KR20100014318A - X8r dielectric composition for use with nickel electrodes - Google Patents

Abstract

Multilayer ceramic chip capacitors which satisfy X8R requirements and which are compatible with reducing atmosphere sintering conditions so that non-noble metals such as nickel and nickel alloys thereof may be used for internal and external electrodes are made in accordance with the invention. The capacitors exhibit desirable dielectric properties (high capacitance, low dissipation factor, high insulation resistance), excellent performance on highly accelerated life testing, and very good resistance to dielectric breakdown. The dielectric layers comprise a barium titanate base material doped with other metal oxides such as BaO, YO, ZrO, SiO, MgO, MnO, MoO, CaO, LuO, YbO, or WOin various combinations.

Description

X8R dielectric composition for use in nickel electrodes {X8R DIELECTRIC COMPOSITION FOR USE WITH NICKEL ELECTRODES}

The present invention relates to a barium titanate-based dielectric composition, and more particularly to a relatively small proportion of guest ions, such as zirconium, manganese, molybdenum, magnesium, yttrium, silicon, and additional barium dispersed in a barium titanate crystal matrix. It relates to a barium titanate-based dielectric composition having. Such dielectric compositions can be used to form multilayer ceramic chip capacitors having internal base metal electrodes formed of nickel or nickel alloys.

Multilayer ceramic chip capacitors are widely used as miniature-sized high capacitance and high reliability electronic components. As the demand for high performance electronic equipment increases, multilayer ceramic chip capacitors also face market demands for smaller size, higher capacitance, lower cost and higher reliability.

Multilayer ceramic chip capacitors are generally fabricated by forming alternating layers of internal electrode forming pastes and dielectric layer-forming pastes. Such layers are generally formed by sheeting, printing or similar techniques, followed by co-firing.

In general, the internal electrode consists of a conductor such as silver, gold, palladium, platinum (ie, "noble metal") or alloys thereof. Precious metals are expensive but can be partially replaced by using relatively inexpensive base metals such as nickel, copper and their alloys. As used herein, "base metal" is a metal other than silver, gold, palladium and platinum. The nonmetal internal electrode can be oxidized when fired in the atmosphere, so that the dielectric layer and the nonmetal internal electrode layer must be cofired in a reducing atmosphere. However, firing in a reducing atmosphere causes the dielectric layer to be reduced, which reduces the electrical resistivity. Multilayer ceramic chip capacitors using non-reducing dielectric materials have been proposed, but such devices generally have a short lifetime of insulation resistance (IR) and low reliability.

The Electronics Industry Association (EIA) defines criteria for the temperature coefficient of capacitance (TCC), known as the X8R characteristic. The X8R characteristic requires that the change in capacitance be less than ± 15% for a reference temperature of 25 ° C over a temperature range of -55 ° C to + 150 ° C. X8R components exhibit less than 2.5% capacitance aging per decade.

Summary of the Invention

The present invention provides a dielectric composition that can be used to make ceramic multilayer capacitors that are compatible with internal electrodes containing nonmetals such as nickel or nickel alloys. Capacitors can be formed from the dielectric compositions of the present invention to exhibit stable dielectric constants with low dielectric loss and good reliability under very accelerated life test conditions.

The dielectric composition of the present invention comprises a constant dense microstructure of grain having an average diameter of about 0.5-1.5 microns. Constant and dense grain microstructure is important for achieving high reliability multi-layer capacitors with dielectric layers thinner than about 10 microns.

In one embodiment, the dielectric composition of the present invention comprises a blend of oxides or carbonates of zirconium, barium, manganese, molybdenum, magnesium, yttrium and silicon, in addition to BaTiO ₃ prior to firing. Yet another embodiment of the present invention is an electronic device comprising a multilayer chip comprising a dielectric layer comprising a blend of BaTiO ₃ and oxides or carbonates of zirconium, barium, manganese, molybdenum, magnesium, yttrium and silicon prior to firing.

In another embodiment, the present invention provides a method of forming an electronic component comprising applying particles of dielectric material to a substrate and firing the substrate at a temperature sufficient to sinter the dielectric material, wherein the dielectric material is baked A blend (% by weight) of the ingredients previously in Table 1 is included. Each numerical value (percent, temperature, etc.) in the present invention is considered to be "about."

Oxide composition of the dielectric composition to which oxides are added in moles per 100 moles of BaTiO ₃ ZrO ₂ BaO MnO MoO ₃ MgO Y ₂ O ₃ SiO ₂ 0.01-2 2-5 0.05-0.3 0-0.4 0.05-2.5 0.5-2 0.3-2

It is known that equivalent compositions can be developed using the corresponding carbonates, such as BaCO ₃ , MgCO ₃ , or other metal salts, as long as the final ratio of metal ions in the dielectric composition is achieved by the compositions in Table 1 Will be understood by those skilled in the art.

Another route is not only BaTiO ₃ (ie, pre-sintered oxides) but also oxides or carbonates of barium, manganese, magnesium, yttrium and silicon and oxides or carbonates of at least one of calcium, zirconium, ruthetium, ytterbium, molybdenum and tungsten To start.

Another embodiment of the invention is a method for manufacturing a multilayer ceramic chip capacitor having X8R characteristics, comprising the following steps:

a. A dielectric material is provided comprising a blend of the following components prior to sintering:

i. BaTiO ₃ , and in the following, per 100 mole parts of BaTiO ₃ :

ii. About 0.01-2 moles of ZrO _2,

iii. About 1-6 moles of BaCO ₃ ,

iv. About 0.05-0.5 mole parts of MnCO ₃ ,

v. About 0.01-0.4 mole parts of MoO ₃ ,

  vi. About 0.05-2.5 molar parts of MgO,

vii. About 0.5-7 mole parts of Y ₂ O ₃ , and

viii. About 0.3-4 mole parts of SiO ₂ .

b. Forming an alternatingly stacked layer of internal dielectric material and a layer of internal electrode material comprising a transition metal,

c. Firing the stack in the atmosphere to a temperature sufficient to sinter the electrode material without oxidation and fusion of the dielectric material.

Another embodiment of the invention is a method for forming an electronic component, comprising the following steps:

a. i. Dielectric paste described herein, and

   ii. Metal-containing electrode paste comprising at least one metal selected from the group consisting of transition metals other than Ag, Au, Pd, and Pt

   Layers of

   iii. Board

   Applied alternately onto the to form a stack,

b. Sintering the electrode metal and firing the stack in an atmosphere having a partial oxygen pressure of about 10 ⁻⁸ atmospheres or less at a temperature sufficient to fuse the dielectric material.

Yet another embodiment of the present invention is a method for forming an electronic component comprising:

a. i. Dielectric paste described herein, and

   ii. Metal-containing electrode paste comprising at least one metal selected from the group consisting of Pd, Pt, and Pd-Ag alloys

   Layers of

   iii. Board

   Applied alternately onto the to form a stack,

b. Sintering the electrode metal and firing the stack to a temperature sufficient to fuse the dielectric material.

Capacitors meet the needs for a variety of applications in the automotive and industrial markets and in other electronic devices exposed to high temperatures. The increasing use of electronic devices "under the hood" of automobiles has created a need for this product range.

These and other features of the invention are described in more detail below, which are shown in the following description which sets forth the claims and the specific embodiments of the invention in detail, but which illustrate some of the various ways in which the principles of the invention may be used. .

1 is a cross-sectional view of a multilayer ceramic chip capacitor according to an embodiment of the invention.

FIG. 2 illustrates the relationship between TCC and temperature in disk capacitor sample C-4 of FIG. 6. The largest box in the graph represents the X8R specification. The vertical line in this box is at 125 ° C.

Multilayer chip capacitors are fabricated by alternately stacking a dielectric layer and internal electrodes to form a green chip. Two types of internal electrodes are used here. The first includes nonmetals including nickel or nickel alloys, or other nonmetals such as copper. Nickel is preferred. Electronic components having a nonmetallic electrode are fired in a low-oxygen atmosphere to prevent oxidation of the nonmetal. The second type of internal electrode is a precious metal electrode which may comprise silver, gold, palladium and platinum. In general, electronic components containing noble metal electrodes can be fired in the atmosphere because they have little to do with oxidation. The dielectric composition forming the dielectric layer is prepared by wet milling a part of the dielectric having the organic vehicle system. The dielectric composition is deposited on a carrier film (such as polyester or polypropylene), belt (such as stainless steel), paper or substrate (such as alumina or glass). Sheets of dielectric material are alternately stacked with electrodes to form green chips. The dielectric composition broadly comprises the oxides of Table 1.

Table 1 (Repeated)

Oxide composition of the dielectric composition to which oxides are added in moles per 100 moles of BaTiO ₃

ZrO ₂ BaO MnO MoO ₃ MgO Y ₂ O ₃ SiO ₂ 0.01-2 2-5 0.05-0.3 0-0.4 0.05-2.5 0.5-2 0.3-2

After the green chip is formed, the organic vehicle is removed by heating to a temperature of about 350 ° C. or less in the atmosphere. The pressure for the vehicle to be removed is not critical. In the case of a nonmetallic electrode, when the vehicle is removed, the green chip is calcined in a reducing atmosphere of wet nitrogen and hydrogen having an oxygen partial pressure of about 10 ^-12 -10 ^-8 atm at a temperature of about 1200-1350 ° C. Chips with precious metal electrodes can be fired in the atmosphere or in an atmosphere where no special precautions are taken. Various heating profiles can be used to remove the binder and bake the chip.

The form of multilayer ceramic capacitors is well known in the art. 1 illustrates an exemplary structure of a multilayer ceramic chip capacitor 1. The external electrode 4 of the capacitor 1 is arranged in electrical connection with the internal electrode layer 3 on the side of the capacitor chip 1. Capacitor chip 1 has a plurality of alternatingly stacked dielectric layers 2. The shape of the capacitor chip 10 is mainly rectangular but is not important. In addition, size is not critical and chips may generally have suitable dimensions depending on the particular application in the range 1.0-5.6 mm x 0.5-5.0 mm x 0.5-1.9 mm. The inner electrode layers 3 are stacked such that at opposite ends they are alternately exposed at opposite sides of the chip 1. That is, one group of inner electrode layers 3 is exposed on one side of the chip 1 and the other group of inner electrode layers 3 is exposed on the opposite side of the chip 1. One outer electrode 4 is applied to one side of the capacitor chip 1 in electrical contact with one group of inner electrode layers 3 and the other outer electrode 4 is in electrical contact with the other group of inner electrode layers 3. In contact with the opposite side of the chip 1.

The dielectric layer consists of a dielectric material formed by sintering zirconium, manganese, molybdenum magnesium, yttrium, silicon and additional barium and BaTiO ₃ , as shown in Table 1. Sintering aids such as SiO ₂ can be used. It is understood that other forms such as the hydroxides of the above oxides or organometallic compounds such as carbonates, acetates, nitrates and metal formates, oxalates, etc., have the same effect as long as the desired metal ions are provided in the desired amounts. It is obvious to those familiar with the technology.

Another composition of the dielectric composition added oxide in moles per 100 moles of BaTiO ₃ ZrO ₂ BaO MnO MoO ₃ MgO Y ₂ O ₃ SiO ₂ CaO Lu ₂ O ₃ Yb ₂ O ₃ WO ₃ 0.1-1.75 2.5-4.5 0.1-0.4 0.02-0.3 0.05-2 1-6 1-3 1.5-6 0.1-0.5 0.5-2 0.25-2.5 1-4 0.1-3.5 2-5 0.05-0.5 0.01-0.4 0.05-2.5 0.5-2.0 0.3-2.0 0-3 0-2.5 0-2 0-0.2

Other compounds may also be present in the genetic material as long as they do not adversely affect the dielectric properties. Such compounds are commonly found in raw materials as impurities.

The dielectric composition generally has microcrystalline grains having an average size of about 0.5-3 microns with a grain size of about 0.7 microns or less. Each dielectric layer has a thickness of about 20 microns or less. Preferably, each dielectric layer is about 4-15 microns thick. More preferably, the thickness of each dielectric layer is about 6-12 microns. The compositions of the present invention can be used to make multilayer ceramic chip capacitors with thin dielectric layers. The number of dielectric layers stacked on the chip capacitor is generally about 800 or less, preferably about 3-400.

The multilayer ceramic chip capacitor of the present invention has a structure shown in FIG. 1 by stacking a dielectric (ceramic) sheet on which an electrode pattern is printed by screen printing, or alternately screen printing ceramic and electrode paste to form a green stack. It is prepared by forming a. In both methods for forming the ceramic layer, the powder is dispersed in a solvent and a binder is added to provide the desired viscosity for processing and the desired mechanical strength after drying. The ceramic sheet may be formed, for example, by doctor-blading in which the electrode pattern is printed after drying. In addition, the ceramic sheet may be formed by screen printing the green stack formation in the intermediate drying of the alternating printing of the electrode and the dielectric paste. The green chip is separated in such a way that neighboring electrodes connect to opposite ends of the MLCC structure as in FIG. After firing, the chips are tumbled dry in a medium such as alumina and silica to round the corners. Thereafter, for example, a conductive paste containing copper is applied to both ends to connect the exposed inner electrodes together to make ends, ie, outer electrodes. The chip is then fired at about 800 ° C. in a dry nitrogen atmosphere to sinter the conductor (eg copper) into a solid conductive pad at both ends to form a multilayer capacitor. The end is the external electrode 4 as shown in FIG.

One embodiment of the invention is a multilayer comprising a fired aggregate of alternatingly stacked layers of dielectric materials described herein and layers of internal electrode materials comprising transition metals other than Ag, Au, Pd, or Pt. Ceramic chip capacitors. In such multilayer ceramic chip capacitors, the dielectric layer has a thickness of about 15 microns or less after firing, and the capacitors exhibit a dielectric constant (K) of about 2000 or more and a dissipation factor (DF) of about 2% or less and meet EIA X8R criteria. .

Another embodiment of the invention is an alternating stack of a layer of knee electrode material comprising a dielectric material described herein and at least one transition metal selected from the group consisting of Pd, Pt, and Pd-Ag alloys and combinations thereof And a multilayer ceramic chip capacitor comprising a fired aggregate of layers. In such multilayer ceramic chip capacitors, the dielectric layer has a thickness of about 15 microns or less after firing, and the capacitors exhibit a dielectric constant (K) of about 2000 or more and a dissipation factor (DF) of about 2% or less and meet EIA X8R criteria. .

Another embodiment provides a metal-containing layer comprising an oxide-containing dielectric material layer comprising the dielectric paste composition described herein and at least one metal selected from the group consisting of transition metals other than Ag, Au, Pd, and Pt. The layers of electrode paste are applied alternately on a substrate to form a stack, and the stack is fired in an atmosphere having a partial oxygen pressure of about 10 ⁻⁸ atmospheres or less at a temperature sufficient to sinter the electrode metal and fuse the dielectric material. The method for forming an electronic component, comprising the step of. .

Another embodiment provides a layer of an oxide-containing dielectric material comprising a dielectric paste composition described herein and a metal-containing electrode paste comprising at least one metal selected from the group consisting of Pd, Pt, and Pd-Ag alloys. Applying layers alternately on a substrate to form a stack, sintering the electrode metal, and firing the stack to a temperature sufficient to fuse the dielectric material. .

Each main component of the electronic component is described in turn.

Dielectric paste. Pastes for forming the dielectric layer can be obtained by mixing the organic vehicle with the raw dielectric material as described herein. Also useful are precursor compounds that convert to oxides and complex oxides upon firing as described above. Dielectric materials are obtained by selecting these oxides or compounds containing precursors of these oxides and mixing them in appropriate proportions. The proportion of such compounds in the raw dielectric material is determined so that the desired dielectric layer composition can be obtained after firing. The raw dielectric material is generally used in powder form having an average particle size of about 0.1-1.5 microns, preferably about 1 micron or less and more preferably 0.5-0.9 microns.

Organic vehicle. The organic vehicle is a binder in an organic solvent or a binder in water. The choice of binder used here is not important; Conventional binders such as ethyl cellulose, polyvinyl butanol, ethyl cellulose and hydroxypropyl cellulose and combinations thereof are suitable with the solvent. Organic solvents are also not important and, depending on the particular application (ie, printing or sheeting), butyl carbitol, acetone, toluene, ethanol, diethylene glycol butyl ether; 2,2,4-trimethyl pentanediol monoisobutyrate (Texanol ^® ); Alpha-terpineol; Beta-terpineol; Gamma terpineol; Tridecyl alcohol; Diethylene glycol ethyl ether (Carbitol ^® ). Diethylene glycol butyl ether (Butyl Carbitol ^® ) and propylene glycol; And conventional organic solvents such as blends thereof. Products sold under the trademark Texanol ^® are available from Eastman Chemical Company, Kingsport, Tennessee, USA; Those sold under the trademarks Dowanol ^® and Carbitol ^® are available from Dow Chemical Co., Midland, Michigan, USA. In addition, the vehicle for the ceramic slurry may be water.

When water is the vehicle, the binder may be selected from polyvinyl alcohol (PVA) or polyvinyl acetate (PVAC) in combination with water. It should be noted that PVA and PVAC are generally not compatible with boron-containing ceramic dielectric powders. Aqueous slurries comprising boron containing glass together with PVA and / or PVAC tend to undergo severe gelation. Therefore, ceramic dielectric powder free of boron, as described in the present invention, is particularly important for aqueous slurry processing. In addition, since emulsion type acrylate binders are used in an environment of water, it is believed that such does not occur, gelation can be avoided.

There is no particular limitation on the organic vehicle content of each paste (dielectric or electrode paste). The paste often contains about 1-5 wt% binder and about 10-50 wt organic solvent, with the balance being a metal component (relative to the electrode) or dielectric component (relative to the dielectric layer). If desired, each paste may contain up to about 10 wt% of other additives such as dispersants, plasticizers, dielectric compounds, and insulating compounds.

Internal electrode. The paste for forming the inner electrode layer is obtained by mixing an organic vehicle with a conductive material containing a nonmetal (such as nickel or copper) or a noble metal (such as silver, gold, palladium or platinum). Combinations of each base metal or precious metal and alloys thereof are also useful. Conductive materials as used herein include conductors such as conductive metals and alloys as described above and various compounds which, for example, convert oxides, organometallic compounds and resinates to such conductors upon firing. Any pure, commercially available nickel paste is suitable here. A suitable precious metal paste containing silver is EL45-006. Both are commercially available from Ferro Corporation, Cleveland, Ohio.

Referring to FIG. 1, the conductor forming the inner electrode layer 3 is preferably used but not important because the dielectric material of the dielectric layer 2 has reducing resistance. Common base metals include nickel and alloys thereof. Preferred nickel alloys contain at least one other metal selected from Mn, Cr, Co and Cu. Preference is given to alloys containing at least about 95 wt% nickel. It should be appreciated that nickel and nickel alloys may contain up to about 0.1 wt% phosphorus and other trace components (ie impurities). The thickness of the inner electrode layer can be adjusted to suit a particular application but is generally about 5 microns or less in thickness. Preferably, the inner electrode layer has a thickness of about 0.5-3 microns, more preferably about 1.2-1.5 microns. The precious metal inner electrode layer 3 may be selected from Ag, Au, Pd or Pt (or a combination thereof). Preferably the precious metal is selected from Pt, Pd, Pt-Pd alloys and Pd-Ag alloys. When Pd-Ag alloys are used, their weight ratio is preferably about 99: 1 to about 7: 3.

External electrode. The conductors forming the external electrode 4 are preferably but not important inexpensive metals such as nickel, copper and their alloys optionally containing Mn, Cr, Co or Al. The thickness of the outer electrode layer can be adjusted to suit a particular application but is generally about 10-50 microns, preferably about 20-40 microns. The paste for forming the external electrode is produced in the same manner as for the internal electrode.

Green chips can be made from dielectric layer-forming pastes and internal electrode layer-forming pastes. In the case of the printing method, the green chip alternately prints the paste in the form of lamina on a substrate of a polyester film, for example polyethylene terephthalate (PET) and cuts the lamina stack into a predetermined shape, which is It is prepared by separating from. Also useful is a sheeting method wherein green chips are produced by forming green sheets from dielectric layer-forming pastes, printing internal electrode layer-forming pastes on each green sheet, and stacking printed green sheets. After the organic vehicle is removed from the green chip, it is fired. The organic vehicle has a holding temperature of about 150-350 ° C., preferably about 200-300 ° C., more preferably about 250 ° C. at a rate of 0.01-20 ° C./hour, more preferably 0.03-0.1 ° C./hour in the atmosphere. And heating under a holding time of about 30-700 minutes, preferably about 200-300 minutes.

Plasticity. The green chip is fired in an atmosphere determined by the shape of the conductor in the inner electrode layer-forming paste. If the inner electrode layer consists of nonmetallic conductors such as nickel and nickel alloys, the firing atmosphere should have a low oxygen concentration, for example a wet H ₂ / N ₂ atmosphere. Such atmosphere may have an oxygen partial pressure of about 10 ^{-12-10 -8} atm. Sintering at partial pressures below 10 ^-12 atm should be avoided because at such low pressures the conductors may sinter abnormally and short out from the dielectric layer. At oxygen partial pressures above about 10 ⁻⁸ atm, the internal nonmetallic electrode layer may be oxidized. An oxygen partial pressure of about 10 ⁻¹¹ −10 ⁻⁹ atm is most preferred for nonmetal electrodes.

For noble metal internal electrodes, the firing atmosphere (ie, the presence or absence of oxygen) is less important because the noble metal is less susceptible to oxidation or in some cases not sensitive to oxidation.

For firing the temperature is raised from room temperature to a peak temperature of about 1150-1350 ° C, more preferably about 1250-1350 ° C. This temperature is maintained for about 2 hours to enhance densification. Lower holding temperatures provide insufficient densification while higher holding temperatures can produce very large grains. Firing is preferably carried out in a reducing atmosphere. Exemplary firing atmospheres include humidified mixtures of wet N ₂ or N ₂ and H ₂ gases. The sinter ramp rate is about 50-500 ° C./hour, preferably about 200-300 ° C./hour; A holding temperature of about 1200-1350 ° C., preferably about 1250-1350 ° C., and more preferably about 1280-1340 ° C. The holding time is about 0.5-8 hours, preferably about 1-3 hours; The cooling rate is 50-500 ° C./hour, preferably 200-300 ° C./hour.

Organic vehicle removal and firing can be performed continuously or separately. Processes in the continuous case include removing the organic vehicle, changing the atmosphere without cooling, heating to the firing temperature, maintaining the temperature for a certain time and then cooling. In individual cases, after the organic vehicle is removed and cooled, the temperature of the chip is raised to the sintering temperature and the atmosphere is changed to a reducing atmosphere.

The resulting chip can be polished at the end face, for example, by barrel tumbling and / or blasting, before the external electrode-forming paste is printed or conveyed and fired to form the external electrode (end). Firing of the external electrode-forming paste may be performed in a dry nitrogen atmosphere (about 10 ⁻⁶ atm oxygen partial pressure) at about 600-800 ° C. for about 10 minutes −1 hour.

If necessary, pads are formed on the external electrodes by plating or other methods known in the art. The multilayer ceramic chip capacitor of the present invention can be installed on a printed circuit board, for example, by welding.

The following examples are provided to illustrate preferred embodiments of the invention and are not intended to limit the scope of the invention.

Example 1. As shown in Table 3, dielectric compositions were prepared by mixing and milling BaTiO ₃ (BT) and oxides and carbonates to obtain guest ions. To this end, 250 g of BT were weighed into a 1 liter polyethylene bottle with the indicated amounts (as moles) of guest ions per 100 moles of BT. After addition of water and a dispersant, Dispex ^® A-40 (commercially available from Ciba Specialty Chemicals Maastricht BV, Maastricht, The Netherlands) and about 1.8 kg of 2 mm zirconia (YTZ) balls, the powder was added to water in 0.5 Milled to D ₅₀ between -0.7 microns. This powder is then dried at 150 ° C. and the disc pressed to provide a nickel electrode. These discs are sintered at humidified H ₂ / N ₂ at a temperature between 1280-1340 ° C. and reoxidized at 1000 ° C. humidified N ₂ . The TCC characteristics of the disks are tested and the K-value is measured from the capacity value at 25 ° C. The results are shown in Table 4.

Composition change of dielectric composition to moles of metal added per 100 moles of BT Sample Ba Y Zr Si Mg Mn Mo A-1 3.25 3.0 0.5 1.76 1.2 0.2 0.1 A-2 2.70 4.0 0.5 1.76 1.2 0.2 0.1 A-3 3.75 4.0 1.00 1.76 1.2 0.2 0.1 A-4 3.20 4.0 1.00 1.76 1.2 0.2 0.033 A-5 3.25 4.0 0.5 1.76 1.2 0.2 0.033 A-6 2.70 3.0 0.5 1.76 1.2 0.2 0.033 A-7 3.20 3.0 1.00 1.76 1.2 0.2 0.1 A-8 3.75 3.0 1.00 1.76 1.2 0.2 0.033 A-9 3.75 3.0 1.00 1.76 1.2 0.2 0.1 A-10 3.75 3.0 1.00 1.76 1.4 0.2 0.033 A-11 3.75 3.0 1.00 1.76 1.6 0.2 0.033 A-12 4.25 3.0 1.5 1.76 1.2 0.2 0.033

Disk and MLCC Results of Composition Changes in Table 3 disk MLCC Sample □ K Df [%] TCC @ 150 ℃ [%] K IR [G □] TCC @ 150 ℃ [%] A-1 5.87 2275 0.90 -7 2400 38.5 -14 A-2 5.85 2400 1.03 -7.5 2900 30 -18 A-3 5.80 2275 1.10 -4 2400 47 -12 A-4 5.88 2350 1.11 -5.8 2500 48 -14 A-5 5.76 2320 1.00 -6.5 2800 51 -15 A-6 5.89 2400 1.00 -9.2 2700 39 -19 A-7 5.92 2350 0.90 -7.6 2700 37 -16 A-8 5.92 2200 1.01 -6.5 1850 75 -19 A-9 5.89 2300 0.97 -3.5 2150 49 -19 A-10 5.90 2050 0.94 -6 1830 80 -15 A-11 5.90 2080 0.95 -6 1970 66 -14 A-12 5.89 2080 0.95 -6 2025 69 -16

What is important in this experiment is the trend between composition change and TCC at 150 ° C. for disk 롸 MLCCs. Due to the applied electric field, the TCC rotates clockwise (more negative) to deviate from the TCC curve specification of the MLCCs at the upper temperature limit of the X8R specification (ie 150 ° C.). Thus, the TCC at 150 ° C. is high enough for the disc capacitor to ensure that the MLCC made of the dielectric composition of the present invention meets the X8R specification. However, whether the MLCC meets this specification is measured not only by a sufficiently high TCC at 150 ° C. but also by the dielectric constant (K) value in the disc. It has been found that materials with high K-values demonstrate greater clockwise rotation in MLCCs when compared to low K-value materials.

Example 2. A dielectric composition was prepared according to the procedure of Example 1 using the composition on the left side of Table 5. The powder was dried at 150 ° C. and tested in a disk capacitor. The results of the electrical test are presented in Table 5 (three columns to the right).

Dielectric composition composition change and disc properties of the composition to moles of metal added per 100 moles of BT Sample Ba Y Ca Zr Lu Si Mg Mn Mo W K Df [%] TCC 150 ℃ B-1 2.75 3.0 1.76 0.87 0.2 0.1 0.1 2380 0.95 -12 B-2 5.5 6.0 3.52 1.74 0.4 0.2 0.2 2450 1.05 -11 B-3 2.0 2.25 0.75 1.76 0.87 0.2 0.1 0.1 2200 1.03 -16 B-4 2.0 1.5 1.5 1.76 0.87 0.2 0.1 0.1 2200 0.95 -9 B-5 2.0 0.75 2.25 1.76 0.87 0.2 0.1 0.1 2040 1.01 -9 B-6 1.9 3.0 1.76 0.87 0.2 0.1 2611 3.68 -23 B-7 2.75 3.0 3.0 3.0 1.76 0.87 0.2 0.1 0.1 2800 1.05 -22 B-8 5.75 3.0 3.0 1.76 0.87 0.2 0.1 0.1 3000 1.07 -20 B-9 3.0 3.0 1.76 1.2 0.2 0.1 0.1 2230 0.94 -12 B-10 4.25 3.0 1.5 1.76 0.87 0.2 0.1 0.1 2440 1.20 -14 B-11 3.75 3.0 0.75 1.76 1.2 0.2 0.1 0.1 2120 0.89 -11 B-12 3.75 3.0 0.75 1.76 1.2 0.2 0.1 0.1 2100 0.90 -7

Example 3. A dielectric composition was prepared according to the procedure of Example 1 using the composition on the left side of Table 6. The powder was dried at 150 ° C. and tested in a disk capacitor. The results of the electrical test are shown in Table 6 (three columns to the right).

Dielectric composition composition change of Example 3 to moles of metal added per 100 moles of BT and disc properties of the composition Sample Ba Y Zr Lu Yb Si Mg Mn Mo K Df [%] TCC [150 ℃] C-1 3.75 3 One 1.76 1.6 0.2 0.033 2240 1.11 -7 C-2 3.75 3 One 1.76 1.6 0.2 0.033 2090 1.04 -6 C-3 3.75 3 One 1.76 1.6 0.2 0.067 2280 1.02 -5 C-4 3.75 3 One 1.76 1.6 0.2 0.1 2270 1.00 -6 C-5 1.9 3.0 1.76 0.87 0.2 0.1 2400 1.09 -19 C-6 1.8 3.0 1.76 0.87 0.2 1775 2.24 -20 C-7 3.75 3 One 1.76 1.6 0.3 0.033 2350 0.80 -6 C-8 3.75 3 One 1.76 1.6 0.4 0.033 2260 0.74 -7 C-9 2.8 3.0 1.76 1.2 0.2 2300 1.01 -12 C-10 1.85 3.0 1.76 1.2 0.2 2350 0.99 -18 C-11 3.75 3 One 1.96 1.6 0.2 0.033 2360 0.87 -8 C-12 3.75 3 One 2.5 1.6 0.2 0.033 2620 0.92 -8 C-13 3.55 3.0 0.75 1.76 1.2 0.2 2150 0.91 -7 C-14 3.55 1.5 0.75 1.5 1.76 1.2 0.2 2000 0.96 -4 C-15 3.55 1.5 0.75 1.5 1.76 1.2 0.2 2100 1.04 -4 C-16 3.55 3.0 0.75 1.76 1.2 0.2 2120 0.92 -10 C-17 3.55 1.5 0.75 1.5 1.76 1.2 0.2 2070 0.94 -6

Additional advantages and modifications will readily occur to those skilled in the art. Accordingly, the invention in its broader scope is not limited to the specific details and exemplary embodiments described and illustrated herein. Accordingly, various modifications may be made without departing from the spirit and scope of the general inventive concept as defined in the appended claims and the like.

Claims (20)

A powder composition for use in forming a dielectric material for use in a multilayer ceramic chip capacitor, a. BaTiO ₃ , and in the following, per 100 mole parts of BaTiO ₃ : b. About 0.01-2 moles of ZrO _2, c. About 1-6 moles of BaCO ₃ , d. About 0.05-0.5 mole parts of MnCO ₃ , e. About 0.01-0.4 mole parts of MoO ₃ , f. About 0.05-2.5 molar parts of MgO, g. About 0.5-7 mole parts of Y ₂ O ₃ , and h. About 0.3-4 molar parts of SiO ₂ A composition comprising the blend of before sintering. The method of claim 1, a. BaTiO ₃ , and in the following, per 100 mole parts of BaTiO ₃ : b. About 0.1-1.75 moles of ZrO _2, c. About 2.5-4.5 molar parts of BaCO ₃ , d. About 0.1-0.4 molar parts of MnCO ₃ , e. About 0.02-0.3 mole parts of MoO ₃ , f. About 0.5-2 moles of MgO, g. About 1-6 molar parts of Y ₂ O ₃ , and h. About 1-3 molar parts of SiO ₂ A composition comprising a blend of. A powder composition for use in forming a dielectric material for use in a multilayer ceramic chip capacitor, a. BaTiO ₃ , and in the following, per 100 mole parts of BaTiO ₃ : b. About 1.5-6 moles of BaCO ₃ , c. About 0.1-0.5 mole parts of MnCO ₃ , d. About 0.5-2 moles of MgO, e. About 0.25-3.5 molar parts of Y ₂ O ₃ , and f. About 1-4 molar parts of SiO ₂ A composition comprising a blend of. According to claim 3, per 100 molar parts of BaTiO ₃ : a. About 2-4 moles of CaCO ₃ , b. About 0.5-3.5 molar parts of ZrO ₂ , c. About 0.5-2.5 molar parts of Lu ₂ O ₃ , d. About 0.5-2 mole parts of Yb ₂ O ₃ , e. About 0.01-0.5 mole parts of MoO ₃ , and f. About 0.1-0.5 mole parts of WO ₃ , and g. Combination of these The composition further comprises a component selected from the group consisting of. The composition of claim ₃ , further comprising about 0.5-2.5 molar parts of Lu ₂ O ₃ . 4. The composition of claim 3 further comprising about 0.5-3.5 molar parts of ZrO ₂ . 4. The composition of claim ₃ further comprising about 0.02-0.3 mole parts of MoO ₃ . In the multilayer ceramic chip capacitor, a. An alternating stacked layer of the material of claim 1, and b. Layer of internal electrode material comprising a transition metal other than Ag, Au, Pd, or Pt Multilayer ceramic chip capacitors comprising a fired aggregate of. The multilayer ceramic chip capacitor of claim 8, wherein the capacitor has a dielectric constant of at least about 2000 and a dissipation factor of about 2% or less and meets the EIA X8R criterion. A multilayer ceramic chip capacitor comprising a fired aggregate consisting of: a. An alternating stacked layer of the dielectric material of claim 1, and b. A layer of internal electrode material comprising a transition metal selected from the group consisting of Pd, Pt, and Pd-Ag alloys and combinations thereof. The multilayer ceramic chip capacitor of claim 10, wherein the capacitor has a dielectric constant of at least about 2000 and a dissipation factor of about 2% or less and meets EIA X8R criteria. A multilayer ceramic chip capacitor comprising a fired aggregate consisting of: a. An alternating stacked layer of the dielectric material of claim 2, and b. A layer of internal electrode material comprising a metal selected from the group consisting of Pd, Pt or Pd-Ag. 13. The multilayer ceramic chip capacitor of claim 12, wherein the capacitor has a dielectric constant of at least about 2000 and a dissipation factor of about 2% or less and meets the EIA X8R criterion. A method for forming an electronic component, comprising the following steps: a. i. An oxide-containing dielectric material comprising the paste of claim 1, and    ii. Metal-containing electrode paste comprising at least one metal selected from the group consisting of transition metals other than Ag, Au, Pd, and Pt    Layers of    iii. Board    Applied alternately onto the to form a stack, b. Sintering the electrode metal and firing the stack in an atmosphere having a partial oxygen pressure of about 10 ⁻⁸ atmospheres or less at a temperature sufficient to fuse the dielectric material. A method for forming an electronic component comprising the following steps: a. i. An oxide-containing dielectric material comprising the paste of claim 1, and    ii. Metal-containing electrode paste comprising at least one metal selected from the group consisting of Pd, Pt, and Pd-Ag alloys    Layers of    iii. Board    Applied alternately onto the to form a stack, b. Sintering the electrode metal and firing the stack to a temperature sufficient to fuse the dielectric material. The method of claim 15, wherein the electrode paste comprises a Pd-Ag alloy having a weight ratio of about 99: 1-7: 3. 16. The method of claim 15, wherein firing is performed in an atmosphere having a partial oxygen pressure of about 10 ^{-12-10 -8} atmospheres. A method for manufacturing a multilayer ceramic chip capacitor having X8R characteristics, comprising the following steps: A method for manufacturing a multilayer ceramic chip capacitor having X8R characteristics, comprising the following steps: a. Providing a dielectric material comprising: i. BaTiO ₃ , and in the following, per 100 mole parts of BaTiO ₃ : ii. About 0.01-2 moles of ZrO _2, iii. About 1-6 moles of BaCO ₃ , iv. About 0.05-0.5 mole parts of MnCO ₃ , v. About 0.01-0.4 mole parts of MoO ₃ ,   vi. About 0.05-2.5 molar parts of MgO, vii. About 0.5-7 mole parts of Y ₂ O ₃ , and viii. About 0.3-4 mole parts of SiO ₂ . b. Forming an alternatingly stacked layer of internal dielectric material and a layer of internal electrode material comprising a transition metal, c. Firing the stack in the atmosphere to a temperature sufficient to sinter the electrode material and fuse the dielectric material. The method of claim 18, wherein the internal electrode material comprises a transition metal other than Ag, Au, Pd, or Pt, and the atmospheric pressure has a partial appeal pressure of about 10 ⁻⁸ or less. 19. The method of claim 18, wherein the internal electrode material comprises a transition metal selected from the group consisting of Pd, Pt, and Pd-Ag alloys, and combinations thereof.

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