WO2015162298A1 - Aluminium pastes for thick film hybrides - Google Patents
Aluminium pastes for thick film hybrides Download PDFInfo
- Publication number
- WO2015162298A1 WO2015162298A1 PCT/EP2015/059087 EP2015059087W WO2015162298A1 WO 2015162298 A1 WO2015162298 A1 WO 2015162298A1 EP 2015059087 W EP2015059087 W EP 2015059087W WO 2015162298 A1 WO2015162298 A1 WO 2015162298A1
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- WIPO (PCT)
- Prior art keywords
- metallization
- paste according
- aluminum
- ceramic substrate
- glass
- 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.)
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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 as
- 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 makes it possible to electrically contact the Si wafer with the silver electrode with a low contact resistance, see e.g. WO 2002/061854 A1.
- the doping of the back side serves as a substrate
- 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 e.g. EP 2 418 656 A1.
- Antimony oxide is added to reduce the bending of the wafer when baking the two-dimensionally 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.
- This metallization paste for hybrid circuits on ceramic substrates is characterized by the fact that it comprises finely divided aluminum, a primer 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 prepared by various methods such as screen printing,
- Stencil printing, pad printing, spraycoating and other coating methods can be applied to surfaces of ceramic substrates such as Al2O3, AIN, ZrO2.
- 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 area to volume ratio, thereby minimizing the oxidation susceptibility of the aluminum.
- the particle size of the finely divided aluminum should be between 0.5 and 50 ⁇ (size determination by the laser scattering method according to ISO 13320: 2009) and is preferably 1 to 10 ⁇ , so that the particles by common
- Screen mesh such as VA160-18 with 45 ⁇ mesh size fit.
- a glass for example ZnO-SiO 2 -B 2 O 3
- 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 preferably used which has a high affinity to both the surface of the ceramic substrates as well as to Al 2 O 3, which is formed on the surface of aluminum spheres during baking.
- 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, ⁇ 2, ZrO2, B12O3 and / or Li 2 O.
- the moderators can be melted into the glass or added as a binary oxide to the base glass.
- 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 may be baked in air, for example, in a belt furnace or in a chamber furnace in a total process of 30 to 150 minutes with a temperature peak of 600 to 1000 ° C for 1 to 15 minutes.
- the metallization is electrically conductive and has an adhesive strength of over
- Metallization surface measured.
- 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
- Total addition amount of the glass was 5% by weight.
- 1% by weight of tetradecanol was added as moderator and the mixture was pasted with terpineol with 1% by weight of ethylcellulose.
- 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.
- the bond strength in the nut test was 30 N / mm2, the electrical conductivity of the applied hybrid at 4.2 ohms.
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- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Conductive Materials (AREA)
Abstract
Description
Aluminiumpaste für Dickfilmhybride Aluminum paste for thick film hybrid
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 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, as
Wärmeleitpasten oder -kleber mit einer Wärmeleitfähigkeit von etwa 1 bis 5 W/mK eingesetzt werden. Wärmeleitpasten or adhesive with a thermal conductivity of about 1 to 5 W / mK are used.
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. WO 2002/061854 A1 . 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 makes it possible to electrically contact the Si wafer with the silver electrode with a low contact resistance, see e.g. WO 2002/061854 A1.
Bei Solarzellen mit back surface field dient die Dotierung der Rückseite einer In the case of solar cells with a back surface field, the doping of the back side serves as a substrate
Solarzelle mit Aluminium ebenfalls nicht der elektrischen Kontaktierung der Solar cell with aluminum also not the electrical contact of the
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. EP 2 418 656 A1 . 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 e.g. EP 2 418 656 A1.
Die genannte Schrift offenbart darüber hinaus, dass der Metallisierungspaste The cited document moreover discloses that the metallizing paste
Antimonoxid zugesetzt wird, um das Verbiegen des Wafers beim Einbrennen der flächig aufgebrachten Paste zu vermindern. Antimony oxide is added to reduce the bending of the wafer when baking the two-dimensionally 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. 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.
Die Aufgabe wird mit einer Metallisierungspaste 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 is achieved with a metallization with the features of claim 1. This metallization paste for hybrid circuits on ceramic substrates is characterized by the fact that it comprises finely divided aluminum, a primer 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, 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 prepared by various methods such as screen printing,
Schablonendruck, Tampondruck, Spraycoaten und anderen Beschichtungsverfahren auf Oberflächen von Keramik-Substraten wie AI2O3, AIN, ZrO2 aufgebracht werden. Stencil printing, pad printing, spraycoating and other coating methods can be applied to surfaces of ceramic substrates such as Al2O3, AIN, ZrO2.
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-zuVolumen-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 area to volume ratio, thereby minimizing the oxidation susceptibility of the aluminum.
Die Teilchengröße des feinteiligen Aluminiums sollte zwischen 0,5 und 50 μιτι (Größenbestimmung mit dem Laserstreuverfahren gemäß ISO 13320:2009) liegen und beträgt vorzugsweise 1 bis 10 μιτι, so dass die Teilchen durch gängigen The particle size of the finely divided aluminum should be between 0.5 and 50 μιτι (size determination by the laser scattering method according to ISO 13320: 2009) and is preferably 1 to 10 μιτι, so that the particles by common
Siebgewebe, wie beispielsweise VA160-18 mit 45 μιτι Maschenweite, passen. Screen mesh, such as VA160-18 with 45 μιτι 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. Bevorzugt wird jedoch ein ZnO-SiO2-B2O3-Glas verwendet, das eine hohe Affinität sowohl zur Oberfläche der Keramik-Substrate als auch zu AI2O3 hat, das während des Einbrennens auf der Oberfläche der Aluminiumkugeln entsteht. 1 to 15% by weight of a glass, for example ZnO-SiO 2 -B 2 O 3, serve as adhesion promoters 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. However, a ZnO-SiO 2 B 2 O 3 glass is preferably used which has a high affinity to both the surface of the ceramic substrates as well as to Al 2 O 3, which is formed on the surface of aluminum spheres during baking.
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, ΤΊΟ2, ZrO2, B12O3 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, ΤΊΟ2, ZrO2, B12O3 and / or Li 2 O. The moderators can be melted into the glass or added as a binary oxide to the base glass.
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, 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 (auch in Kombination) eingesetzt werden. Butylcarbitol, Texanal (also in combination) can be used.
Die aufgebrachte und an Luft bei etwa 60 bis 1 10°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 may be baked in air, for example, in a belt furnace or in a chamber furnace in a total process of 30 to 150 minutes with a temperature peak of 600 to 1000 ° C for 1 to 15 minutes.
Die Metallisierung ist elektrisch leitfähig und hat eine Haftfestigkeit von über The metallization is electrically conductive and has an adhesive strength of over
25 N/mm2. Für die Bestimmung der Haftfestigkeit wird die Abzugskraft eines geklebten Probekörpers, einer Sechskantmutter, senkrecht zur 25 N / mm 2 . For the determination of the adhesive strength is the withdrawal force of a bonded specimen, a hex nut, perpendicular to
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 Metallization surface measured. 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
Silbermetallisierungen. Silbermetallisierungen.
Die Erfindung wird im Folgenden anhand eines Beispiels konkretisiert: 94 Gew.-% Aluminiumpulver mit einer mittleren Partikelgröße d50 von etwa 4μηη wird mit einem Glas-Pulver der Korngröße d50 von 2 bis 4 μιτι vermischt. Die The invention is explained in more detail below with reference to an example: 94 wt .-% aluminum powder having an average particle size d50 of about 4μηη is mixed with a glass powder of particle size d50 from 2 to 4 μιτι. The
Gesamtzugabemenge des Glases betrug 5 Gew.-%. Außerdem wurde 1 Gew.-% Tetradecanol als Moderator zugegeben und das Gemisch mit Terpineol mit 1 Gew.- % Ethylcellulose angepastet. Total addition amount of the glass was 5% by weight. In addition, 1% by weight of tetradecanol was added as moderator and the mixture was pasted with terpineol with 1% by weight of ethylcellulose.
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. 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.
getrocknet und in einem Rollenofen bei einer Peaktemperatur von etwa 870°C für 10 Minuten gesintert. Die gesamte Sinterzeit betrug 45 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
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP15720938.8A EP3134903B1 (en) | 2014-04-25 | 2015-04-27 | Aluminium pastes for thick film hybrides |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102014207840 | 2014-04-25 | ||
| DE102014207840.7 | 2014-04-25 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2015162298A1 true WO2015162298A1 (en) | 2015-10-29 |
Family
ID=53055018
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2015/059087 Ceased WO2015162298A1 (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) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1087646A2 (en) * | 1999-09-24 | 2001-03-28 | dmc2 Degussa Metals Catalysts Cerdec AG | Process for producing a conductive coating on glass or enamelled steel and substrates coated thereby |
| WO2010011429A1 (en) * | 2008-06-26 | 2010-01-28 | E. I. Du Pont De Nemours And Company | Glass compositions used in conductors for photovoltaic cells |
| WO2011122369A1 (en) * | 2010-03-28 | 2011-10-06 | セントラル硝子株式会社 | Low-melting-point glass composition, and electrically conductive paste material produced using same |
| EP2418656A1 (en) * | 2010-08-12 | 2012-02-15 | Cheil Industries Inc. | Aluminium paste and solar cell using the same |
| US20120168689A1 (en) * | 2010-12-30 | 2012-07-05 | China Steel Corporation | Lead-free conductive paste composition |
| US20120222890A1 (en) * | 2009-11-24 | 2012-09-06 | National Institute of Avanced Industrial Science and Technology | Conductive substrate and process for producing same |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10104726A1 (en) | 2001-02-02 | 2002-08-08 | Siemens Solar Gmbh | Process for structuring an oxide layer applied to a carrier material |
-
2015
- 2015-04-27 WO PCT/EP2015/059087 patent/WO2015162298A1/en not_active Ceased
- 2015-04-27 DE DE102015207697.0A patent/DE102015207697A1/en not_active Withdrawn
- 2015-04-27 EP EP15720938.8A patent/EP3134903B1/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1087646A2 (en) * | 1999-09-24 | 2001-03-28 | dmc2 Degussa Metals Catalysts Cerdec AG | Process for producing a conductive coating on glass or enamelled steel and substrates coated thereby |
| WO2010011429A1 (en) * | 2008-06-26 | 2010-01-28 | E. I. Du Pont De Nemours And Company | Glass compositions used in conductors for photovoltaic cells |
| US20120222890A1 (en) * | 2009-11-24 | 2012-09-06 | National Institute of Avanced Industrial Science and Technology | Conductive substrate and process for producing same |
| WO2011122369A1 (en) * | 2010-03-28 | 2011-10-06 | セントラル硝子株式会社 | Low-melting-point glass composition, and electrically conductive paste material produced using same |
| EP2418656A1 (en) * | 2010-08-12 | 2012-02-15 | Cheil Industries Inc. | Aluminium paste and solar cell using the same |
| US20120168689A1 (en) * | 2010-12-30 | 2012-07-05 | China Steel Corporation | Lead-free conductive paste composition |
Also Published As
| Publication number | Publication date |
|---|---|
| EP3134903A1 (en) | 2017-03-01 |
| DE102015207697A1 (en) | 2015-10-29 |
| EP3134903B1 (en) | 2019-06-12 |
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