CA1215440A - Multilayer ceramic capacitor - Google Patents
Multilayer ceramic capacitorInfo
- Publication number
- CA1215440A CA1215440A CA000465757A CA465757A CA1215440A CA 1215440 A CA1215440 A CA 1215440A CA 000465757 A CA000465757 A CA 000465757A CA 465757 A CA465757 A CA 465757A CA 1215440 A CA1215440 A CA 1215440A
- Authority
- CA
- Canada
- Prior art keywords
- layers
- pressure
- acterized
- char
- multilayer capacitor
- 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
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/005—Electrodes
- H01G4/008—Selection of materials
- H01G4/0085—Fried electrodes
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/64—Burning or sintering processes
- C04B35/645—Pressure sintering
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/001—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
- C22C32/0015—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides with only single oxides as main non-metallic constituents
- C22C32/0021—Matrix based on noble metals, Cu or alloys thereof
Abstract
ABSTRACT:
Multilayer ceramic capacitor.
A multilayer ceramic capacitor characterized by a stack of alternate dielectric layers of oxidic ceramic material and electrode layers consisting of a mixture of a metal having a high electric conductivity and ceramic particles of a material having a sintering temperature which is above the sintering temperature of the oxidic ceramic material of the dielectric layers.
As a result of this electrode composition the capacitor can be manufactured by means of a uniaxial pressure sintering process in which the stack is sintered while simultaneously applying pressure in the direction transverse to the plane of the layers. This leads to die-lectric layers which are substantially free from pores and have a thickness of at most 20µm.
Multilayer ceramic capacitor.
A multilayer ceramic capacitor characterized by a stack of alternate dielectric layers of oxidic ceramic material and electrode layers consisting of a mixture of a metal having a high electric conductivity and ceramic particles of a material having a sintering temperature which is above the sintering temperature of the oxidic ceramic material of the dielectric layers.
As a result of this electrode composition the capacitor can be manufactured by means of a uniaxial pressure sintering process in which the stack is sintered while simultaneously applying pressure in the direction transverse to the plane of the layers. This leads to die-lectric layers which are substantially free from pores and have a thickness of at most 20µm.
Description
S~14C~
PIIN 10,795C 1 8~8.198 ~lultilayer ceramic capacitor.
The invention relates to a multilayer capacitor composed of alternate layers of a dielectric o~idic ceramic ma-terial and an electrode material, forming a compact unit on the basis of the application of temperature and pressure.
~ ultilayer capacitors of the above-described type (so-called monolithic ceramic capacitors) have so far generally been manu-factured on an industrial scale as follows.
A slurry of finely ground ceramic, dielectric powder mixed with a binder is deposited in thin layers which are dried to form foils and are then provided with electrodes by means of silk-screening a metal paste on them. Said foils are stacked and compressed and severed into separate capacitor bodies. Said capacitor bodies are sintered at temperatures between 1200 and 1400 dependent on the composition of -the ceramic, dielectric material. During sintering the ceramic, dielectric powder shrinks in a compact manner and its density increases to a dense polycrystalline structure. Simultaneously the powder particles of the metal paste sinter to form electrode layers of metal which form a cohering assembly with the dielectric layers~
In practice, however, it is difficult -to make a stack of perfect thin layers. Shor~ircuits at low voltages may occur (these are ascribed to too high a porosity and to the occurrence of cracks and delaminations, i.e. the non-adherence of layers in the final product, respectively).
The porosity could be restricted by causing the sintering to take place while simultaneously applying pressure (so-called pressure-sintering)0 If said pressure s(~a PEIN. 10.795C 2 is not applied on all sides (isostatically) but in a direction transverse to the plane of the layer (uni-axially), the occurrence of delaminations could also be prevented. Experiments which have led to the present invention, however, have demonstrated that when a uniaxial pressure-sintering process is used to manufacture multilayer capacitors a new problem may occur: the final products sometimes do not :satisfy the requirements imposed because the metal of the electrode layers tends to mix to.a greater or smaller extent with the oxidic ceramic material of the dielectric :layers. This is ascribed to the condition that as.a result of the high pressures which are exerted during the uniax:ial pressure-sintering process, the flow limit of the metal of the electrode layers is surpassedO The metal which in these conditions is com-paratively soft is then easily pressed into the ceramic material which:at the beginning of the sintering has not yet reached its maximum density. This pressure problem is the more serious:accordin.g.as the ceramic layers.are thinner.
The invention solves this problem in that it provides:a multilayer capa~itor of the type described in the opening paragraph which is characterized by layers of electrode material ~hich consist of.a mixture of:7 to 60% by.volume of metal ha~ing:a high electric conducti-vity and of 40 to 93% by.volume of ceramic particles of .a material having:a sintering temperature which is above the sintering temperature of the oxidic ceramic material of the dielectric layers. More in particular the elec-trode material is:a mixture of:an inert oxide:and anoble metal.
The.addition of:a given quantity of ceramic par-ticles, which do not take part in the sintering process, to the metal of the ele~trode layers causes a space to remain for the metal between the dielectric ceramic layers s, ~
1,~15~
P~IN 10.795 C 3 ~,8.19~4 during the uniaxial pressure-sintering process. The ceramic particl0s which remain in the electrode layers in unchanged condition~ function~ as it were~ as pillars which ensure that the metal cannot be pressed into the ceramic layers. The "pillars" have a relieving effect as a result of which the pressure is not directly on the metal. In order that said function be carried out effectively, the share of ceramic particles in the electrode layer should preferably ~t be less than 400/V by volume. With a share of more than 90% by volume of ceramic particles the conduc-tivity of the electrode layers may become too small for certain applications. Dependent inter alia on the size of the particles a r0asonable conductivity is s-till rea-lized with a share of 7% by volume of metal in the elec-trode layer.
Representative materials for the metal of theelectrode layers are, for example, Pd (melting point 1552C), Pt (melting point 1774 C), Ni (melting point 1445 ), Ag (melting point 961C), Cu (melting point 1083C) and alloys thereof Suitable materials for the ceramic particles in the electrode layers are, for example, ZrO2 and Al203.
Barium titanate may also be used if it has a sintering reactivity which differs from the sintering reactivity of the barium titanate of the dielectric such that it sinters badly with it. Representative oxidic ceramic materials for the dielectric are titanates zirkonates, titanate-zirkonates and tungstenates. Most of them are ferro-electric at room temperature. An exception is Sr tltanate which is not ferro-electric at room temperature. This and other non ferro-electric materials may also be used as a dielectric in capacitors according to the invention.
In order to realize multilayer capacitors which satisfy certain high quality requiremen-ts, barium titanate is preferably used for the dielectric layers. For various purposes small but specific quantities of Co 9 Ni, Mn, Mg, Ta, Bi and/or Nb may be added to this. In order that the 1 5 ~ 4 ~
PIIN 10.795C L~ o.8.1984 barium titanate obtains the desired dielectric properties, it should be fired in an oxidizing atmosphere ( high partial oxygen pressure)~ In manufacturing multi-layer capacitors by means of a conventional sintering process, Pd has so far usually been used as an electrode material.
The invention enables the use of a uniaxial pressure-sintering process as a result of which the peak temperature may be approximately 200 C lower than in the conventional sintering process. This means that the electrode material .nay consist of an Ag-Pd alloy instead of pure Pd. The lower the pressure-sintering temperature, the higher nay be the Ag content (and the lower the price of the Ag-Pd alloy), Experiments have demonstrated that, if the Ag content increases, in particular above 30 At,%
without the addition of particles of cer~mic material not taking part in the sintering process, which the invention prescribes, the possibility that the electrode layers are pressed into the ceramic material becomes larger and larger. According to a particular embodiment of the invention, the electrode metal may even consist entirely or substantially entirely of Ag.
Within the scope of the conventional sin-tering process of multilayer capacitors it has already been suggested to add ceramic particles to the material of the electrode layers. However, this served quite a different purpose from that endeavoured by the invention, namely the compensation of -the difference in coefficients of expansion between electrode material and ceramic or the better sintering together of electrode material and ceramic. In both cases the ceramic material to be added to the electrode metal essentially had the same composition as the ceramic material of the dielectric layers. Since in the conventional sintering process no pressure is exerted on the multilayer structures, the problem for which the invention p~ides a solution does not occur thereO
The invention will be described in greater detail with reference to an embodiment.
~15~0 PIIN 10.795C g 8.8.1984 Fig, 1 shows R pressure-sintering system;
Fig. 2 is an elevation partly in cross-section of a multilayer ceramic capacitor;
Fig. 3 shows the phase diagram of Ag-Pd.
S For the manufacture of multilayer ceramic capa~
citors according to the invention, a pressure-sinteri~g system may be used as is shown in fig, 1. In principle this is a pressure system consisting of a hydraulic press (1) having a cylinder (2) with a water-cooled head. The pressures which are exerted depend upon the peak tempera-ture which is applied during the pressure-sintering process.
The interesting pressure range is between 200 bar and 5 kbar.
The pressure can be read on a manometer (3) o The pressure is transferred via a (top) die (4) of refractory (= capable of withstanding high temperatures) material, for example Al203 of SiC.
A packet (5) to be compressed is placed on a lower die (6) also of a refractory material. It is ensured that the die surfaces which put the pressure on the packet are parallel as accurately as possible. The dies (4, 6) are accommodated in a tube furnace (7) having a heating coil ~8). The hydraulic system (1, 2) provides the possibility of controlling the pressure build-up, while the closed envelope provides the possibility of operating under different gas conditions.
For making the dielectric ceramic foils~ for example, a low-doped barium-titanate is used, preferably having such a particle size that after hot-pressing the grain size is smaller than 1/um.
By means of a barium titanate powder which comprises 1.2% by weight of Nb205 and o~30/o by weight of Co304, a dielectric constant ~ r of 3, can be realized and a capacitor can be obtained having a tempera-ture coefficient of the capacitance TC - CT C25 100/
which is smaller than 15% in the temperature range from -55 C to 125 C. Herewith it satisfies the so called X7R
5 ~
PMN 10.795 C 6 ~.8.198L~
specifica-tion. (For comparison may serve that in order to satisfy the Z5U specification the temperature coefficient of the capacitance must be between ~22% and -560/o in the temperature range from ~10C to 85 c) . The powder is mixed with an organic binder (for example polyvinyl alcohol)0 Of the moulding mass thus obtained, ~eets are drawn in a thickness of a few tens of microns, in particular 20-5~ microns. After drying, foils are cut herefrom to the correct si~e. Patterns of electrode material consisting of a mixture of oxidic ceramic powder and metallic powder in a binder, are provided on the foils by means o~ silk-screening. The respective sheets are stacked so that a packet (5) is formed in which in each ultimate capacitor body the electrode patterns (9, 10) alternately extend to one side and to the opposite side so that every two successive electrode patterns overlap each other partly (fig. 2). In order to obtain a good bonding of the layers mutually the packet (5) is first laminated by subjecting it to a pressure of approximately 3 kbar at a temperature of approximately 75C. The binder is then fired from the *oils. This may be done in a separate furnace. When a uniaxial pressure-sin~ring process is used, however, firing .nay be carried out very practically by perforMing it in the pressure~sintering apparatus during the heating of the complete packets to the peak temperature.
The packet 5 to be subjected to a pressure-sintering process is placed between the dies 4 and 6 of the pressure system 1 with between the dies and the ~Ipper and lower sides7 respectively9 of the packet, an anti-adhesive layer which may comprise, for example, ZrO2.
~ eating the fur]lace 7 with the packet 5 placed therein to the pressure~sintering temperature takes place in approximately 90 minutes. Dependent on the composition of the oxidic ceramic dielectric material the pressure-sintering temperature may be between approximately 900 and 1200 C. The pressure-sintering temperatures are PHN 10,795 C 7 8.8.1984 approximately 200C lower than -the sintering temperatures in the conventional sintering process. When the pressure-sintering temperature is reachecl~ the pressure is applied.
Dependent on the pressure-sintering temperature this is between 200 bar and 5 kbar. In the present experiments the pressure-sintering temperature was approximately 1080C and the pressure was approximately 500 bar. Dependent on the adjusted temperature and pressure, a sintering time up to appro.cimately 120 minutes may be necessary. The pressure is then removed and the assembly is cooled to room tempera-ture.
The compact packet obtained after hot pressing and cooling to room temperature is sawn into pieces so as to obtain separate monolithic ceramic capacitor chips.
Of each such body, the sides (11, 12) into which the electrodes open are metaLized so as to ~orm head contacts (fig. 2). The resulting capacitors showed the following properties.
Dimension N n d ~ tanc R V
( ) ( F) (10~4) 50 (V) Herein~ N : number of dielectric layers d : thickness dielectric layer~
n : number of samples C : capacitance tan ~ : dissipation factor (tangent of t~e loss angle) Riso: insulation resistance V0 : breakdown voltage.
It appears from these results that a very high capacitance per volume unit can be realized~ When dielectric la~ers are realized which are thinner than 17/um the/uF
region is even achieved.
i~l5~'~g;t PHN 10.795 C 8 8.8.19g4 Fig. 3 shows the phase diagram of the Ag-Pd system, Dependent on the Ag content the melting-point of Ag-Pd is between 961C and 1552CI The inven-tion enables the use of Ag-Pd with a considerable Ag content as an electrode metal.
It has been found that the electrode metal may even consist entirely of Ag, and hence may be free from Pd. In a successfully realized multilayer ceramic capacitor of the above- men~oned type, the electrode material contained 50% by weight of Ag and 50/0 by weigh-t of ZrO2.
The pressure-sintering temperature was 1115C, the pressure approximately 500 bar and the pressure sintering time was 5 minutes. The surprising phenomenon was that in this method the pressure sintering temperature used (1115C) is considerably above the melting-point of the Ag used as the electrode metal (961C). It might be expected that in these circumstances the electrode metal is pressedinto the ceramic material of the dielectric layers~ but this proves to be not the case. I-t would be more obvious to apply pressure sintering temperatures which remain below the melting-point of the electrode metal, so in the case of Ag below 9~1 C~ However, at the pressures used in the present method, the density of the ceramic material remains unsatisfactory.
Summarizing it may be said that the invention enables the manufacture of multilayer ceramic capacitors having dielectric layers in a -thickness of at most 20/um which are substantially free from pores (density > 99%) .
PIIN 10,795C 1 8~8.198 ~lultilayer ceramic capacitor.
The invention relates to a multilayer capacitor composed of alternate layers of a dielectric o~idic ceramic ma-terial and an electrode material, forming a compact unit on the basis of the application of temperature and pressure.
~ ultilayer capacitors of the above-described type (so-called monolithic ceramic capacitors) have so far generally been manu-factured on an industrial scale as follows.
A slurry of finely ground ceramic, dielectric powder mixed with a binder is deposited in thin layers which are dried to form foils and are then provided with electrodes by means of silk-screening a metal paste on them. Said foils are stacked and compressed and severed into separate capacitor bodies. Said capacitor bodies are sintered at temperatures between 1200 and 1400 dependent on the composition of -the ceramic, dielectric material. During sintering the ceramic, dielectric powder shrinks in a compact manner and its density increases to a dense polycrystalline structure. Simultaneously the powder particles of the metal paste sinter to form electrode layers of metal which form a cohering assembly with the dielectric layers~
In practice, however, it is difficult -to make a stack of perfect thin layers. Shor~ircuits at low voltages may occur (these are ascribed to too high a porosity and to the occurrence of cracks and delaminations, i.e. the non-adherence of layers in the final product, respectively).
The porosity could be restricted by causing the sintering to take place while simultaneously applying pressure (so-called pressure-sintering)0 If said pressure s(~a PEIN. 10.795C 2 is not applied on all sides (isostatically) but in a direction transverse to the plane of the layer (uni-axially), the occurrence of delaminations could also be prevented. Experiments which have led to the present invention, however, have demonstrated that when a uniaxial pressure-sintering process is used to manufacture multilayer capacitors a new problem may occur: the final products sometimes do not :satisfy the requirements imposed because the metal of the electrode layers tends to mix to.a greater or smaller extent with the oxidic ceramic material of the dielectric :layers. This is ascribed to the condition that as.a result of the high pressures which are exerted during the uniax:ial pressure-sintering process, the flow limit of the metal of the electrode layers is surpassedO The metal which in these conditions is com-paratively soft is then easily pressed into the ceramic material which:at the beginning of the sintering has not yet reached its maximum density. This pressure problem is the more serious:accordin.g.as the ceramic layers.are thinner.
The invention solves this problem in that it provides:a multilayer capa~itor of the type described in the opening paragraph which is characterized by layers of electrode material ~hich consist of.a mixture of:7 to 60% by.volume of metal ha~ing:a high electric conducti-vity and of 40 to 93% by.volume of ceramic particles of .a material having:a sintering temperature which is above the sintering temperature of the oxidic ceramic material of the dielectric layers. More in particular the elec-trode material is:a mixture of:an inert oxide:and anoble metal.
The.addition of:a given quantity of ceramic par-ticles, which do not take part in the sintering process, to the metal of the ele~trode layers causes a space to remain for the metal between the dielectric ceramic layers s, ~
1,~15~
P~IN 10.795 C 3 ~,8.19~4 during the uniaxial pressure-sintering process. The ceramic particl0s which remain in the electrode layers in unchanged condition~ function~ as it were~ as pillars which ensure that the metal cannot be pressed into the ceramic layers. The "pillars" have a relieving effect as a result of which the pressure is not directly on the metal. In order that said function be carried out effectively, the share of ceramic particles in the electrode layer should preferably ~t be less than 400/V by volume. With a share of more than 90% by volume of ceramic particles the conduc-tivity of the electrode layers may become too small for certain applications. Dependent inter alia on the size of the particles a r0asonable conductivity is s-till rea-lized with a share of 7% by volume of metal in the elec-trode layer.
Representative materials for the metal of theelectrode layers are, for example, Pd (melting point 1552C), Pt (melting point 1774 C), Ni (melting point 1445 ), Ag (melting point 961C), Cu (melting point 1083C) and alloys thereof Suitable materials for the ceramic particles in the electrode layers are, for example, ZrO2 and Al203.
Barium titanate may also be used if it has a sintering reactivity which differs from the sintering reactivity of the barium titanate of the dielectric such that it sinters badly with it. Representative oxidic ceramic materials for the dielectric are titanates zirkonates, titanate-zirkonates and tungstenates. Most of them are ferro-electric at room temperature. An exception is Sr tltanate which is not ferro-electric at room temperature. This and other non ferro-electric materials may also be used as a dielectric in capacitors according to the invention.
In order to realize multilayer capacitors which satisfy certain high quality requiremen-ts, barium titanate is preferably used for the dielectric layers. For various purposes small but specific quantities of Co 9 Ni, Mn, Mg, Ta, Bi and/or Nb may be added to this. In order that the 1 5 ~ 4 ~
PIIN 10.795C L~ o.8.1984 barium titanate obtains the desired dielectric properties, it should be fired in an oxidizing atmosphere ( high partial oxygen pressure)~ In manufacturing multi-layer capacitors by means of a conventional sintering process, Pd has so far usually been used as an electrode material.
The invention enables the use of a uniaxial pressure-sintering process as a result of which the peak temperature may be approximately 200 C lower than in the conventional sintering process. This means that the electrode material .nay consist of an Ag-Pd alloy instead of pure Pd. The lower the pressure-sintering temperature, the higher nay be the Ag content (and the lower the price of the Ag-Pd alloy), Experiments have demonstrated that, if the Ag content increases, in particular above 30 At,%
without the addition of particles of cer~mic material not taking part in the sintering process, which the invention prescribes, the possibility that the electrode layers are pressed into the ceramic material becomes larger and larger. According to a particular embodiment of the invention, the electrode metal may even consist entirely or substantially entirely of Ag.
Within the scope of the conventional sin-tering process of multilayer capacitors it has already been suggested to add ceramic particles to the material of the electrode layers. However, this served quite a different purpose from that endeavoured by the invention, namely the compensation of -the difference in coefficients of expansion between electrode material and ceramic or the better sintering together of electrode material and ceramic. In both cases the ceramic material to be added to the electrode metal essentially had the same composition as the ceramic material of the dielectric layers. Since in the conventional sintering process no pressure is exerted on the multilayer structures, the problem for which the invention p~ides a solution does not occur thereO
The invention will be described in greater detail with reference to an embodiment.
~15~0 PIIN 10.795C g 8.8.1984 Fig, 1 shows R pressure-sintering system;
Fig. 2 is an elevation partly in cross-section of a multilayer ceramic capacitor;
Fig. 3 shows the phase diagram of Ag-Pd.
S For the manufacture of multilayer ceramic capa~
citors according to the invention, a pressure-sinteri~g system may be used as is shown in fig, 1. In principle this is a pressure system consisting of a hydraulic press (1) having a cylinder (2) with a water-cooled head. The pressures which are exerted depend upon the peak tempera-ture which is applied during the pressure-sintering process.
The interesting pressure range is between 200 bar and 5 kbar.
The pressure can be read on a manometer (3) o The pressure is transferred via a (top) die (4) of refractory (= capable of withstanding high temperatures) material, for example Al203 of SiC.
A packet (5) to be compressed is placed on a lower die (6) also of a refractory material. It is ensured that the die surfaces which put the pressure on the packet are parallel as accurately as possible. The dies (4, 6) are accommodated in a tube furnace (7) having a heating coil ~8). The hydraulic system (1, 2) provides the possibility of controlling the pressure build-up, while the closed envelope provides the possibility of operating under different gas conditions.
For making the dielectric ceramic foils~ for example, a low-doped barium-titanate is used, preferably having such a particle size that after hot-pressing the grain size is smaller than 1/um.
By means of a barium titanate powder which comprises 1.2% by weight of Nb205 and o~30/o by weight of Co304, a dielectric constant ~ r of 3, can be realized and a capacitor can be obtained having a tempera-ture coefficient of the capacitance TC - CT C25 100/
which is smaller than 15% in the temperature range from -55 C to 125 C. Herewith it satisfies the so called X7R
5 ~
PMN 10.795 C 6 ~.8.198L~
specifica-tion. (For comparison may serve that in order to satisfy the Z5U specification the temperature coefficient of the capacitance must be between ~22% and -560/o in the temperature range from ~10C to 85 c) . The powder is mixed with an organic binder (for example polyvinyl alcohol)0 Of the moulding mass thus obtained, ~eets are drawn in a thickness of a few tens of microns, in particular 20-5~ microns. After drying, foils are cut herefrom to the correct si~e. Patterns of electrode material consisting of a mixture of oxidic ceramic powder and metallic powder in a binder, are provided on the foils by means o~ silk-screening. The respective sheets are stacked so that a packet (5) is formed in which in each ultimate capacitor body the electrode patterns (9, 10) alternately extend to one side and to the opposite side so that every two successive electrode patterns overlap each other partly (fig. 2). In order to obtain a good bonding of the layers mutually the packet (5) is first laminated by subjecting it to a pressure of approximately 3 kbar at a temperature of approximately 75C. The binder is then fired from the *oils. This may be done in a separate furnace. When a uniaxial pressure-sin~ring process is used, however, firing .nay be carried out very practically by perforMing it in the pressure~sintering apparatus during the heating of the complete packets to the peak temperature.
The packet 5 to be subjected to a pressure-sintering process is placed between the dies 4 and 6 of the pressure system 1 with between the dies and the ~Ipper and lower sides7 respectively9 of the packet, an anti-adhesive layer which may comprise, for example, ZrO2.
~ eating the fur]lace 7 with the packet 5 placed therein to the pressure~sintering temperature takes place in approximately 90 minutes. Dependent on the composition of the oxidic ceramic dielectric material the pressure-sintering temperature may be between approximately 900 and 1200 C. The pressure-sintering temperatures are PHN 10,795 C 7 8.8.1984 approximately 200C lower than -the sintering temperatures in the conventional sintering process. When the pressure-sintering temperature is reachecl~ the pressure is applied.
Dependent on the pressure-sintering temperature this is between 200 bar and 5 kbar. In the present experiments the pressure-sintering temperature was approximately 1080C and the pressure was approximately 500 bar. Dependent on the adjusted temperature and pressure, a sintering time up to appro.cimately 120 minutes may be necessary. The pressure is then removed and the assembly is cooled to room tempera-ture.
The compact packet obtained after hot pressing and cooling to room temperature is sawn into pieces so as to obtain separate monolithic ceramic capacitor chips.
Of each such body, the sides (11, 12) into which the electrodes open are metaLized so as to ~orm head contacts (fig. 2). The resulting capacitors showed the following properties.
Dimension N n d ~ tanc R V
( ) ( F) (10~4) 50 (V) Herein~ N : number of dielectric layers d : thickness dielectric layer~
n : number of samples C : capacitance tan ~ : dissipation factor (tangent of t~e loss angle) Riso: insulation resistance V0 : breakdown voltage.
It appears from these results that a very high capacitance per volume unit can be realized~ When dielectric la~ers are realized which are thinner than 17/um the/uF
region is even achieved.
i~l5~'~g;t PHN 10.795 C 8 8.8.19g4 Fig. 3 shows the phase diagram of the Ag-Pd system, Dependent on the Ag content the melting-point of Ag-Pd is between 961C and 1552CI The inven-tion enables the use of Ag-Pd with a considerable Ag content as an electrode metal.
It has been found that the electrode metal may even consist entirely of Ag, and hence may be free from Pd. In a successfully realized multilayer ceramic capacitor of the above- men~oned type, the electrode material contained 50% by weight of Ag and 50/0 by weigh-t of ZrO2.
The pressure-sintering temperature was 1115C, the pressure approximately 500 bar and the pressure sintering time was 5 minutes. The surprising phenomenon was that in this method the pressure sintering temperature used (1115C) is considerably above the melting-point of the Ag used as the electrode metal (961C). It might be expected that in these circumstances the electrode metal is pressedinto the ceramic material of the dielectric layers~ but this proves to be not the case. I-t would be more obvious to apply pressure sintering temperatures which remain below the melting-point of the electrode metal, so in the case of Ag below 9~1 C~ However, at the pressures used in the present method, the density of the ceramic material remains unsatisfactory.
Summarizing it may be said that the invention enables the manufacture of multilayer ceramic capacitors having dielectric layers in a -thickness of at most 20/um which are substantially free from pores (density > 99%) .
Claims (9)
1. A multilayer capacitor composed of alternate layers of a dielectric oxidic ceramic material and an electrode material, forming a compact unit on the basis of the applica-tion of temperature and pressure, characterized in that the capacitor forms a unit on the basis of a thermal treatment by simultaneously applying pressure in a direction transverse to the plane of the layers, and has layers of electrode material consisting of a mixture of 7 to 60% by volume of metal having a high conductivity and of 40 to 93% by volume of particles of a ceramic material having a sintering temperature which is above the sintering temperature of the oxidic ceramic material of the dielectric layers.
2. A multilayer capacitor as claimed in Claim 1, char-acterized in that the electrode material comprises an inert oxide as a ceramic material.
3. A multilayer capacitor as claimed in Claim 2, char-acterized in that the ceramic material of the electrode layers is ZrO2.
4. A multilayer capacitor as claimed in Claim 1, char-acterized in that the electrode material comprises a noble metal as the metal.
5. A multilayer capacitor as claimed in Claim 4, char-acterized in that the noble metal is an Ag-Pd alloy.
6. A multilayer capacitor as claimed in Claim 5, char-acterized in that the Ag-Pd alloy comprises at least 30 at of Ag.
7. A multilayer capacitor as claimed in Claim 4, char-acterized in that the noble metal is Ag.
8. A multilayer capacitor as claimed in Claim 1, char-acterized in that the oxidic ceramic material of the dielec-tric layers is barium titanate.
9. A multilayer capacitor as claimed in Claim 1, char-acterized in that the layers of dielectric oxidic ceramic material have a thickness of at most 20 µm and a density of at least 99%.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL8401865A NL8401865A (en) | 1984-06-13 | 1984-06-13 | Multilayer ceramic capacitor - made by uniaxial pressure sintering of alternate layers of ceramic and ceramic-metal mixt. |
| NL8401865 | 1984-06-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1215440A true CA1215440A (en) | 1986-12-16 |
Family
ID=19844071
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000465757A Expired CA1215440A (en) | 1984-06-13 | 1984-10-18 | Multilayer ceramic capacitor |
Country Status (2)
| Country | Link |
|---|---|
| CA (1) | CA1215440A (en) |
| NL (1) | NL8401865A (en) |
-
1984
- 1984-06-13 NL NL8401865A patent/NL8401865A/en not_active Application Discontinuation
- 1984-10-18 CA CA000465757A patent/CA1215440A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| NL8401865A (en) | 1986-01-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0137565B1 (en) | Multilayer ceramic capacitor | |
| US4082906A (en) | Low temperature fired ceramic capacitors | |
| US4612689A (en) | Method of manufacturing multilayer capacitors | |
| US4158219A (en) | Heterophasic ceramic capacitor | |
| EP0630032B1 (en) | Non-reducible dielectric ceramic composition | |
| KR20190118957A (en) | Multilayer ceramic capacitor and manufacturing method of the same | |
| EP0716054A2 (en) | Firing and sintering process for a ceramic, electronic component | |
| EP0337373A2 (en) | Multi-layered dielectric element | |
| US4503482A (en) | Ceramic dielectric basis on bismuth-containing BaTiO3 | |
| WO1991009814A1 (en) | Ceramic composition and electronic component made therefrom | |
| EP0368619B1 (en) | Dielectric ceramic composition | |
| CA1311536C (en) | Monolithic compound-ceramic capacitor | |
| US4218723A (en) | Heterophasic ceramic composition | |
| US4870538A (en) | High energy density capacitor and method of fabrication | |
| CA1215440A (en) | Multilayer ceramic capacitor | |
| Villegas et al. | Preparation, microstructural development and dielectric properties of Pb (Mg 1/3 Nb 2/3) O 3-Pb (Ti x Zr 1− x) O 3 multilayer ceramic capacitors | |
| JPH08239265A (en) | Dielectric ceramic composition,laminated ceramic capacitor made thereof and its production | |
| US4474894A (en) | Dielectric on the basis of lead titanates, method of manufacturing same, and a multilayer capacitor comprising the dielectric | |
| EP0200484B1 (en) | Ultralow fire ceramic composition | |
| JP2689439B2 (en) | Grain boundary insulation type semiconductor porcelain body | |
| JP2000216042A (en) | Manufacture of laminated ceramic capacitor | |
| JPS6097613A (en) | Multilayer ceramic condenser | |
| JPH0793225B2 (en) | Ceramic capacitor and manufacturing method thereof | |
| JP3914635B2 (en) | Manufacturing method of ceramic electronic component | |
| JP2752100B2 (en) | Manufacturing method of multilayer ceramic capacitor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |