being carried out under non-reduced atmosphere under 800-1000 ℃.
- The method of 6 claims 4, wherein this transition combination thing contains inorganic bond.
- The method of 7 claims 4, wherein the undressed band of this filling pottery is a kind of ceramic thick film.
- 8 the process of claim 1 wherein that this electric functional layer is selected from the group of resistance or conductor.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US554326 | 1990-07-19 | ||
| US55432695A | 1995-11-02 | 1995-11-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1159134A true CN1159134A (en) | 1997-09-10 |
Family
ID=24212930
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96121923A Pending CN1159134A (en) | 1995-11-02 | 1996-11-02 | Thick film compositions for via fill and capture pad applications |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPH09172084A (en) |
| KR (1) | KR0173553B1 (en) |
| CN (1) | CN1159134A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1645560B (en) * | 2004-01-05 | 2010-09-29 | 国际商业机器公司 | A suspension for filling via holes in silicon and method for making the same |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001035814A (en) * | 1999-07-22 | 2001-02-09 | Vacuum Metallurgical Co Ltd | Method of forming silver wiring pattern |
-
1996
- 1996-11-02 KR KR1019960051684A patent/KR0173553B1/en not_active IP Right Cessation
- 1996-11-02 CN CN96121923A patent/CN1159134A/en active Pending
- 1996-11-05 JP JP8293042A patent/JPH09172084A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1645560B (en) * | 2004-01-05 | 2010-09-29 | 国际商业机器公司 | A suspension for filling via holes in silicon and method for making the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH09172084A (en) | 1997-06-30 |
| KR0173553B1 (en) | 1999-10-15 |
| KR970027020A (en) | 1997-06-24 |
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