EP0000864A1 - Process for manufacturing thick film varistors - Google Patents

Process for manufacturing thick film varistors Download PDF

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Publication number
EP0000864A1
EP0000864A1 EP78100192A EP78100192A EP0000864A1 EP 0000864 A1 EP0000864 A1 EP 0000864A1 EP 78100192 A EP78100192 A EP 78100192A EP 78100192 A EP78100192 A EP 78100192A EP 0000864 A1 EP0000864 A1 EP 0000864A1
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Prior art keywords
varistor
paste
thick
varistors
thick film
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EP78100192A
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German (de)
French (fr)
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EP0000864B1 (en
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Naresh Chakrabarty
Richard Einzinger
Artur Weitze
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Siemens AG
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Siemens AG
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01CRESISTORS
    • H01C7/00Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
    • H01C7/10Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material voltage responsive, i.e. varistors
    • H01C7/1006Thick film varistors
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01CRESISTORS
    • H01C17/00Apparatus or processes specially adapted for manufacturing resistors
    • H01C17/06Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base
    • H01C17/065Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base by thick film techniques, e.g. serigraphy
    • H01C17/06506Precursor compositions therefor, e.g. pastes, inks, glass frits
    • H01C17/06513Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the resistive component
    • H01C17/06533Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the resistive component composed of oxides
    • H01C17/06546Oxides of zinc or cadmium
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00Metal working
    • Y10T29/49Method of mechanical manufacture
    • Y10T29/49002Electrical device making
    • Y10T29/49082Resistor making

Definitions

  • the invention relates to a method for producing thick film varistors with zinc oxide as the main component, in which the varistor materials and an organic binder are applied as varistor paste to an insulating substrate and are converted into a thick film varistor by sintering the varistor paste.
  • I denotes the current flowing through the varistor, V the applied voltage, C a constant and the exponent n the so-called slope of the varistor.
  • the numerical value of the slope n should be as possible be high since this exponent indicates the degree of deviation of the varistor from an ohmic characteristic.
  • the known varistors are generally designed as discrete components, which are produced by pressing and sintering the pulverized varistor materials. From US Pat. No. 3,725,836 it is also already known to manufacture varistors in thick-film technology and to integrate them directly into thick-film circuits. To produce these known thick-film varistors, which belong to the group of ZnO varistors, the varistor materials are mixed with glass frit and an organic binder, applied as a screen-printable varistor paste to an insulating substrate and sintered to form the varistor. The electrodes required for contacting the varistor can then also be applied to the surface of the varistor using thick-film technology. The slope n of the thick-film varistors produced in this way is in the order of magnitude between 4 and 8 and is therefore too low for most applications.
  • the invention is therefore based on the object of specifying a method for producing thick-film varistors with improved values of the slope n.
  • This object is achieved in that a glass-free varistor paste is used in a method of the type mentioned.
  • glass frit is always used as an inorganic binder in conductor pastes, resistance pastes and the known varistor pastes.
  • the pastes mentioned are sintered, the glass frit forms a solid glass matrix, which ensures the cohesion of the other solids and the bond to the substrate.
  • varistor pastes with zinc oxide as the main component even without the presence of glass frit.
  • the absence of the glass frit significantly improves the electrical properties of the finished thick-film varistors, ie it is possible to easily achieve steepnesses of the varistors with a numerical value of the exponent n of over 20.
  • varistor paste which contains 87.5 to 98.0% by weight of zinc oxide, based on the solids content.
  • a varistor paste which contains bismuth oxide, tricobalt tetroxide and manganese dioxide is advantageously used.
  • the addition of these oxides to the zinc oxide favors the crystal formation in the manufacture of the thick film varistor and thus leads to a further improvement in the electrical properties.
  • a varistor paste which, based on the solids content, contains 87.5 to 98.0% by weight of zinc oxide, contains.
  • Thick film varistors produced with such a varistor paste are particularly suitable for higher operating voltages. These operating voltages are, for example, in the range of 200 volts per millimeter active varistor material.
  • a varistor paste which, based on the solids content, contains 87.5 to 96.5% by weight of zinc oxide, contains.
  • Thick film varistors produced with such a varistor paste are particularly suitable for lower operating voltages. These operating voltages are, for example, in the range of 30 V / mm active varistor material.
  • the response voltage of the thick-film varistor can also be influenced by the choice of temperature.
  • the peak temperature is preferably maintained for a period of between 5 and 20 minutes when the varistor paste is sintered.
  • a further advantage of the crystal formation and thus a further improvement of the electrical properties can be achieved in that the thick film varistor is cooled after sintering at a temperature gradient between 2 and 8 ° C / min.
  • the varistor paste is applied to the insulating substrate such that the thick film varistor by sintering, a thickness / um has between 100 and 200.
  • a thickness / um has between 100 and 200.
  • a varistor paste capable of screen printing was first produced from the varistor materials.
  • the powdery solids were weighed in as follows: After weighing the solids were wet-mixed in a ball mill for 18 hours and milled, then freed via suction filters from water and then dried for 24 hours in a drying oven at a temperature of 150 0 C. The maximum grain size distribution of the powder mixture after this treatment was 1 / um.
  • the finished varistor paste was then in the Screen printing process printed on an insulating substrate made of Al 2 0 3 ceramic at the locations provided for varistors.
  • the approximately 150 ⁇ m thick layer of the varistor paste was then dried in a drying oven at a temperature of approximately 60 ° C.
  • the varistor properties were formed.
  • the sintering was carried out in an oxidizing atmosphere at a temperature between 1100 and 1200 ° C, the peak temperature being held for 10 minutes. The temperature increase during heating in this case was about 10 ° C per minute while a temperature drop was observed of 0 7 C per minute during cooling.
  • the thick-film varistors prepared by the above-described procedure are particularly suitable for operating voltages in the range of 200 volts per millimeter of active varistor material.
  • the powdered varistor materials were first weighed out as follows:
  • the powdery varistor materials were then processed in the manner described in Example 1 to form a varistor paste capable of screen printing and printed on an insulating substrate made of Al 2 O 3 ceramic using the screen printing process.
  • the 150 / dried by a strong layer of the varistor paste at a temperature of about 60 ° C.
  • the subsequent sintering was carried out at a temperature between 1100 and 1200 ° C, the peak temperature being held for 10 minutes.
  • the temperature increase during heating was about 10 0 C per minute, while cooling to a temperature of about 1000 ° C a temperature drop of 3 ° C per minute and below 1000 ° C a temperature drop of 6 to 7 ° C per minute has been.
  • the varistor electrodes and the other elements of the thick-film circuit can be produced in a known manner.
  • the fully contacted thick-film varistors again had excellent electrical properties compared to the known glass-containing thick-film varistors.
  • the thick film prepared according to the procedure described above varistors are in particular for operating voltages in the range of 30 volts per millimeter active varistor material suitable.
  • thick-film circuits with integrated thick-film varistors can be produced.
  • thick film varistors as discrete components.
  • a large number of varistor elements are applied and sintered on an insulating substrate using the screen printing process.
  • conductor tracks for contacting the varistor elements are applied using screen printing technology, dried and sintered.
  • the substrate is then perforated in a known manner, for example with the aid of a laser, and separated into individual elements. These individual elements can then be soldered into printed circuits or layer circuits as so-called varistor chips.

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  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Thermistors And Varistors (AREA)

Abstract

Zur Herstellung von Dickfilm-Varistoren mit Zinkoxid als Hauptkomponente wird aus den Varistormaterialien und einem Bindemittel eine siebdruckfähige Varistorpaste hergestellt, die anschliessend auf ein isolierendes Substrat aufgebracht und gesintert wird. Gemäss der Erfindung wird eine glasfreie Varistorpaste verwendet, welche lediglich ein organisches Bindemittel, aber keine Glasfritte enthält.To produce thick-film varistors with zinc oxide as the main component, a varistor paste that can be screen-printed is produced from the varistor materials and a binder, which is then applied to an insulating substrate and sintered. According to the invention, a glass-free varistor paste is used, which contains only an organic binder, but no glass frit.

Description

Die Erfindung betrifft ein Verfahren zur Herstellung von Dickfilm-Varistoren mit Zinkoxid als Hauptkomponente, bei welchem die Varistormaterialien und ein organisches Bindemittel als Varistorpaste auf ein isolierendes Substrat aufgebracht und durch Sintern der Varistorpaste in einen Dickfilmvaristor überführt werden.The invention relates to a method for producing thick film varistors with zinc oxide as the main component, in which the varistor materials and an organic binder are applied as varistor paste to an insulating substrate and are converted into a thick film varistor by sintering the varistor paste.

Varistoren sind spannungsabhängige Widerstände, die bis zu einer bestimmten Spannung, der sog. Varistor-Ansprechspannung einen möglichst hohen Widerstand aufweisen sollen. Wird die Spannung über die Varistor-Ansprechspannung hinaus erhöht, so tritt ein steiler Leitfähigkeitsanstieg ein, wobei die Strom-Spannungscharakteristik durch die folgende Gleichung ausgedrückt werden kann:
I = (V/C)n
Varistors are voltage-dependent resistors that should have the highest possible resistance up to a certain voltage, the so-called varistor response voltage. If the voltage is increased above the varistor response voltage, a steep increase in conductivity occurs, and the current-voltage characteristic can be expressed by the following equation:
I = ( V / C ) n

Hierbei ist mit I der durch den Varistor fließende Strom, mit V die angelegte Spannung, mit C eine Konstante und mit dem Exponenten n die sog. Steilheit des Varistors bezeichnet. Der Zahlenwert der Steilheit n soll möglichst hoch sein, da dieser Exponent den Grad der Abweichung des Varistors von einer ohmschen Charakteristik angibt.I denotes the current flowing through the varistor, V the applied voltage, C a constant and the exponent n the so-called slope of the varistor. The numerical value of the slope n should be as possible be high since this exponent indicates the degree of deviation of the varistor from an ohmic characteristic.

Die bekannten Varistoren sind in der Regel als diskrete Bauelemente ausgebildet, welche durch Pressen und Sintern der pulverisierten Varistormaterialien hergestellt werden. Aus der US-PS 3 725 836 ist es auch bereits bekannt, Varistoren in Dickschichttechnik herzustellen und direkt in Dickschichtschaltungen zu integrieren. Zur Herstellung dieser bekannten zur Gruppe der ZnO-Varistoren gehörenden Dickfilm-Varistoren werden die Varistormaterialien mit Glasfritte und einem organischen Bindemittel vermischt, als siebdruckfähige Varistorpaste auf ein isolierendes Substrat aufgebracht und zur Bildung des Varistors gesintert. Die zur Kontaktierung des Varistors erforderlichen Elektroden können dann ebenfalls in Dickschichttechnik auf die Oberfläche des Varistors aufgebracht werden. Die Steilheit n der auf diese Weise hergestellten Dickfilm-Varistoren liegt in der Größenordnung zwischen 4 und 8 und ist somit für die meisten Anwendungsfälle zu gering.The known varistors are generally designed as discrete components, which are produced by pressing and sintering the pulverized varistor materials. From US Pat. No. 3,725,836 it is also already known to manufacture varistors in thick-film technology and to integrate them directly into thick-film circuits. To produce these known thick-film varistors, which belong to the group of ZnO varistors, the varistor materials are mixed with glass frit and an organic binder, applied as a screen-printable varistor paste to an insulating substrate and sintered to form the varistor. The electrodes required for contacting the varistor can then also be applied to the surface of the varistor using thick-film technology. The slope n of the thick-film varistors produced in this way is in the order of magnitude between 4 and 8 and is therefore too low for most applications.

Der Erfindung liegt daher die Aufgabe zugrunde, ein Verfahren zur Herstellung von Dickfilmvaristoren mit verbesserten Werten der Steilheit n anzugeben.The invention is therefore based on the object of specifying a method for producing thick-film varistors with improved values of the slope n.

Diese Aufgabe wird erfindungsgemäß dadurch gelöst, daß bei einem Verfahren der eingangs genannten Art eine glasfreie Varistorpaste verwendet wird.This object is achieved in that a glass-free varistor paste is used in a method of the type mentioned.

In der Dickschichttechnik wird bei Leiterbahnpasten, Widerstandspasten und den bekannten Varistorpasten stets Glasfritte als anorganisches Bindemittel eingesetzt. Beim Sintern der genannten Pasten bildet die Glasfritte eine feste Glasmatrix, welche den Zusammenhalt der übrigen Feststoffe und die Bindung zum Substrat gewährleistet. Gemäß der vorliegenden Erfindung wurde nun herausgefunden, daß bei Varistorpasten mit Zinkoxid als Hauptkomponente überraschenderweise auch ohne Anwesenheit von Glasfritte ein stabiler Zusammenhalt der Feststoffe und eine gute Bindung zum Substrat erzielt werden kann. Andererseits werden durch die Abwesenheit der Glasfritte die elektrischen Eigenschaften der fertigen Dickfilm-Varistoren erheblich verbessert, d. h. es können ohne weiteres Steilheiten der Varistoren mit einem Zahlenwert des Exponenten n von über 20 erzielt werden.In thick-film technology, glass frit is always used as an inorganic binder in conductor pastes, resistance pastes and the known varistor pastes. When the pastes mentioned are sintered, the glass frit forms a solid glass matrix, which ensures the cohesion of the other solids and the bond to the substrate. According to the present invention, it has now been found that, surprisingly, a stable cohesion of the solids and a good bond to the substrate can be achieved with varistor pastes with zinc oxide as the main component even without the presence of glass frit. On the other hand, the absence of the glass frit significantly improves the electrical properties of the finished thick-film varistors, ie it is possible to easily achieve steepnesses of the varistors with a numerical value of the exponent n of over 20.

Hinsichtlich der Bindung und der elektrischen Eigenschaften des Varistors ist es besonders günstig, wenn eine Varistorpaste verwendet wird, welche auf den Feststoffanteil bezogen 87,5 bis 98,0 Gew.-% Zinkoxid enthält.With regard to the binding and the electrical properties of the varistor, it is particularly advantageous if a varistor paste is used which contains 87.5 to 98.0% by weight of zinc oxide, based on the solids content.

Vorteilhaft wird eine Varistorpaste verwendet, welche Wismutoxid, Trikobalt-Tetroxid und Mangandioxid enthält. Der Zusatz dieser Oxide zum Zinkoxid begünstigt die Kristallausbildung bei der Herstellung des Dickfilm-Varistors und führt somit zu einer weiteren Verbesserung der elektrischen Eigenschaften.A varistor paste which contains bismuth oxide, tricobalt tetroxide and manganese dioxide is advantageously used. The addition of these oxides to the zinc oxide favors the crystal formation in the manufacture of the thick film varistor and thus leads to a further improvement in the electrical properties.

Bei einer ersten bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens wird eine Varistorpaste verwendet, welche auf den Feststoffanteil bezogen 87,5 bis 98,0 Gew.-% Zinkoxid,

Figure imgb0001
enthält. Mit einer derartigen Varistorpaste hergestellte Dickfilm-Varistoren sind insbesondere für höhere Betriebsspannungen geeignet. Diese Betriebsspannungen liegen beispielsweise im Bereich von 200 Volt pro Millimeter aktivem Varistormaterial.In a first preferred embodiment of the method according to the invention, a varistor paste is used which, based on the solids content, contains 87.5 to 98.0% by weight of zinc oxide,
Figure imgb0001
contains. Thick film varistors produced with such a varistor paste are particularly suitable for higher operating voltages. These operating voltages are, for example, in the range of 200 volts per millimeter active varistor material.

Bei einer zweiten bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens wird eine Varistorpaste verwendet, welche auf den Feststoffanteil bezogen 87,5 bis 96,5 Gew.-% Zinkoxid,

Figure imgb0002
enthält. Mit einer derartigen Varistorpaste hergestellte Dickfilm-Varistoren sind insbesondere für niedrigere Betriebsspannungen geeignet. Diese Betriebsspannungen liegen beispielsweise im Bereich von 30 V/mm aktivem Varistormaterial.In a second preferred embodiment of the method according to the invention, a varistor paste is used which, based on the solids content, contains 87.5 to 96.5% by weight of zinc oxide,
Figure imgb0002
contains. Thick film varistors produced with such a varistor paste are particularly suitable for lower operating voltages. These operating voltages are, for example, in the range of 30 V / mm active varistor material.

Weiterhin hat es sich als besonders günstig herausgestellt, die Varistorpaste bei einer Temperatur zwischen 1100 und 1360°C zu sintern. Durch die Wahl der Temperatur kann hierbei auch die Ansprechspannung des Dickfilm-Varistors beeinflußt werden. Vorzugsweise wird die Spitzentemperatur beim Sintern der Varistorpaste für eine Zeitdauer zwischen 5 und 20 Minuten aufrechterhalten.Furthermore, it has proven particularly favorable to sinter the varistor paste at a temperature between 1100 and 1360 ° C. The response voltage of the thick-film varistor can also be influenced by the choice of temperature. The peak temperature is preferably maintained for a period of between 5 and 20 minutes when the varistor paste is sintered.

Eine weitere Begünstigung der Kristallausbildung und somit eine weitere Verbesserung der elektrischen Eigenschaften kann dadurch erzielt werden, daß der Dickfilm- Varistor nach dem Sintern bei einem Temperaturgefälle zwischen 2 und 8°C/min abgekühlt wird.A further advantage of the crystal formation and thus a further improvement of the electrical properties can be achieved in that the thick film varistor is cooled after sintering at a temperature gradient between 2 and 8 ° C / min.

Vorzugsweise wird die Varistorpaste derart auf das isolierende Substrat aufgebracht, daß der Dickfilm-Varistor nach dem Sintern eine Stärke zwischen 100 und 200 /um aufweist. Bei derartigen Stärken der Dickfilm-Varistoren werden besonders günstige elektrische Eigenschaften erzielt.Preferably, the varistor paste is applied to the insulating substrate such that the thick film varistor by sintering, a thickness / um has between 100 and 200. Such thicknesses of the thick film varistors result in particularly favorable electrical properties achieved.

Beispiel 1example 1

Zur Herstellung eines Dickfilm-Varistors wurde zunächst aus den Varistormaterialien eine siebdruckfähige Varistorpaste hergestellt. Hierzu wurden die pulverförmigen Feststoffe wie folgt eingewogen:

Figure imgb0003
Nach der Einwaage wurden die Feststoffe in Kugelmühlen 18 Stunden lang naß gemischt und gemahlen, sodann über Filternutschen vom Wasser befreit und anschließend in einem Trockenofen bei einer Temperatur von 1500C 24 Stunden lang getrocknet. Das Maximum der Korngrößenverteilung des Pulvergemisches lag nach dieser Behandlung bei 1 /um.To produce a thick film varistor, a varistor paste capable of screen printing was first produced from the varistor materials. For this purpose, the powdery solids were weighed in as follows:
Figure imgb0003
After weighing the solids were wet-mixed in a ball mill for 18 hours and milled, then freed via suction filters from water and then dried for 24 hours in a drying oven at a temperature of 150 0 C. The maximum grain size distribution of the powder mixture after this treatment was 1 / um.

Zu einem Ansatz des derart hergestellten Pulvergemisches von 100 g wurden 75 g eines organischen Bindemittels gemischt und auf einem Walzenstuhl homogenisiert. Als organisches Bindemittel wurde hierbei eine in der Dickschichttechnik übliche Lösung von 10% Äthylzellulose in 90% Terpineol-Isomerengemisch verwendet. Andere bekannte organische Bindemittel, wie z. B. eine Lösung aus Nitrozellulose in Butylcarbitolacetat sind in gleicher Weise geeignet. Die auf diese Weise hergestellte Varistorpaste war in ihrer Viskosität und ihrem Fließverhalten so eingestellt, daß sie im Siebdruckverfahren verarbeitet werden konnte.75 g of an organic binder were mixed into a batch of 100 g of the powder mixture thus prepared and homogenized on a roller mill. A solution of 10% ethyl cellulose in 90% terpineol isomer mixture, which is customary in thick-film technology, was used as the organic binder. Other known organic binders, such as. B. a solution of nitrocellulose in butyl carbitol acetate are equally suitable. The viscosity and flow behavior of the varistor paste produced in this way was adjusted so that it could be processed using the screen printing process.

Dementsprechend wurde die fertige Varistorpaste dann im Siebdruckverfahren auf ein isolierendes Substrat aus Al203-Keramik an den für Varistoren vorgesehenen Stellen aufgedruckt. Anschließend wurde die ca. 150 /um starke Schicht der Varistorpaste in einem Trockenofen bei einer Temperatur von ca. 600C getrocknet. Beim nachfolgenden Sinterprozeß, bei welchem die Feststoffe der Varistorpaste untereinander und an das Substrat gebunden wurden, bildeten sich die Varistoreigenschaften aus. Das Sintern erfolgte in oxydierender Atmosphäre bei einer Temperatur zwischen 1100 und 1200°C, wobei die Spitzentemperatur 10 Minuten lang gehalten wurde. Der Temperaturanstieg beim Aufheizen betrug hierbei etwa 10°C pro Minute, während beim Abkühlen ein Temperaturabfall von 70C pro Minute eingehalten wurde.Accordingly, the finished varistor paste was then in the Screen printing process printed on an insulating substrate made of Al 2 0 3 ceramic at the locations provided for varistors. The approximately 150 μm thick layer of the varistor paste was then dried in a drying oven at a temperature of approximately 60 ° C. In the subsequent sintering process, in which the solids of the varistor paste were bound to one another and to the substrate, the varistor properties were formed. The sintering was carried out in an oxidizing atmosphere at a temperature between 1100 and 1200 ° C, the peak temperature being held for 10 minutes. The temperature increase during heating in this case was about 10 ° C per minute while a temperature drop was observed of 0 7 C per minute during cooling.

Da alle anderen bekannten Dickschicht-Prozesse im Temperaturbereich von ca. 500°C bis 1000°C ablaufen, ist es erforderlich, daß die Dickfilm-Varistoren vor den anderen Dickschichtelementen wie Leiterbahnen und Widerständen hergestellt werden. Dementsprechend wurden im vorliegenden Fall die Leiterbahnen bzw. Elektroden zur Kontaktierung der Dickfilm-Varistoren nach dem Sintern der Varistoren in bekannter Weise nach dem Siebdruckverfahren gedruckt, getrocknet und anschließend gesintert. Die fertig kontaktierten Dickfilmvaristoren weisen im Vergleich zu den bekannten glashaltigen Dickfilm-Varistoren hervorragende elektrische Eigenschaften auf. Bei Verwendung von in Dickschichttechnik hergestellten Elektroden auf der Basis von Gold-Platin einer Dicke der Dickfilm-Varistoren von 130 /um ergab sich beispielsweise eine Steilheit von n = 25. Die nach der vorstehend beschriebenen Verfahrensweise hergestellten Dickfilm-Varistoren sind insbesondere für Betriebsspannungen im Bereich von 200 Volt pro Millimeter aktivem Varistormaterial geeignet.Since all other known thick-film processes take place in the temperature range from approximately 500 ° C. to 1000 ° C., it is necessary for the thick-film varistors to be produced before the other thick-film elements such as conductor tracks and resistors. Accordingly, in the present case, the conductor tracks or electrodes for contacting the thick film varistors after sintering the varistors were printed in a known manner using the screen printing process, dried and then sintered. The fully contacted thick film varistors have excellent electrical properties compared to the known thick film varistors containing glass. When using produced in thick-film technology electrodes based on gold-platinum a thickness of the thick-film varistors of 130 / um, for example, resulted in a slope of n = 25. The thick-film varistors prepared by the above-described procedure are particularly suitable for operating voltages in the range of 200 volts per millimeter of active varistor material.

Beispiel 2Example 2

Zur Herstellung eines Dickfilm-Varistors wurden zunächst die pulverförmigen Varistormaterialien wie folgt eingewogen:

Figure imgb0004
To produce a thick film varistor, the powdered varistor materials were first weighed out as follows:
Figure imgb0004

Nach der Einwaage wurden dann die pulverförmigen Varistormaterialien in der in Beispiel 1 beschriebenen Weise zu einer siebdruckfähigen Varistorpaste verarbeitet und im Siebdruckverfahren auf ein isolierendes Substrat aus Al203-Keramik aufgedruckt. Anschließend wurde die ca. 150 /um starke Schicht der Varistorpaste bei einer Temperatur von ca. 60°C getrocknet. Das nachfolgende Sintern erfolgte bei einer Temperatur zwischen 1100 und 1200°C, wobei die Spitzentemperatur 10 Minuten lang gehalten wurde. Der Temperaturanstieg beim Aufheizen betrug hierbei etwa 100C pro Minute, während beim Abkühlen bis zu einer Temperatur von ca. 1000°C ein Temperaturabfall von 3°C pro Minute und unterhalb 1000°C ein Temperaturabfall von 6 bis 7°C pro Minute eingehalten wurde.After weighing in, the powdery varistor materials were then processed in the manner described in Example 1 to form a varistor paste capable of screen printing and printed on an insulating substrate made of Al 2 O 3 ceramic using the screen printing process. Subsequently, the 150 / dried by a strong layer of the varistor paste at a temperature of about 60 ° C. The subsequent sintering was carried out at a temperature between 1100 and 1200 ° C, the peak temperature being held for 10 minutes. The temperature increase during heating was about 10 0 C per minute, while cooling to a temperature of about 1000 ° C a temperature drop of 3 ° C per minute and below 1000 ° C a temperature drop of 6 to 7 ° C per minute has been.

Nach dem Abkühlen der derart auf das A1203-Substrat aufgebrachten Dickfilm-Varistoren, können die Varistor-Elektroden und die übrigen Elemente der Dickschichtschaltung in bekannter Weise hergestellt werden. Die fertig kontaktierten Dickfilm-Varistoren wiesen wieder im Vergleich zu den bekannten glashaltigen Dickfilm- Varistoren hervorragende elektrische Eigenschaften auf. Bei Verwendung von in Dickschichttechnik hergestellten Elektroden auf der Basis von Gold-Platin und einer Stärke der Dickfilm-Varistoren von 130 /um ergab sich beispielsweise eine Steilheit von n = 25. Die nach der vorstehend beschriebenen Verfahrensweise hergestellten Dickfilm- Varistoren sind insbesondere für Betriebsspannungen im Bereich von 30 Volt pro Millimeter aktivem Varistormaterial geeignet.After the thick-film varistors applied to the A1 2 0 3 substrate have cooled in this way, the varistor electrodes and the other elements of the thick-film circuit can be produced in a known manner. The fully contacted thick-film varistors again had excellent electrical properties compared to the known glass-containing thick-film varistors. When using electrodes made in thick-film technology based on gold-platinum and a starch the thick-film varistors of 130 / um, for example, resulted in a slope of n = 25. The thick film prepared according to the procedure described above varistors are in particular for operating voltages in the range of 30 volts per millimeter active varistor material suitable.

Mit Hilfe des erfindungsgemäßen Verfahrens können, wie es in den Beispielen 1 und 2 beschrieben wurde, Dickschichtschaltungen mit integrierten Dickfilm-Varistoren hergestellt werden. Es ist jedoch auch möglich Dickfilm- Varistoren als diskrete Bauelemente herzustellen. Hierzu wird beispielsweise auf ein isolierendes Substrat eine Vielzahl von Varistor-Elementen im Siebdruckverfahren aufgebracht und gesintert. Anschließend werden Leiterbahnen zur Kontaktierung der Varistor-Elemente in Siebdrucktechnik aufgebracht, getrocknet und gesintert. Daraufhin wird das Substrat beispielsweise mit Hilfe eines Lasers in bekannter Weise perforiert und in Einzelelemente aufgetrennt. Diese Einzelelemente können dann als sogenannte Varistor-Chips in gedruckte Schaltungen oder Schichtschaltungen eingelötet werden.With the aid of the method according to the invention, as described in Examples 1 and 2, thick-film circuits with integrated thick-film varistors can be produced. However, it is also possible to produce thick film varistors as discrete components. For this purpose, for example, a large number of varistor elements are applied and sintered on an insulating substrate using the screen printing process. Subsequently, conductor tracks for contacting the varistor elements are applied using screen printing technology, dried and sintered. The substrate is then perforated in a known manner, for example with the aid of a laser, and separated into individual elements. These individual elements can then be soldered into printed circuits or layer circuits as so-called varistor chips.

Claims (9)

1. Verfahren zur Herstellung von Dickfilm-Varistoren mit Zinkoxid als Hauptkomponente, bei welchem die Varistormaterialien und ein organisches Bindemittel als Varistorpaste auf ein isolierendes Substrat aufgebracht und durch Sintern der Varistorpaste in einen Dickfilm-Varistor überführt werden, dadurch gekennzeichnet , daß eine glasfreie Varistorpaste verwendet wird.1. A method for producing thick film varistors with zinc oxide as the main component, in which the varistor materials and an organic binder are applied as varistor paste to an insulating substrate and are converted into a thick film varistor by sintering the varistor paste, characterized in that a glass-free varistor paste is used becomes. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet , daß eine Varistorpaste verwendet wird, welche auf den Feststoffanteil bezogen 87,5 bis 98,0 Gew.-% Zinkoxid enthält.2. The method according to claim 1, characterized in that a varistor paste is used which contains 87.5 to 98.0 wt .-% zinc oxide based on the solids content. 3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet , daß eine Varistorpaste verwendet wird, welche Wismutoxid, Trikobalt-Tetroxid und Mangandioxid enthält.3. The method according to claim 1 or 2, characterized in that a varistor paste is used which contains bismuth oxide, tricobalt tetroxide and manganese dioxide. 4. Verfahren nach Anspruch 3, dadurch gekennzeichnet , daß eine Varistorpaste verwendet wird, welche auf den Feststoffanteil bezogen
Figure imgb0005
4. The method according to claim 3, characterized in that a varistor paste is used, which is based on the solids content
Figure imgb0005
5. Verfahren nach Anspruch 3, dadurch gekennzeichnet , daß eine Varistorpaste verwendet wird, welche auf den Feststoffanteil bezogen
Figure imgb0006
5. The method according to claim 3, characterized in that a varistor paste is used, which is based on the solids content
Figure imgb0006
6. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet , daß die Varistorpaste bei einer Temperatur zwischen 1100 und 1360°C gesintert wird.6. The method according to any one of the preceding claims, characterized in that the varistor paste is sintered at a temperature between 1100 and 1360 ° C. 7. Verfahren nach Anspruch 6, dadurch gekennzeichnet , daß die Spitzentemperatur beim Sintern der Varistorpaste für eine Zeitdauer zwischen 5 und 20 Minuten aufrechterhalten wird.7. The method according to claim 6, characterized in that the peak temperature is maintained during the sintering of the varistor paste for a period of between 5 and 20 minutes. 8. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet , daß der Dickfilm-Varistor nach dem Sintern bei einem Temperaturgefälle zwischen 2 und 8°C pro Minute abgekühlt wird.8. The method according to any one of the preceding claims, characterized in that the thick film varistor is cooled after sintering at a temperature gradient between 2 and 8 ° C per minute. 9. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet , daß die Varistorpaste derart auf das isolierende Substrat aufgebracht wird, daß der Dickfilm-Varistor nach dem Sintern eine Stärke zwischen 100 und 200 /um aufweist.9. The method according to any one of the preceding claims, characterized in that the varistor paste is applied to the insulating substrate such that the thick film varistor has a thickness between 100 and 200 / um after sintering.
EP78100192A 1977-08-05 1978-06-19 Process for manufacturing thick film varistors Expired EP0000864B1 (en)

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DE2735484A1 (en) 1979-02-15
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JPS5429096A (en) 1979-03-03
JPS5928962B2 (en) 1984-07-17
US4186367A (en) 1980-01-29
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CA1117223A (en) 1982-01-26
IT1097664B (en) 1985-08-31

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