WO2002004379A2 - Materiau electroconducteur fritte, element ceramique multicouche comprenant ledit materiau et procede permettant de le produire - Google Patents

Materiau electroconducteur fritte, element ceramique multicouche comprenant ledit materiau et procede permettant de le produire Download PDF

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Publication number
WO2002004379A2
WO2002004379A2 PCT/DE2001/002513 DE0102513W WO0204379A2 WO 2002004379 A2 WO2002004379 A2 WO 2002004379A2 DE 0102513 W DE0102513 W DE 0102513W WO 0204379 A2 WO0204379 A2 WO 0204379A2
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WO
WIPO (PCT)
Prior art keywords
component
ceramic
electrically conductive
starting
conductive material
Prior art date
Application number
PCT/DE2001/002513
Other languages
German (de)
English (en)
Other versions
WO2002004379A3 (fr
Inventor
Friederike Lindner
Leonore Schwegler
Alfons Kelnberger
Original Assignee
Robert Bosch Gmbh
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Robert Bosch Gmbh filed Critical Robert Bosch Gmbh
Publication of WO2002004379A2 publication Critical patent/WO2002004379A2/fr
Publication of WO2002004379A3 publication Critical patent/WO2002004379A3/fr

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C1/00—Details
    • H01C1/14—Terminals or tapping points or electrodes specially adapted for resistors; Arrangements of terminals or tapping points or electrodes on resistors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C1/00—Details
    • H01C1/14—Terminals or tapping points or electrodes specially adapted for resistors; Arrangements of terminals or tapping points or electrodes on resistors
    • H01C1/146—Terminals or tapping points or electrodes specially adapted for resistors; Arrangements of terminals or tapping points or electrodes on resistors the resistive element surrounding the terminal
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
    • H01C17/006—Apparatus or processes specially adapted for manufacturing resistors adapted for manufacturing resistor chips
    • 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
    • H01C7/10—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 voltage responsive, i.e. varistors
    • H01C7/12—Overvoltage protection resistors
    • 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
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/01—Manufacture or treatment
    • H10N30/05—Manufacture of multilayered piezoelectric or electrostrictive devices, or parts thereof, e.g. by stacking piezoelectric bodies and electrodes
    • H10N30/053—Manufacture of multilayered piezoelectric or electrostrictive devices, or parts thereof, e.g. by stacking piezoelectric bodies and electrodes by integrally sintering piezoelectric or electrostrictive bodies and electrodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/80—Constructional details
    • H10N30/87—Electrodes or interconnections, e.g. leads or terminals
    • H10N30/871—Single-layered electrodes of multilayer piezoelectric or electrostrictive devices, e.g. internal electrodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/80—Constructional details
    • H10N30/87—Electrodes or interconnections, e.g. leads or terminals
    • H10N30/877—Conductive materials

Definitions

  • the invention relates to a sintered, electrically conductive material, in particular for use as an inner electrode material in a ceramic multilayer component, a ceramic multilayer component with such a material, and a method for producing such a ceramic multilayer component according to the preamble of the independent claims.
  • Ceramic piezo actuators which consist of a multiplicity of thin, ceramic, piezoactive layers, which are each separated from one another via inner electrode layers and can be electrically contacted and controlled via them, are widely known. For this purpose, reference is made, for example, to the application DE 199 51 016.4.
  • piezo actuators often consist of a PZT ceramic, that is to say of a ceramic based on
  • the piezoactive layers experience this when an external electrical voltage is applied to the inner electrode layers the inverse piezo effect a stretching or compression.
  • typical control voltages from 100 volts to 300 volts, the change in length that occurs is in the range from 0.1% to 0.3%.
  • a material is required as the inner electrode material in a ceramic multilayer component in the form of a piezo actuator, which both debinds the ceramic green foils initially used, i.e. the burning of the organic components contained in the green foils under an oxygen or air atmosphere, as well as the subsequent sintering process withstands typical temperatures from 950 ° C to 1100 ° C. In the simplest case, this means that the inner electrode material must both be stable to oxidation and must have a melting point that is higher than the maximum sintering temperature used.
  • noble metals or noble metal alloys in particular in many cases a silver-palladium alloy with a composition of 70% by mass of silver and 30% by mass of palladium, have been used as the inner electrode material.
  • Such an Ag-Pd alloy is less expensive than platinum and has a melting point that is still sufficiently high for sintering.
  • Ag-Pd alloys have the disadvantage that there is a diffusion of silver in the course of the cofiring process of the ceramic green sheets with the PZT ceramic and the Ad / Pd inner electrode material comes into the PZT ceramic, whereby the silver is built into the Pb positions in the PZT ceramic, which leads to an impairment of the electromechanical properties of the PZT ceramic.
  • Another disadvantage is that when large amounts of silver are diffused into the PZT ceramic, silver secondary phases can form after silver saturation has been reached, which reduces the specific electrical resistance of the PZT material, which is electrically insulating as a whole, and ultimately leads to undesired ones electrical breakdowns in the ceramic insulation layers of the ceramic multilayer component can result. These undesirable effects become more apparent the higher the proportion of silver in the inner electrode material.
  • the silver-palladium alloy used is still an expensive raw material due to the relatively high palladium content, it is desirable to either drastically reduce the noble metal content in the inner electrode material used, or to replace it entirely with a less expensive material.
  • the sintered, electrically conductive material according to the invention has the advantage over the prior art that it can be used in a ceramic multilayer component, for example a piezo actuator, as the inner electrode material, it being distinguished in particular by the fact that the powdery metallic starting component contained therein can also be a base metal or a base metal alloy.
  • the organic component added before the sintering of the starting mixture ensures that it surrounds the powder particles of the metallic starting component at least largely in the form of an at least largely carbonized layer during and after the sintering, so that the powder particles are at least largely protected against oxidation.
  • the material according to the invention is in the form of a two-phase material with a metallic phase and a carbon phase at least largely surrounding this metallic phase.
  • the ceramic multilayer component provided with such a sintered, electrically conductive material in the form of inner electrode layers has the advantage that inner electrode layers made of this material are initially significantly cheaper than known inner electrode materials, and furthermore the problem that arises when using silver-palladium alloys the diffusion of silver into neighboring ceramic insulation layers does not occur.
  • well-conductive inner electrode layers are formed between the ceramic insulation layers in the ceramic multilayer component, which are comparable in terms of their electrical conductivity to known inner electrode layers.
  • the powdery metallic starting component is used in the form of a highly crystalline metal powder which is already in the starting mixture with a high-temperature stable organic protective layer from the one used organic starting component has been provided.
  • a high-temperature-stable protective layer is understood to mean a material which, in contrast to the organic constituents in the ceramic green sheets, which later form the ceramic insulation layers, is not or only slightly thermally decomposed under the process conditions prevailing during debinding.
  • the organic starting component which initially forms the organic protective layer around the highly crystalline metal powder is a material which is not or only slightly thermally decomposable up to a temperature of 350 ° C., in particular in an oxygen-containing gas atmosphere. It has turned out to be particularly advantageous if the organic starting component is a polyimide, a polybenzoxazole, a polyether, a polycarbonate or a polyketone.
  • the powdery metallic starting component in the starting mixture for the electrically conductive material is provided with a protective layer made of the organic starting component, this initially protects the metallic powder particles during the debinding at least against complete oxidation, and on the other hand pyrolyzes during the subsequent one Sintering process at low oxygen partial pressure or with complete exclusion of oxygen to carbon.
  • Green foils and an organic protective coating of the powder particles of the metallic starting component that can only be decomposed at significantly higher temperatures thus have the essential advantage that the metal powder is initially protected by the more heat-resistant organic coating during debinding.
  • the organic protective coating is achieved in the following temperature range of approx. 400 ° C to 700 ° C carbonized from the organic starting component due to a lack of oxygen around the metallic powder particles, so that an electrically conductive material is formed which can be used in the ceramic multilayer component as an electrode layer made of metal and carbon.
  • Material does not adversely affect the conductivity of the material obtained, and also shows no or only a negligible tendency to diffuse into adjacent ceramic layers, so that this inner electrode material does not cause any undesired contamination or no undesired doping of adjacent ceramic insulation layers.
  • the protective layer surrounding the metallic starting component in the form of a layer which is at least largely carbonized to carbon also has the advantage that it reduces renden character, so that in the temperature range that usually has to be run through in the sintering process, the carbon formed by coking reduces a metal oxide possibly initially formed from the metallic starting component again to metal. At the same time, this carbon only reduces lead oxide in acceptable small amounts, while titanium dioxide, barium oxide and zirconium dioxide are not reduced.
  • FIG. 1 shows a ceramic multilayer component with a multiplicity of ceramic insulation layers and inner electrode layers and FIG. 2 explains the production of this ceramic multilayer component starting from a multilayer green body during debinding and subsequent sintering.
  • the production of the sintered electrically conductive material is explained using the example of the production of a ceramic multilayer component in the form of a piezo actuator, in which this sintered electrically conductive material forms the inner electrode layers.
  • a starting mixture is first prepared in the form of a paste, which contains a powdery metallic starting component and an organic starting component.
  • the proportion of the metallic starting component in the starting mixture is 30% by weight to 70% by weight.
  • the mixture of metallic and organic starting component is further a solvent such as terpineol or an alcohol and optionally other components such as long-chain ethers or ester added, so that after a final mixing, a paste-like starting mixture is formed, in which the powder particles of the metallic starting component are at least largely provided with a surface coating made of the organic starting component.
  • the powdery metallic starting component is a highly crystalline copper powder with an average particle size of 100 nm to 10 ⁇ m.
  • a polyimide with a thermal decomposition temperature in an oxygen atmosphere of more than 350 ° C. is used as the organic starting component. In this way it is ensured that the organic starting component is not or only slightly thermally decomposed during the debinding of the multilayer green body produced later at temperatures of up to 350 ° C.
  • the surface coating of the copper powder used with the polyimide can take place both before the preparation of the paste-like starting mixture and in situ during the production of the paste.
  • the copper powder used it is also possible to use a different, preferably highly electrically conductive non-precious metal or a highly electrically conductive non-noble metal alloy whose melting point is above the temperatures that occur during the subsequent sintering.
  • non-noble metals or non-noble metal alloys whose melting point is more than 1100 ° C. are preferred.
  • a number of known, laminable ceramic green foils are also used prepared which, in addition to a binder and a solvent as ceramic component, contain a PZT ceramic of the composition Pb (Zr x Ti ⁇ _ x ) O3 with 0.4 ⁇ x ⁇ 0.6.
  • dopants such as rare earth metals, alkali metals and / or alkaline earth metals with a typical proportion of less than 8 mol% can also be added to these ceramic green films in a manner known per se.
  • the pasty starting mixture is applied to the surface of the prepared ceramic green foils at least on one side and at least in some areas.
  • the ceramic green sheets thus provided with the starting mixture are then stacked to form a multi-layer green body, which is then laminated and debindered.
  • the debinding takes place in an air atmosphere at the lowest possible temperatures of, for example, 100 ° C. to 350 ° C., in particular 100 ° C.
  • this green body is sealing-sintered to form a ceramic multi-layer component 5 according to FIG. 1, which begins at a temperature of 400 ° C. and which ends at a temperature of 1100 ° C.
  • This sealing sintering continues under low oxygen partial pressure, preferably, however, with the complete exclusion of oxygen, for example in a pure nitrogen atmosphere.
  • the organic starting component in the starting mixture which has been applied to the surface of the ceramic green foils to form inner electrode layers, at least largely cokes to carbon due to lack of oxygen, which encloses the highly crystalline copper powder particles.
  • a ceramic multilayer component 5 is formed from a regular sequence of ceramic insulating layers 11 an insighten arranged one above the other, which at least in regions consist of internal electrodes 10 made of the sintered electrically conductive material produced in the manner explained.
  • the thickness of the insulating layers 11 according to FIG. 1 is between 50 ⁇ m and 130 ⁇ m, while the inner electrode layers 10 ⁇ have a thickness of 0.5 ⁇ m to 5 ⁇ m.
  • a thickness of the inner electrode layers 10 ⁇ of approximately 1 ⁇ m to 2 ⁇ m is preferred.
  • the polyimide used as the organic starting component ensures that it converts to carbon in the temperature range from 400 ° C to 700 ° C by coking.
  • FIG. 2 once again explains the process sequence described above for producing the ceramic multilayer component 5, starting from a multilayer ceramic green body. It is shown that at a temperature of approximately 20 ° C. there is initially a multi-layer green body consisting of a sequence of stacked ceramic green foils 11 with electrode paste 10 located between them.
  • the electrode paste 10 is the paste produced with the starting mixture for the electrically conductive material. It is further shown in FIG. 2 that the electrode paste 10 contains coated powder particles 30 which consist of a metallic powder particle 20 which is provided on the surface with an organic starting component 21, polyimide in the example explained.
  • FIG. 2 further shows that the debinding of the ceramic green body initially produced is completed at approximately 400 ° C. before the actual sintering process begins, which reaches a final temperature of approximately 1100 ° C.
  • the ceramic green body produced initially shows only a slight shrinkage during debinding, but this becomes significantly larger during sintering.
  • the ceramic green sheets 10 form at least largely organic insulating layers 11 ⁇ made of PZT ceramic during sintering, which are separated from one another by the sintered electrically conductive material via the inner electrode layers 10 ⁇ .
  • the powder particles 30 initially coated at 20 ° C.
  • the inner electrode layer 10 in the actual sense often no longer contains any powder particles that can be separated exactly from one another, but is designed in the form of a compact layer that has two phases, on the one hand a metallic phase and on the other hand a carbon phase.

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  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Conductive Materials (AREA)
  • Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • General Electrical Machinery Utilizing Piezoelectricity, Electrostriction Or Magnetostriction (AREA)

Abstract

L'invention concerne un matériau électroconducteur fritté, produit à partir d'un mélange initial contenant un constituant initial métallique pulvérulent et un constituant initial organique. A cet effet, après le frittage, le constituant initial organique (21) entoure les particules pulvérulentes (20,20') du constituant initial métallique, en une couche (21') cokéfiée au moins dans une large mesure en charbon. L'invention concerne en outre un élément céramique multicouche (5), en particulier un actionneur piézo-électrique, ainsi qu'un procédé permettant de le produire. A cet effet, l'élément multicouche (5) présente une pluralité de couches isolantes (11') céramiques superposées, séparées mutuellement au moins par endroits, par des couches d'électrodes intérieures (10') en matériau électroconducteur. Il est prévu, selon le procédé de l'invention, de préparer le mélange initial, de préparer une pluralité de pellicules vertes (11) céramiques laminables, d'appliquer au moins d'un côté le mélange initial sur la surface des pellicules vertes (11) céramiques, d'empiler les pellicules vertes (11) céramiques munies du mélange initial afin de former un corps vert multicouche, de démouler le corps vert et de fritter ledit corps vert multicouche pour former l'élément multicouche céramique (5).
PCT/DE2001/002513 2000-07-11 2001-07-06 Materiau electroconducteur fritte, element ceramique multicouche comprenant ledit materiau et procede permettant de le produire WO2002004379A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10033588.8 2000-07-11
DE10033588A DE10033588C2 (de) 2000-07-11 2000-07-11 Keramisches Mehrlagenbauteil und Verfahren zu dessen Herstellung

Publications (2)

Publication Number Publication Date
WO2002004379A2 true WO2002004379A2 (fr) 2002-01-17
WO2002004379A3 WO2002004379A3 (fr) 2002-06-27

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PCT/DE2001/002513 WO2002004379A2 (fr) 2000-07-11 2001-07-06 Materiau electroconducteur fritte, element ceramique multicouche comprenant ledit materiau et procede permettant de le produire

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DE (2) DE20022469U1 (fr)
WO (1) WO2002004379A2 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1808906A2 (fr) * 2006-01-12 2007-07-18 Robert Bosch Gmbh Actionneur piézo-électrique avec protection améliorée contre les courts-circuits
JP2014154569A (ja) * 2013-02-05 2014-08-25 Murata Mfg Co Ltd 積層型圧電セラミック素子およびその製造方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102011081278A1 (de) * 2011-08-19 2013-02-21 Siemens Aktiengesellschaft Piezokeramisches Mehrschicht-Bauelement

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19951016A1 (de) 1999-10-22 2001-05-31 Bosch Gmbh Robert Piezoelektrischer Keramikkörper

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Publication number Priority date Publication date Assignee Title
US4885038A (en) * 1986-05-01 1989-12-05 International Business Machines Corporation Method of making multilayered ceramic structures having an internal distribution of copper-based conductors
JPH02224283A (ja) * 1989-02-27 1990-09-06 Mitsui Toatsu Chem Inc 積層電歪素子
JPH04324687A (ja) * 1991-04-24 1992-11-13 Onoda Cement Co Ltd 卑金属電極材料
US5302562A (en) * 1992-10-28 1994-04-12 International Business Machines Corporation Method of controlling the densification behavior of a metallic feature in a ceramic material
DE19753930A1 (de) * 1997-12-05 1999-06-10 Ceramtec Ag Verfahren zur Anbringung von Außenelektroden an Festkörperaktoren
ATE481743T1 (de) * 1999-12-16 2010-10-15 Epcos Ag Zwischenprodukt für ein piezoelektrisches bauelement

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19951016A1 (de) 1999-10-22 2001-05-31 Bosch Gmbh Robert Piezoelektrischer Keramikkörper

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1808906A2 (fr) * 2006-01-12 2007-07-18 Robert Bosch Gmbh Actionneur piézo-électrique avec protection améliorée contre les courts-circuits
EP1808906A3 (fr) * 2006-01-12 2011-01-05 Robert Bosch Gmbh Actionneur piézo-électrique avec protection améliorée contre les courts-circuits
JP2014154569A (ja) * 2013-02-05 2014-08-25 Murata Mfg Co Ltd 積層型圧電セラミック素子およびその製造方法

Also Published As

Publication number Publication date
DE20022469U1 (de) 2002-01-31
WO2002004379A3 (fr) 2002-06-27
DE10033588A1 (de) 2002-01-31
DE10033588C2 (de) 2002-05-16

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