EP1497838B1 - Procédé pour la fabrication d'un composant ptc - Google Patents

Procédé pour la fabrication d'un composant ptc Download PDF

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Publication number
EP1497838B1
EP1497838B1 EP03747078A EP03747078A EP1497838B1 EP 1497838 B1 EP1497838 B1 EP 1497838B1 EP 03747078 A EP03747078 A EP 03747078A EP 03747078 A EP03747078 A EP 03747078A EP 1497838 B1 EP1497838 B1 EP 1497838B1
Authority
EP
European Patent Office
Prior art keywords
oxygen content
sintering
ceramic
temperature
layers
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.)
Expired - Fee Related
Application number
EP03747078A
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German (de)
English (en)
Other versions
EP1497838A1 (fr
Inventor
Lutz Kirsten
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
TDK Electronics AG
Original Assignee
Epcos AG
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Filing date
Publication date
Application filed by Epcos AG filed Critical Epcos AG
Publication of EP1497838A1 publication Critical patent/EP1497838A1/fr
Application granted granted Critical
Publication of EP1497838B1 publication Critical patent/EP1497838B1/fr
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C7/00—Non-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
    • H01C7/18—Non-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 comprising a plurality of layers stacked between terminals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
    • H01C17/06—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base
    • H01C17/065—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base by thick film techniques, e.g. serigraphy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C7/00—Non-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
    • H01C7/02—Non-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 having positive temperature coefficient
    • H01C7/021—Non-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 having positive temperature coefficient formed as one or more layers or coatings

Definitions

  • the invention relates to a method for producing a PTC component.
  • PTC elements For ceramic PTC thermistors, i. Components with positive temperature coefficient of resistance, so-called PTC elements, are not commonly used temperature-stable electrodes made of precious metal suitable. These can not establish an ohmic contact between the ceramic and the metallic electrodes. Therefore, PTC elements with noble metal (inner) electrodes have an inadmissibly high resistance. However, the base metal suitable as the electrode material usually does not survive the sintering process required for the construction of multilayer devices.
  • a PTC device which is a multilayer component of stacked ceramic layers and which is sintered or post-annealed in an atmosphere with high oxygen content. Debinding and sintering of the layer stack take place in an atmosphere which has a lowered oxygen content compared to air.
  • the PTC device contains internal electrodes with tungsten. Although tungsten survives the sintering process.
  • a PTC component is to be understood as a component having a base body containing superimposed ceramic layers which are separated from one another by electrode layers, in which the ceramic layers contain a ceramic material which has a positive temperature coefficient at least in a characteristic part of the R / T characteristic.
  • the device has laterally mounted collecting electrodes, wherein the electrode layers are contacted alternately with these collecting electrodes.
  • the oxygen content during sintering where i. a. higher temperatures than used in debinding, further lowered.
  • the method according to the invention allows the production of PTC components having a volume V and an ohmic resistance R measured between the collecting electrodes at a temperature between 0 ° C and 40 ° C, where V ⁇ R ⁇ 600.
  • the ceramic starting material is finely ground and homogeneously mixed with a binder material.
  • the film is then produced by film drawing or tape casting in a desired thickness.
  • FIG. 1 shows such a green sheet 1 in perspective view.
  • an electrode paste 2 is applied to the area provided for the electrode.
  • a number of particular thick film methods preferably imprints, for example by screen printing are suitable.
  • At least in the region of an edge of the green sheet 1, such as in FIG. 1 represented, or only in the region of a corner of the green sheet remains a non-covered by electrode paste and here referred to as passive region 3 surface area. It is also possible not to apply the electrode as a flat layer, but structured, possibly as a perforated pattern.
  • the electrode paste 2 consists of metallic, metallic tungsten or a tungsten compound comprising particles for producing the desired conductivity, optionally sinterable ceramic particles to adapt the fading properties of the electrode paste to the ceramic and a burn-out organic binder to a moldability of the ceramic mass or a To ensure cohesion of the green body. It can be used pure tungsten particles, tungsten alloy particles, tungsten compound or mixed particles of tungsten and other metals.
  • the electrode layers and thus the electrode paste may also contain other tungsten compounds such as tungsten carbide, tungsten nitride or tungsten oxide (WO). The only point is that the tungsten is present in an oxidation state which is less than +6, so that it can still fulfill its function in the barrier degradation.
  • the printed green sheets 9 are stacked in a desired number so as to form a film stack that (green) ceramic layers 1 and electrode layers 2 are arranged alternately one above the other.
  • the electrode layers are also connected in alternation on different sides of the component with collecting electrodes in order to connect the individual electrodes in parallel.
  • a uniform electrode geometry is selected for this, wherein the first and second green sheets 9 differ in that they are rotated in the film stack against each other by 180 °.
  • the binder still formelastische film stack is brought by pressing and optionally cutting into the desired outer shape. Thereafter, the film stack is unbound and sintered, either separately or in one step.
  • FIG. 2 shows a finished multilayer component 8 in schematic cross-section.
  • ceramic layers 4 and electrode layers 5 are arranged one above the other alternately.
  • collecting electrodes 6, 6 ' are generated, which are each in electrical contact with each second electrode layer 5.
  • a metallization usually made of silver on the ceramic, for example by electroless deposition.
  • This can then be galvanically reinforced, for example by applying a layer sequence Ag / Ni / Sn. This improves the solderability on boards.
  • other possibilities of metallization or generation of the collecting electrodes 6, 6 ' for example sputtering, are also suitable.
  • That in the FIG. 2 illustrated component 8 has on both main surfaces of ceramic layers as final layers.
  • ceramic layers for this purpose, for example, be installed as a top layer of an unprinted green sheet 1 before sintering in the film stack, so that the stack does not end with an electrode layer 2.
  • several unprinted green sheets 1 can be installed without an electrode layer and pressed together with the remaining green film stack and sintered.
  • FIG. 3 shows a printed with an electrode pattern 2 green sheet, which allows dividing into several components, each with a smaller footprint.
  • the passive areas 3 not printed with electrode paste are arranged in such a way that that can be adjusted by alternately stacking first and second green sheets of suitable for contacting alternating displacement of the electrodes in the stack. This can be achieved if the first and second green sheets are each mutually rotated by, for example, 180 °, or if first and second green sheets generally have a staggered electrode pattern.
  • the cutting lines 7, along which the green sheet or the layer stack produced therefrom can be singulated into individual components, are identified by dashed lines. However, it is also possible electrode patterns in which the cutting guides can be placed to singulate so that no electrode layer must be severed. Each second electrode layer is then contactable from the stack edge. If appropriate, the stacks after singulation and sintering before the application of the collecting electrodes 6, 6 'are still ground to expose the electrode layers to be contacted.
  • FIG. 4 shows a layer stack thus produced in schematic cross section. It can be seen that, when the layer stack is singulated along the cutting lines 7, components are produced which individually have the desired offset of the electrodes 4.
  • the division of such a multilayer film stack comprising several component layouts into individual film stacks of the desired component base surface preferably takes place after the film stack has been pressed, for example by cutting or punching. Subsequently, the film stacks are sintered. However, it is also possible first to sinter the multilayer sheet of multilayer film stacks and then to singulate the individual components by sawing the finished sintered ceramic. Finally, collecting electrodes 6 are applied again.
  • a PTC device consists of a barium titanate ceramic of the general composition (Ba, Ca, Sr, Pb) TiO 3 doped with donors and / or acceptors, for example with manganese and yttrium.
  • the component may comprise, for example, 5 to 20 or even more ceramic layers together with the associated electrode layers, but at least two internal electrode layers.
  • the ceramic layers usually each have a thickness of 30 to 200 microns. However, they can also have larger or smaller layer thicknesses.
  • the outer dimension of a PTC device may vary, but is typically in the range of a few millimeters for SMD processable devices.
  • a suitable size is, for example, the type 2220 known from capacitors. Geometries and component tolerances result from the standard CECC 32101-801 or from other standards. However, the PTC device may be even smaller.
  • FIGS. 5 A to D show a temperature / oxygen profile for the debindering or sintering of a layer stack with variable oxygen content.
  • FIGS. 5 A to D each show an identical temperature profile, which is combined with different oxygen profiles.
  • the temperature profile is indicated by the solid curve G.
  • Range I between times 0 and 560 minutes is the range of debindering. The temperature rises evenly from 20 ° C to 500 ° C. In this time range, the oxygen content is 2% by volume.
  • Area I is followed by area II, which starts at 560 minutes and ends at 1000 minutes. In this area II, the sintering of the layer stack takes place.
  • the temperature is based on the final temperature 500 ° C of debindering further increased up to a temperature of 1200 ° C and then lowered again.
  • the oxygen content can be maintained at either 2% by volume, ie at the value of debindering (curve A in FIG. 5 A) or the oxygen content is at the end of the debinder at a lower value such as 1 vol .-% (curve B in Figure 5 A) or 0.5 vol .-% (curve C in FIG. 5 A) lowered.
  • FIG. 5C Another possibility is to lower the oxygen content in stages, in opposite directions to the rising temperature (compare curve D in FIG. 5B) , in FIG. 5C a further variant is shown, according to which, according to curve E, the oxygen content during sintering is lowered continuously to a value of 0.5% by volume.
  • Curve F shown to lower the oxygen content with increasing temperature and to let rise gradually after exceeding the maximum temperature of 1200 ° C. This has the advantage that at lower temperatures than the maximum sintering temperature again increased oxygen is available for the ceramic, which improves the properties of the ceramic. As a result, the grain boundary active layers of the PTC ceramic can be better assembled.
  • an atmosphere is used for the processes debindering or sintering, which is a mixture of nitrogen or noble gas or other inert gas with air or oxygen.
  • nitrogen and air may be mixed so as to result in an oxygen content of the atmosphere of 2% by volume.
  • the layer stacks are debinded, wherein the sintering takes place in the same atmosphere.
  • barium titanate ceramics can be used, the sintering taking place at the usual temperatures.
  • Table 1 shows component resistances of PTC components manufactured according to the method of the invention in the form 1210 with 23 electrodes as a function of the oxygen content during sintering and compared with the sintering in air.
  • Table 1 Oxygen content in Vol .-% Component resistance in ⁇ 21 (air) 40 7 25 1 9 0.5 2.5
  • Table 2 shows PTC component resistances as a function of the volume of the PTC device.

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  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Thermistors And Varistors (AREA)
  • Fixed Capacitors And Capacitor Manufacturing Machines (AREA)

Claims (10)

  1. Procédé de fabrication d'un composant PTC comprenant les stades :
    a) on produit une pile de couches en feuilles (1) céramiques crues ayant des couches (5) d'électrode entre elles,
    b) on élimine le liant et on fritte la pile de couches dans une atmosphère qui a une teneur en oxygène abaissée par rapport à l'air, caractérisé en ce que l'on continue à abaisser la teneur en oxygène après l'élimination du liant.
  2. Procédé suivant la revendication 1,
    dans lequel la teneur en oxygène de l'atmosphère est plus petite que 8 % en volume.
  3. Procédé suivant l'une des revendications 1 ou 2, dans lequel on effectue l'élimination du liant à une température inférieure à 600°C.
  4. Procédé suivant l'une des revendications 1 à 3, dans lequel on effectue le frittage dans un intervalle de température compris entre 1000°C et 1200°C.
  5. Procédé suivant l'une des revendications 1 à 4, dans lequel on maintient la température de la pile de couches, après l'élimination du liant, au moins jusqu'à ce que le frittage soit terminé, à une température qui correspond au moins à la température maximum de l'élimination du liant.
  6. Procédé suivant l'une des revendications 1 à 5, dans lequel on effectue l'élimination du liant à une teneur en oxygène comprise entre 0,5 et inférieure à 8 % en volume.
  7. Procédé suivant l'une des revendications 1 à 6, dans lequel on effectue le frittage à une teneur en oxygène comprise entre 0,1 et 5 % en volume.
  8. Procédé suivant l'une des revendications 1 à 7, dans lequel on abaisse continuellement la teneur en oxygène après l'élimination du liant.
  9. Procédé suivant l'une des revendications 1 à 7, dans lequel, après l'élimination du liant, on abaisse la teneur en oxygène en ayant une température croissante.
  10. Procédé suivant l'une des revendications 1 à 9, dans lequel, après avoir dépassé une température maximum, on augmente à nouveau la teneur en oxygène.
EP03747078A 2002-04-23 2003-04-14 Procédé pour la fabrication d'un composant ptc Expired - Fee Related EP1497838B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10218154 2002-04-23
DE10218154A DE10218154A1 (de) 2002-04-23 2002-04-23 PTC-Bauelement und Verfahren zu dessen Herstellung
PCT/DE2003/001264 WO2003092019A1 (fr) 2002-04-23 2003-04-14 Composant ptc et procedes de fabrication

Publications (2)

Publication Number Publication Date
EP1497838A1 EP1497838A1 (fr) 2005-01-19
EP1497838B1 true EP1497838B1 (fr) 2008-07-02

Family

ID=29224698

Family Applications (1)

Application Number Title Priority Date Filing Date
EP03747078A Expired - Fee Related EP1497838B1 (fr) 2002-04-23 2003-04-14 Procédé pour la fabrication d'un composant ptc

Country Status (5)

Country Link
US (1) US7633374B2 (fr)
EP (1) EP1497838B1 (fr)
JP (1) JP4302054B2 (fr)
DE (2) DE10218154A1 (fr)
WO (1) WO2003092019A1 (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10218154A1 (de) 2002-04-23 2003-11-13 Epcos Ag PTC-Bauelement und Verfahren zu dessen Herstellung
JP3831363B2 (ja) * 2003-06-24 2006-10-11 Ｔｄｋ株式会社 有機質正特性サーミスタ及びその製造方法並びにその酸素含有量の測定方法
DE102006017796A1 (de) 2006-04-18 2007-10-25 Epcos Ag Elektrisches Kaltleiter-Bauelement
TW200834612A (en) * 2007-02-05 2008-08-16 Du Pont Polymeric positive temperature coefficient thermistor and process for preparing the same
EP2223072B1 (fr) * 2007-11-09 2018-09-05 BAE Systems PLC Améliorations portant sur des procédés de fabrication d'éléments structuraux
DE102008029426A1 (de) * 2008-06-23 2010-01-07 Epcos Ag Verfahren zur Herstellung eines Vielschichtbauelements, Vielschichtbauelement und Schablone
JP5293971B2 (ja) 2009-09-30 2013-09-18 株式会社村田製作所 積層セラミック電子部品、および積層セラミック電子部品の製造方法
CN102810372A (zh) * 2012-08-10 2012-12-05 深圳顺络电子股份有限公司 负温度系数热敏电阻及其制备方法

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GB1186116A (en) * 1966-12-19 1970-04-02 Nippon Telegraph & Telephone Improvements in or relating to the Production of High Dielectric Ceramics
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DE3019098C2 (de) * 1980-05-19 1983-02-10 Siemens AG, 1000 Berlin und 8000 München Keramisches Kaltleitermaterial und Verfahren zu dessen Herstellung
JPS5760802A (en) 1980-09-30 1982-04-13 Tokyo Shibaura Electric Co Current limiting resistance element
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JPH0547508A (ja) 1991-08-08 1993-02-26 Murata Mfg Co Ltd 積層型半導体磁器及びその製造方法
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DE10018377C1 (de) * 2000-04-13 2001-12-06 Epcos Ag Keramisches Vielschichtbauelement und Verfahren zur Herstellung
JP3636075B2 (ja) * 2001-01-18 2005-04-06 株式会社村田製作所 積層ｐｔｃサーミスタ
DE10120517B4 (de) 2001-04-26 2013-06-06 Epcos Ag Elektrischer Vielschicht-Kaltleiter und Verfahren zu dessen Herstellung
EP1386334A1 (fr) * 2001-05-08 2004-02-04 Epcos Ag Composant ceramique multicouche et son procede de production
US20030198892A1 (en) 2002-04-22 2003-10-23 General Electric Company Limited play data storage media and method for limiting access to data thereon
DE10218154A1 (de) 2002-04-23 2003-11-13 Epcos Ag PTC-Bauelement und Verfahren zu dessen Herstellung

Also Published As

Publication number Publication date
EP1497838A1 (fr) 2005-01-19
DE50310068D1 (de) 2008-08-14
US20060132280A1 (en) 2006-06-22
JP4302054B2 (ja) 2009-07-22
DE10218154A1 (de) 2003-11-13
JP2005524226A (ja) 2005-08-11
US7633374B2 (en) 2009-12-15
WO2003092019A1 (fr) 2003-11-06

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