EP3134903B1 - Aluminium pastes for thick film hybrides - Google Patents
Aluminium pastes for thick film hybrides Download PDFInfo
- Publication number
- EP3134903B1 EP3134903B1 EP15720938.8A EP15720938A EP3134903B1 EP 3134903 B1 EP3134903 B1 EP 3134903B1 EP 15720938 A EP15720938 A EP 15720938A EP 3134903 B1 EP3134903 B1 EP 3134903B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- metallization
- ceramic composite
- composite according
- paste
- ceramic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims description 30
- 229910052782 aluminium Inorganic materials 0.000 title claims description 22
- 239000004411 aluminium Substances 0.000 title 1
- 239000000919 ceramic Substances 0.000 claims description 22
- 238000001465 metallisation Methods 0.000 claims description 15
- 239000011521 glass Substances 0.000 claims description 14
- 239000000758 substrate Substances 0.000 claims description 12
- 239000002131 composite material Substances 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 8
- 239000002318 adhesion promoter Substances 0.000 claims description 5
- 229910000410 antimony oxide Inorganic materials 0.000 claims description 4
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims description 4
- 239000001856 Ethyl cellulose Substances 0.000 claims description 3
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 3
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 229920001249 ethyl cellulose Polymers 0.000 claims description 3
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 229940116411 terpineol Drugs 0.000 claims description 3
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004925 Acrylic resin Substances 0.000 claims description 2
- 229920000178 Acrylic resin Polymers 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000007649 pad printing Methods 0.000 claims description 2
- 239000010665 pine oil Substances 0.000 claims description 2
- 238000007639 printing Methods 0.000 claims description 2
- 238000007650 screen-printing Methods 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims 6
- 229910017083 AlN Inorganic materials 0.000 claims 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims 2
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims 2
- 229910052593 corundum Inorganic materials 0.000 claims 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims 2
- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 claims 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 claims 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 7
- 229910052709 silver Inorganic materials 0.000 description 7
- 239000004332 silver Substances 0.000 description 7
- 235000012431 wafers Nutrition 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 2
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000000637 aluminium metallisation Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006121 base glass Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
- H01B1/023—Alloys based on aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/14—Conductive material dispersed in non-conductive inorganic material
- H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
Definitions
- the invention relates to aluminum-containing metallization pastes for the production of hybrid circuits.
- Aluminum metallizations are difficult to handle due to the very low redox potential of the aluminum and thus its easy oxidation and therefore not common.
- polymers with aluminum which are used as thermal pastes or adhesive with a thermal conductivity of about 1 to 5 W / mK.
- Silver pastes with low aluminum doping for example 1 to 3% by weight of aluminum, are used in solar cell technology for the simultaneous doping and contacting of wafers.
- the aluminum content of the pastes used here is used for doping a wafer without back surface field and allows the electrical contacting of the Si wafer with the silver electrode with a low contact resistance, see, for example WO 2002/061854 A1 ,
- the doping of the rear side of a solar cell with aluminum likewise does not serve to electrically contact the solar cell.
- the doping with aluminum counteracts the decrease in the efficiency of a solar cell at low wafer thickness.
- the electrical contact is achieved by a silver content in the aluminum paste or by an additional silver-containing coating, see, for example EP 2 418 656 A1 , Also WO2011 / 122369 A1 and US2012 / 168689 show metallization pastes that are applied to Si wafers.
- EP 1 087 646 A2 shows a metallizing paste with finely divided aluminum with d 50 equal to 5 microns and a glass frit as a primer, which is applied to glass or enameled steel.
- US 2012/222890 A1 shows a conductive substrate with a conductive structure. These consists of aluminum grains, which are placed in a binder and converted into a conductive layer by means of horizontally and vertically applied pressure at 0 - 150 ° C.
- the cited document moreover discloses that antimony oxide is added to the metallizing paste in order to reduce the bending of the wafer during the baking of the applied paste.
- the object of the invention is to provide a contacting or metallizing paste for use in thick-film hybrid technology that is less expensive than conventional silver-containing metallizing paste.
- the object is achieved with a metallization-ceramic composite having the features of claim 1.
- This metallization paste for hybrid circuits on ceramic substrates is characterized in that it comprises finely divided aluminum, an adhesion promoter and a temporary organic vehicle for pasting.
- Antimony oxide as known from the prior art, is not necessary according to the invention, ie the metallizing paste contains no antimony oxide.
- a finely divided aluminum-containing paste with a glass portion and a temporary organic vehicle for pasting and simultaneously protecting the aluminum from oxidation can be applied to surfaces of ceramic substrates such as Al 2 O 3 , AlN by various methods such as screen printing, stencil printing, pad printing, spray coating and other coating methods , ZrO 2 are applied.
- the paste is dried and then sintered in the presence of oxygen at elevated temperature, preferably at temperatures between 600 and 1000 ° C, firmly on the support, so the ceramic substrate.
- the aluminum particles are preferably in finely divided, spherical form. They can be obtained by spraying liquid aluminum in an inert atmosphere.
- the spherical shape produces a minimum surface-to-volume ratio whereby the oxidation susceptibility of the aluminum is minimized.
- the particle size of the finely divided aluminum should be between 0.5 and 50 microns (size determination with the laser scattering method according to ISO 13320: 2009) and is preferably 1 to 10 .mu.m, so that the particles through common screen mesh, such as VA160-18 with 45 microns mesh size , fit.
- a glass for example ZnO-SiO 2 -B 2 O 3 serve as a bonding agent between ceramic and aluminum. Glasses that are suitable for adhesion promotion must be adapted to the material of the ceramic substrate in terms of their chemical nature and with respect to the thermal expansion coefficient.
- a ZnO-SiO 2 -B 2 O 3 glass is used, which has a high affinity to both the surface of the ceramic substrates and Al 2 O 3 , which is formed during baking on the surface of the aluminum balls.
- moderators for adjusting the melting point, glass viscosity and thermal expansion coefficient in amounts of 0 to 10 wt .-% based on the mass of the glass may be included. Examples are CaO, TiO 2 , ZrO 2 , Bi 2 O 3 and / or Li 2 O.
- the moderators can be melted into the glass or added to the base glass as a binary oxide.
- the solid paste material apart from the organic paste vehicle, is then filled with aluminum powder to 100 wt .-%. This results in thus 75 to 99 wt .-% aluminum powder as solid constituents of the metallizing paste.
- organic paste vehicles known media such as ethyl cellulose or acrylic resin dissolved in high boiling solvents such as pine oil, terpineol, butylcarbitol, Texanal (also in combination) can be used.
- the applied paste dried in air at about 60 to 110 ° C can be baked in air, for example in a belt furnace or in a chamber furnace in a total process of 30 to 150 min with a temperature peak of 600 to 1000 ° C for 1 to 15 min.
- the metallization is electrically conductive and has an adhesive strength of over 25 N / mm 2 .
- the adhesive strength is in the usual range of, for example, silver metallizations.
- the thermal conductivity is over 100 W / mK.
- Metallization is a low-cost alternative to silver metallizations.
- the paste was screen printed on a 96% alumina substrate using a 120 mesh stainless steel screen.
- the printed ceramic was then at 80 ° C for 30 min. dried and sintered in a roller oven at a peak temperature of about 870 ° C for 10 minutes. The entire sintering time was 45 min.
- the bond strength in the nut test was 30 N / mm2, the electrical conductivity of the applied hybrid at 4.2 ohms.
Landscapes
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Conductive Materials (AREA)
Description
Die Erfindung betrifft Aluminium-haltige Metallisierungspasten zur Herstellung von Hybridschaltungen.The invention relates to aluminum-containing metallization pastes for the production of hybrid circuits.
Metallisierungen aus Aluminium sind aufgrund des sehr niedrigen Redox-Potentials des Aluminiums und damit seiner leichten Oxidierbarkeit schwer zu handhaben und deshalb nicht verbreitet. Bekannt sind Polymere mit Aluminium, die als Wärmeleitpasten oder -kleber mit einer Wärmeleitfähigkeit von etwa 1 bis 5 W/mK eingesetzt werden.Aluminum metallizations are difficult to handle due to the very low redox potential of the aluminum and thus its easy oxidation and therefore not common. Are known polymers with aluminum, which are used as thermal pastes or adhesive with a thermal conductivity of about 1 to 5 W / mK.
Silberpasten mit geringer Aluminium-Dotierung, beispielsweise 1 bis 3 Gew.-% Aluminium, werden in der Solarzellentechnik zur gleichzeitigen Dotierung und Kontaktierung von Wafern eingesetzt. Der Aluminium-Gehalt der verwendeten Pasten dient hier der Dotierung eines Wafers ohne back surface field und ermöglicht die elektrische Kontaktierung des Si-Wafers mit der Silberelektrode mit einem niedrigen Übergangswiderstand, siehe z.B.
Bei Solarzellen mit back surface field dient die Dotierung der Rückseite einer Solarzelle mit Aluminium ebenfalls nicht der elektrischen Kontaktierung der Solarzelle. Die Dotierung mit Aluminium wirkt der Abnahme des Wirkungsgrads einer Solarzelle bei geringer Waferstärke entgegen. Die elektrische Kontaktierung wird durch einen Silber-Gehalt in der Aluminiumpaste oder durch eine zusätzliche Silberhaltige Beschichtung erzielt, siehe z.B.
Die genannte Schrift offenbart darüber hinaus, dass der Metallisierungspaste Antimonoxid zugesetzt wird, um das Verbiegen des Wafers beim Einbrennen der flächig aufgebrachten Paste zu vermindern.The cited document moreover discloses that antimony oxide is added to the metallizing paste in order to reduce the bending of the wafer during the baking of the applied paste.
Die Aufgabe der Erfindung besteht in der Bereitstellung einer Kontaktierungs- oder Metallisierungspaste zur Verwendung in der Dickfilm-Hybridtechnologie, die preisgünstiger als übliche Silberhaltige Metallisierungspaste ist.
Die Aufgabe wird mit einem Metallisierungs-Keramik-Verbund mit den Merkmalen gemäß Anspruch 1 gelöst. Diese Metallisierungspaste für Hybridschaltungen auf Keramik-Substraten zeichnet sich dadurch aus, dass sie feinteiliges Aluminium, einen Haftvermittler sowie ein temporäres organisches Vehikel zur Anpastung umfasst. Antimonoxid, wie aus dem Stand der Technik bekannt, ist erfindungsgemäß nicht notwendig, d.h. die Metallisierungspaste enthält kein Antimonoxid.The object of the invention is to provide a contacting or metallizing paste for use in thick-film hybrid technology that is less expensive than conventional silver-containing metallizing paste.
The object is achieved with a metallization-ceramic composite having the features of claim 1. This metallization paste for hybrid circuits on ceramic substrates is characterized in that it comprises finely divided aluminum, an adhesion promoter and a temporary organic vehicle for pasting. Antimony oxide, as known from the prior art, is not necessary according to the invention, ie the metallizing paste contains no antimony oxide.
Eine feinteiliges Aluminium enthaltende Paste mit einem Glasanteil und einem temporären organischen Vehikel zur Anpastung und gleichzeitigem Schutz des Aluminiums vor Oxidation kann mit verschiedenen Verfahren wie Siebdruck, Schablonendruck, Tampondruck, Spraycoaten und anderen Beschichtungsverfahren auf Oberflächen von Keramik-Substraten wie Al2O3, AIN, ZrO2 aufgebracht werden.A finely divided aluminum-containing paste with a glass portion and a temporary organic vehicle for pasting and simultaneously protecting the aluminum from oxidation can be applied to surfaces of ceramic substrates such as Al 2 O 3 , AlN by various methods such as screen printing, stencil printing, pad printing, spray coating and other coating methods , ZrO 2 are applied.
Im nächsten Schritt wird die Paste getrocknet und dann unter Anwesenheit von Sauerstoff bei erhöhter Temperatur, vorzugsweise bei Temperaturen zwischen 600 und 1000°C, fest auf den Träger, also das Keramik-Substrat, gesintert.In the next step, the paste is dried and then sintered in the presence of oxygen at elevated temperature, preferably at temperatures between 600 and 1000 ° C, firmly on the support, so the ceramic substrate.
Die Aluminiumteilchen liegen vorzugsweise in feinteiliger, kugeliger Form vor. Sie können durch Spritzen von flüssigem Aluminium in eine inerte Atmosphäre gewonnen werden. Die kugelige Form erzeugt ein minimales Oberflächen-zu-Volumen-Verhältnis, wodurch die Oxidationsanfälligkeit des Aluminiums minimiert wird.The aluminum particles are preferably in finely divided, spherical form. They can be obtained by spraying liquid aluminum in an inert atmosphere. The spherical shape produces a minimum surface-to-volume ratio whereby the oxidation susceptibility of the aluminum is minimized.
Die Teilchengröße des feinteiligen Aluminiums sollte zwischen 0,5 und 50 µm (Größenbestimmung mit dem Laserstreuverfahren gemäß ISO 13320:2009) liegen und beträgt vorzugsweise 1 bis 10 µm, so dass die Teilchen durch gängigen Siebgewebe, wie beispielsweise VA160-18 mit 45 µm Maschenweite, passen.The particle size of the finely divided aluminum should be between 0.5 and 50 microns (size determination with the laser scattering method according to ISO 13320: 2009) and is preferably 1 to 10 .mu.m, so that the particles through common screen mesh, such as VA160-18 with 45 microns mesh size , fit.
Als Haftvermittler zwischen Keramik und Aluminium dienen 1 bis 15 Gew.-% eines Glases, beispielsweise ZnO-SiO2-B2O3. Gläser, die für die Haftvermittlung geeignet sind, müssen hinsichtlich ihrer chemischen Beschaffenheit und bezüglich des thermischen Ausdehnungskoeffizienten an das Material des Keramik-Substrats angepasst sein.1 to 15 wt .-% of a glass, for example ZnO-SiO 2 -B 2 O 3 serve as a bonding agent between ceramic and aluminum. Glasses that are suitable for adhesion promotion must be adapted to the material of the ceramic substrate in terms of their chemical nature and with respect to the thermal expansion coefficient.
Bevorzugt wird jedoch ein ZnO-SiO2-B2O3-Glas verwendet, das eine hohe Affinität sowohl zur Oberfläche der Keramik-Substrate als auch zu Al2O3 hat, das während des Einbrennens auf der Oberfläche der Aluminiumkugeln entsteht.Preferably, however, a ZnO-SiO 2 -B 2 O 3 glass is used, which has a high affinity to both the surface of the ceramic substrates and Al 2 O 3 , which is formed during baking on the surface of the aluminum balls.
Weiterhin können Moderatoren zur Anpassung von Schmelzpunkt, Glasviskosität und thermischem Ausdehnungskoeffizienten in Mengen von 0 bis 10 Gew.-% bezogen auf die Masse des Glases enthalten sein. Beispiele sind CaO, TiO2, ZrO2, Bi2O3 und/oder Li2O. Die Moderatoren können in das Glas eingeschmolzen werden oder als binäres Oxid dem Grundglas zugesetzt werden.Furthermore, moderators for adjusting the melting point, glass viscosity and thermal expansion coefficient in amounts of 0 to 10 wt .-% based on the mass of the glass may be included. Examples are CaO, TiO 2 , ZrO 2 , Bi 2 O 3 and / or Li 2 O. The moderators can be melted into the glass or added to the base glass as a binary oxide.
Das feste Pastenmaterial, also abgesehen vom organischen Pastenvehikel, wird dann mit Aluminiumpulver auf 100 Gew.-% aufgefüllt. Daraus ergeben sich somit 75 bis 99 Gew.-% Aluminiumpulver als feste Bestandteile der Metallisierungspaste.The solid paste material, apart from the organic paste vehicle, is then filled with aluminum powder to 100 wt .-%. This results in thus 75 to 99 wt .-% aluminum powder as solid constituents of the metallizing paste.
Als organische Pastenvehikel können bekannte Medien wie Ethylcellulose oder Acrylharz gelöst in hochsiedenden Lösungsmitteln wie Pine Oil, Terpineol, Butylcarbitol, Texanal (auch in Kombination) eingesetzt werden.As organic paste vehicles known media such as ethyl cellulose or acrylic resin dissolved in high boiling solvents such as pine oil, terpineol, butylcarbitol, Texanal (also in combination) can be used.
Die aufgebrachte und an Luft bei etwa 60 bis 110°C getrocknete Paste kann in Luft beispielsweise in einem Gliederbandofen oder in einem Kammerofen in einem Gesamtprozess von 30 bis150 min mit einem Temperaturpeak von 600 bis 1000°C für 1 bis 15 min eingebrannt werden.The applied paste dried in air at about 60 to 110 ° C can be baked in air, for example in a belt furnace or in a chamber furnace in a total process of 30 to 150 min with a temperature peak of 600 to 1000 ° C for 1 to 15 min.
Die Metallisierung ist elektrisch leitfähig und hat eine Haftfestigkeit von über 25 N/mm2. Für die Bestimmung der Haftfestigkeit wird die Abzugskraft eines geklebten Probekörpers, einer Sechskantmutter, senkrecht zur Metallisierungsoberfläche gemessen. Die bestimmte Haftfestigkeit liegt im üblichen Bereich von beispielsweise Silbermetallisierungen. Die Wärmeleitfähigkeit beträgt über 100 W/mK. Die Metallisierung ist eine preisgünstige Alternative zu Silbermetallisierungen.The metallization is electrically conductive and has an adhesive strength of over 25 N / mm 2 . For the determination of the adhesive strength, the peel force of a bonded specimen, a hexagon nut, is measured perpendicular to the metallization surface. The specific adhesive strength is in the usual range of, for example, silver metallizations. The thermal conductivity is over 100 W / mK. Metallization is a low-cost alternative to silver metallizations.
Die Erfindung wird im Folgenden anhand eines Beispiels konkretisiert:
94 Gew.-% Aluminiumpulver mit einer mittleren Partikelgröße d50 von etwa 4µm wird mit einem Glas-Pulver der Korngröße d50 von 2 bis 4 µm vermischt. Die Gesamtzugabemenge des Glases betrug 5 Gew.-%. Außerdem wurde 1 Gew.-% Tetradecanol als Moderator zugegeben und das Gemisch mit Terpineol mit 1 Gew.-% Ethylcellulose angepastet.The invention is explained in more detail below with reference to an example:
94% by weight of aluminum powder having a mean particle size d50 of about 4 μm is mixed with a glass powder of particle size d50 of 2 to 4 μm. The total addition amount of the glass was 5% by weight. In addition, 1 wt .-% tetradecanol was added as a moderator and the mixture with terpineol with 1 wt .-% ethylcellulose pasted.
Die Paste wurde auf ein 96%iges Aluminiumoxidsubstrat unter Verwendung eines Siebs mit einer Maschenweite von 120 aus rostfreiem Stahl durch Siebdruck aufgebracht. Die bedruckte Keramik wurde anschließend bei 80°C für 30 min. getrocknet und in einem Rollenofen bei einer Peaktemperatur von etwa 870°C für 10 Minuten gesintert. Die gesamte Sinterzeit betrug 45 min.The paste was screen printed on a 96% alumina substrate using a 120 mesh stainless steel screen. The printed ceramic was then at 80 ° C for 30 min. dried and sintered in a roller oven at a peak temperature of about 870 ° C for 10 minutes. The entire sintering time was 45 min.
Die Haftfestigkeit im Mutterntest lag bei 30 N/mm2, die elektrische Leitfähigkeit des aufgebrachten Hybrids bei 4,2 Ohm.The bond strength in the nut test was 30 N / mm2, the electrical conductivity of the applied hybrid at 4.2 ohms.
Claims (9)
- Metallization-ceramic composite for hybrid circuits, comprising a ceramic substrate and a metallization paste applied to the ceramic substrate, wherein
the metallization paste consists of aluminum powder having a particle size of from 0.5 to 50 µm, and an adhesion promoter and a temporary organic vehicle for pasting, wherein
the aluminum particles of the aluminum powder are spherical in shape;
the adhesion promoter comprises a glass;
the glass comprises ZnO-SiO2-B2O3 and optionally moderators such as CaO, TiO2, ZrO2, Bi2O3, and/or Li2O;
ethyl cellulose or acrylic resin, dissolved in a high-boiling solvent, in particular pine oil, terpineol, butyl carbitol, texanol, or combinations of these solvents, is contained as the temporary organic vehicle;
and wherein the metallization paste does not contain antimony oxide, and the metallization paste is sintered onto the ceramic substrate. - Metallization-ceramic composite according to claim 1, characterized in that the aluminum powder has a particle size of between 1 and 10 µm.
- Metallization-ceramic composite according to either of the preceding claims, characterized in that the adhesion promoter makes up 1 to 15 wt.% of the metallization paste.
- Metallization-ceramic composite according to claim 3, characterized in that moderators make up 0 to 10 wt.% based on the mass of the glass.
- Metallization-ceramic composite according to any of the preceding claims, characterized in that the aluminum powder makes up 75-99 wt.%.
- Metallization-ceramic composite according to any of the preceding claims, characterized in that the weight fractions of the aluminum powder, adhesion promoter and the moderators of the metallization paste amount to 100 wt.%.
- Metallization-ceramic composite according to any of the preceding claims, characterized in that the ceramic substrate consists of Al2O3, AlN, ZrO2 or mixed ceramics consisting of Al2O3 and ZrO2 or AlN.
- Method for producing a metallization-ceramic composite according to any of claims 1 to 7, wherein a metallization paste is applied to a ceramic substrate by screen printing, stencil printing, pad printing or spray-coating, is dried and is subsequently sintered.
- Method according to claim 8, wherein the sintering takes place at a temperature of from 600-1000°.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102014207840 | 2014-04-25 | ||
PCT/EP2015/059087 WO2015162298A1 (en) | 2014-04-25 | 2015-04-27 | Aluminium pastes for thick film hybrides |
Publications (2)
Publication Number | Publication Date |
---|---|
EP3134903A1 EP3134903A1 (en) | 2017-03-01 |
EP3134903B1 true EP3134903B1 (en) | 2019-06-12 |
Family
ID=53055018
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP15720938.8A Active EP3134903B1 (en) | 2014-04-25 | 2015-04-27 | Aluminium pastes for thick film hybrides |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP3134903B1 (en) |
DE (1) | DE102015207697A1 (en) |
WO (1) | WO2015162298A1 (en) |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19945866A1 (en) * | 1999-09-24 | 2001-03-29 | Dmc2 Degussa Metals Catalysts | Process for the production of a conductive coating on glass or enamelled steel and substrates coated thereafter |
DE10104726A1 (en) | 2001-02-02 | 2002-08-08 | Siemens Solar Gmbh | Process for structuring an oxide layer applied to a carrier material |
CN102056853A (en) * | 2008-06-26 | 2011-05-11 | E.I.内穆尔杜邦公司 | Glass compositions used in conductors for photovoltaic cells |
US8927054B2 (en) * | 2009-11-24 | 2015-01-06 | National Institute Of Advanced Industrial Science And Technology | Conductive substrate and process for producing same |
JP5569094B2 (en) * | 2010-03-28 | 2014-08-13 | セントラル硝子株式会社 | Low melting point glass composition and conductive paste material using the same |
KR101309809B1 (en) * | 2010-08-12 | 2013-09-23 | 제일모직주식회사 | Aluminium paste for solar cell and solar cell using the same |
TWI432550B (en) * | 2010-12-30 | 2014-04-01 | China Steel Corp | Lead - free conductive adhesive and its manufacturing method |
-
2015
- 2015-04-27 EP EP15720938.8A patent/EP3134903B1/en active Active
- 2015-04-27 DE DE102015207697.0A patent/DE102015207697A1/en not_active Withdrawn
- 2015-04-27 WO PCT/EP2015/059087 patent/WO2015162298A1/en active Application Filing
Non-Patent Citations (1)
Title |
---|
None * |
Also Published As
Publication number | Publication date |
---|---|
DE102015207697A1 (en) | 2015-10-29 |
WO2015162298A1 (en) | 2015-10-29 |
EP3134903A1 (en) | 2017-03-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP4916442B2 (en) | Lead-free and cadmium-free conductive copper thick film paste | |
EP2188816B1 (en) | Electrode paste for solar cell and solar cell electrode using the paste | |
US8257618B2 (en) | Conductor composition V | |
US20130248777A1 (en) | Low silver content paste composition and method of making a conductive film therefrom | |
TW201511036A (en) | Thick print copper pastes for aluminum nitride substrates | |
JPS6035405A (en) | Copper conductor composition | |
US9396832B2 (en) | Electroconductive paste for bonding metal terminal, electronic component with metal terminal, and method for manufacturing same | |
TW201004890A (en) | Resistor compositions using a Cu-containing glass frit | |
KR20140053435A (en) | Silver paste composition used in the preparation of an electrode for a solar cell | |
EP3134903B1 (en) | Aluminium pastes for thick film hybrides | |
EP3309800B1 (en) | Method for producing a layer structure using a paste based on a resistance alloy | |
CN1608298A (en) | Use of conductor compositions in electronic circuits | |
DE112012005812B4 (en) | Conductive silver paste for a rear electrode of a solar element | |
JP6569545B2 (en) | Thick film copper electrode or wiring and method for forming the same | |
KR102546912B1 (en) | Substrates for Flexible Devices | |
DE102007046907A1 (en) | Jacket wire and sheet resistance | |
US20130014816A1 (en) | Conductive paste, method for manufacturing solar cell electrodes and solar cell electrodes | |
US20220238261A1 (en) | High Adhesion Resistive Composition | |
TWI485289B (en) | Metal matrix composite material and its manufacturing method | |
KR101410447B1 (en) | Electroconductive paste and method of producing the same | |
TWI796400B (en) | Powder composition for forming thick film conductor and paste for forming thick film conductor | |
TW202035341A (en) | Electronic component and method for producing same | |
TW201637765A (en) | Aluminum solder paste for thick film hybrid circuit |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE |
|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
17P | Request for examination filed |
Effective date: 20161125 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
AX | Request for extension of the european patent |
Extension state: BA ME |
|
DAV | Request for validation of the european patent (deleted) | ||
DAX | Request for extension of the european patent (deleted) | ||
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: EXAMINATION IS IN PROGRESS |
|
17Q | First examination report despatched |
Effective date: 20180424 |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: GRANT OF PATENT IS INTENDED |
|
INTG | Intention to grant announced |
Effective date: 20190208 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE PATENT HAS BEEN GRANTED |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D Free format text: NOT ENGLISH |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: REF Ref document number: 1143633 Country of ref document: AT Kind code of ref document: T Effective date: 20190615 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D Free format text: LANGUAGE OF EP DOCUMENT: GERMAN |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 502015009321 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: MP Effective date: 20190612 |
|
REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG4D |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190612 Ref country code: HR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190612 Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190612 Ref country code: AL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190612 Ref country code: NO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190912 Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190612 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190912 Ref country code: RS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190612 Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190612 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190913 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190612 Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190612 Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190612 Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190612 Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20191014 Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190612 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190612 Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20191012 Ref country code: SM Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190612 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 502015009321 Country of ref document: DE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190612 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190612 Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190612 |
|
26N | No opposition filed |
Effective date: 20200313 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190612 Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200224 |
|
PG2D | Information on lapse in contracting state deleted |
Ref country code: IS |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190612 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200427 Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200430 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200430 |
|
REG | Reference to a national code |
Ref country code: BE Ref legal event code: MM Effective date: 20200430 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200430 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200427 |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MM01 Ref document number: 1143633 Country of ref document: AT Kind code of ref document: T Effective date: 20200427 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200427 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190612 Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190612 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190612 |
|
P01 | Opt-out of the competence of the unified patent court (upc) registered |
Effective date: 20230515 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20240419 Year of fee payment: 10 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20240418 Year of fee payment: 10 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20240424 Year of fee payment: 10 Ref country code: FR Payment date: 20240425 Year of fee payment: 10 |