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  • 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
  • H01C17/06506—Precursor compositions therefor, e.g. pastes, inks, glass frits
  • H01C17/06513—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the resistive component
  • H01C17/06533—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the resistive component composed of oxides
  • H01C17/06546—Oxides of zinc or cadmium
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  • 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
  • H01C7/102—Varistor boundary, e.g. surface layers
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  • 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
  • H01C7/105—Varistor cores
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  • 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
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Definitions

• Varistor ceramic multilayer component comprising the varistor ceramic, manufacturing method for the varistor ceramic
• a varistor ceramic according to claim 1 is specified.
• a widespread problem of varistor ceramics is to achieve a low dielectric constant ( ⁇ r ).
• varistor ceramic according to claim 1.
• Further embodiments of the varistor ceramic are the subject matter of further claims, as well as multilayer components comprising this varistor ceramic and a production method for the varistor ceramic.
• Varistors are voltage-dependent resistors and are used as overvoltage protection.
• a metal M selected from Y, Ho, Er, Yb, Lu in an amount of 0.1 to 5 atomic%.
• M is Y or Lu.
• the proportion of Co is in a range of 0.1 to 10 atom%, wherein Co is preferably present as Co 2+ .
• the proportion of Si is in a range of 0.001 to 0.5 atom%, wherein Si is preferably present as Si 4+ .
• the proportion of Al is in a range of 0.001 to 0.1 atom%, with Al preferably being present as Al 3+ .
• the proportion of Cr is in a range of 0.001 to 5 at.%, Wherein Cr is preferably present as Cr 3+ .
• the proportion of B is in the range of 0.001 to 5 at.%, B preferably being present as B 3+ .
• C is the capacitance
• ⁇ g the permittivity of vacuum
• ⁇ r the relative permittivity
• A the area between two electrodes and d the thickness of the layer between the electrodes.
• C is the capacitance
• ⁇ g is the permittivity of vacuum
• z is the number of grain-to-grain contacts between two electrodes
• A is the area between the electrodes
• d is the junction thickness of a grain-to-grain contact.
• the varistor ceramic includes, in addition to cobalt oxide and praseodymium oxide additions of a salt or oxide of the metal M with low basicity
• an oxide or salt of the metal M whose cations have a comparatively small ionic radius (eg Y 3+ , Lu 3+ ), is dissolved in the varistor ceramic, so that it has a lower capacitance per grain-grain contact.
• FIG. 1 shows, as a schematic flow diagram, the production process of multilayer varistors comprising the process steps: Al weighing, A2 pre-milling, A3 drying, A4 screening, A5 calcination, A6 regrinding, A7 drying, A8 screening, Bl slurry formation, B2 green films, Cl printing with conductive paste, C2 stacking, C3 cutting, Dl decarburization, D2 sintering, El application of exterior finishing, E2 firing.
• FIG. 2 shows schematically the construction of a multilayer varistor comprising the inner electrodes (1), the varistor ceramic material (2) and the outer termination (3).
• the ceramic body of the multilayer varistor is present as a monolithic ceramic body.
• FIG. 3 shows on the left the characteristic of an ESD pulse and on the right the characteristic of an 8/20 pulse.
• the production of the multilayer varistor can be carried out according to FIG.
• a slurry is prepared by addition of a binder, dispersant and a solvent (Bl), are drawn from the films with a layer thickness between 5 and 60 microns
• the binder is burned in the following decarburization Sch ⁇ tt (Dl) from the green parts at temperatures between 180 0 C and 500 0 C and sintered the components at a temperature between 900 and 1400 ° C (D2). Subsequently, the outer termination layer (El) is applied and this layer is baked at temperatures between 500 0 C and 1000 0 C (E2).
• Dl decarburization Sch ⁇ tt
• the sintering temperature in process step D2) is between 1100 ° C. and 1400 ° C.
• the temperature for the burn-in method step E2) is between 600 ° C and 1000 0 C.
• FIG. 2 shows a schematic side view of a multilayer component.
• the internal electrodes (1) and the layer of the varistor ceramic material (2) follow one another alternately.
• the inner electrodes (1) are alternately connected to one or the other external termination (3). In the middle area overlap the internal electrodes (1).
• FIG. 2 shows a typical structure of a 0402 multi-layer waveguide (dimensions 1.0 mm ⁇ 0.5 mm ⁇ 0.5 mm).
• the overlap area of the internal electrodes (2) and the number of internal electrodes can be adapted to the desired electrical component properties.
• the electrical characterization of the components was carried out by determining the leakage current, the varistor voltage, the fostlinea ⁇ tatskoefflzienten, of the 8/20 Pulsstabilitat, the ESD Pulsstabilitat, the ( ⁇ U) 8/20 -Klemmenschreib at 1 A.
• FIG. 3 shows a pulse progression left and right, respectively.
• the current I is plotted against the time t.
• the specific varistor voltage E v is determined at 1 mA.
• the capacitance is measured at 1 V and 1 kHz.
• the ESD stability is determined with pulses of Figure 3 left: For this purpose, the components with +/- 10 ESD pulses (see Figure 3 right) were charged. The percentage change of U v before and after the pulses and of the leakage current before and after the pulses in percent are calculated and must not have any percentage change of more than 10%. In addition, 8/20 robustness tests (pulse shape, see FIG. 3, right) were carried out. The components were loaded with 8/20 pulses (see Figure 3, right) at IA, 5 A, 10 A, 15 A, 20 A and 25 A, as well as the percent change in the
• the electrical data are summarized in Table 2.
• the addition of yttrium increases the specific varistor voltage from 268 V / mm to 525 V / mm and at the same time decreases the relative permittivity. This change is due to the grain growth inhibiting properties of yttrium composites.
• the ratio ⁇ r / Ev was formed. Table 2 shows that this ratio decreases with increasing yttrium addition. At the same time, high ESD and 8/20 stabilities are obtained with equally good non-permeability.
• the proportion of Zn is preferably greater than or equal to about 90 atomic%, with Zn preferably being present as Zn 2+ .
• the proportion of Pr is preferably in a range of 0.5 to 0.6 atom%, wherein Pr is preferably present as Pr 3 V 4+ .
• the proportion of M is preferably in a range of 1 to 5 atomic%, wherein M is preferably as
• the proportion of Co is preferably in a range of 1.5 to 2.0 at.%, With Co preferably being present as Co 2+ .
• the proportion of Ca is preferably in a range of 0.01 to 0.03 at%, with Ca preferably present as Ca 2+ .
• the content of Si is preferably in a range of 0.01 to 0.15 atom%, Si preferably being present as Si 4+ .
• the proportion of Al is preferably in the range of 0.005 to 0.01 atom%, with Al preferably being present as Al 3+ .
• the proportion of Cr is preferably in a range of 0.05 to 0.2 atom%, with Cr preferably being present as Cr 3+ .
• the amount of B is preferably in a range of 0.001 to 0.01 at.%, B preferably being present as B 3+ .
• the relative permittivity ⁇ r is less than 1000.
• boron oxide can be released from suitable precursors while largely avoiding evaporation losses in order to control the formation of nucleation as a sintering aid in the high temperature range.
• the multilayer varistors of types 0402 and 0201 are characterized by excellent results in leakage current, ESD stability, 8/20 robustness, long-term stability and non-linearity.
• the main component is a share of at least
• the proportion of Zn is preferably more than 70 atom%, with Zn preferably being present as Zn 2+ .
• Varistor ceramic the production process comprises the process steps: a) calcination of the raw ceramic material, b) production of a slip, c) production of green films, d) debindering the green films and e) sintering the green films from d).
• this additionally comprises between process steps d) and e) the process step d1) building of a component.

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