JP5157799B2 - Conductive paste, and dry film and multilayer ceramic capacitor using the conductive paste - Google Patents

Conductive paste, and dry film and multilayer ceramic capacitor using the conductive paste Download PDF

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JP5157799B2
JP5157799B2 JP2008257862A JP2008257862A JP5157799B2 JP 5157799 B2 JP5157799 B2 JP 5157799B2 JP 2008257862 A JP2008257862 A JP 2008257862A JP 2008257862 A JP2008257862 A JP 2008257862A JP 5157799 B2 JP5157799 B2 JP 5157799B2
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伸寿 鈴木
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住友金属鉱山株式会社
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Description

  The present invention relates to a conductive paste that suppresses variations in capacitance in a multilayer ceramic electronic component and reduces dielectric loss, and a dry film and a multilayer ceramic capacitor using the conductive pace.

  As electronic devices such as mobile phones and digital devices become lighter, thinner, and smaller, chip ceramic multilayer capacitors are also required to be smaller, have higher capacity, and have higher performance. It is known to make the dielectric layer thin and to increase the number of layers.

In general, a multilayer ceramic capacitor is manufactured as follows.
First, in order to form a dielectric layer, a conductive green powder is dispersed as a main component on a dielectric green sheet made of an organic binder such as barium titanate (BaTiO 3 ) and polyvinyl butyral, and dispersed in a vehicle containing a resin binder and a solvent. The conductive paste thus formed is printed and dried in a predetermined pattern to remove the solvent, thereby forming a dry film that becomes an internal electrode.
The dielectric green sheets on which the dry film is formed are integrated by thermocompression in a stacked state, then cut into a predetermined shape, and then debindered in an oxidizing atmosphere or inert atmosphere at 500 ° C. or lower. Process. Thereafter, heat firing is performed at about 1300 ° C. in a reducing atmosphere so as not to oxidize the internal electrode, an external electrode is provided on the fired chip, and nickel plating or the like is performed on the external electrode to complete.

  However, in the firing step, the temperature at which the dielectric ceramic powder starts to sinter is about 1200 ° C., and a considerable mismatch occurs with the temperature at which sintering and shrinkage with the conductive metal powder such as nickel starts. Structural defects such as delamination (delamination) and cracks were likely to occur. In particular, as the number of stacked layers increases or the thickness of the ceramic dielectric layer decreases as the size and capacity increase, structural defects become more prominent.

  For example, if the constituent elements of the main component of the dielectric layer and the constituent elements of the dielectric powder contained in the electrode paste are greatly different, the electrical characteristics such as increased dielectric loss will be affected. In order to control the sintering / shrinkage of the internal electrode nickel paste to at least near the temperature at which sintering / shrinkage of the dielectric layer starts, it is usually a barium titanate or zirconate similar to the composition of the dielectric layer. A ceramic powder mainly composed of a perovskite oxide such as strontium is added. As a result, the sintering behavior of the nickel powder is controlled, and the mismatch of the sintering shrinkage behavior of the internal electrode layer and the dielectric layer can be controlled.

  In recent years, monolithic ceramic capacitors have been required to further reduce the thickness of internal electrode layers using nickel powder or the like in accordance with the demand for further miniaturization and large capacity. Therefore, in order to form a high-density internal electrode with a small amount of metal coating and achieve a thin layer and target capacity at the same time, the particle size of conductive metal powder such as nickel and ceramic powder used for conductive paste It is required to make it finer.

  Furthermore, when this ceramic powder cannot prevent the contact of the conductive metal powder in the conductive paste, the effect of bringing the sintering start temperature of the conductive paste close to the sintering start temperature of the ceramic layer is weakened, resulting in delamination. Problems such as cracks and cracks, and deteriorates reliability such as yield reduction. Therefore, when the particle size of the conductive metal powder is made fine, it has a particle size smaller than the particle size of the conductive metal powder in order to intervene between the contacts of the conductive metal powder and delay the sintering start temperature. It is necessary to select a ceramic powder.

  Moreover, in order to make it possible to obtain a large capacitance, it is desired to suppress the ceramic powder to an addition amount as small as possible. The first reason is that sintering with the ceramic particles in the dielectric layer is minimized, and electrical characteristics such as dielectric loss and breakdown voltage are not deteriorated. Secondly, the continuity of the electrode film is not deteriorated by increasing the conductive metal content per electrode unit area.

  In such a technical background, in Patent Document 1, ceramic powder having an average particle size smaller than the average particle size of the conductive metal powder is used as a conductive paste capable of forming a dense film-shaped conductor on a ceramic substrate. The conductive paste used is shown.

Patent Document 2 discloses an internal electrode paste that suppresses grain growth of crystal grains in a dielectric layer and reduces variations in high insulation, dielectric loss, and insulation resistance. The barium titanate-based powder of the ceramic powder used for the internal electrode paste has a lattice constant ratio (c / a) of greater than 1, and a molar ratio of titanium to barium (Ba / Ti) of greater than 1 and 70 nm or less. There is a need for average particle size characteristics.
JP 2002-245874 A JP 2007-95382 A

  However, if a ceramic powder having a particle size smaller than that of the conductive metal powder as disclosed in Patent Document 1 is selected, a sufficient effect as a sintering inhibitor cannot be obtained. If the effect cannot be obtained, a difference in shrinkage occurs between the ceramic layer and the conductive layer, and there remains a problem that defects such as cracks and delamination are likely to occur.

Furthermore, the dielectric loss of the multilayer ceramic capacitor is sufficient only by selecting a ceramic powder having a c / a ratio of greater than 1, a molar ratio (Ba / Ti) of greater than 1 and an average particle size of 70 nm or less in Patent Document 2. There is also a problem that it cannot be reduced.
The problem that the dielectric loss cannot be made sufficiently small is that the dielectric loss is also affected by the smoothness of the film and the filling property of the particles in the dry film formed from the conductive paste. The smoothness of the film and the filling property of the particles change depending on the dispersion of the particle size distribution of the conductive metal powder or the ceramic powder. However, in the invention of Patent Document 2, the dispersion of the dielectric loss is large even for the co-material having the same particle diameter, When the particle size distribution is in the range of 0.15 to 0.4 μm, the smoothness of the film and the filling property of the particles in the dry film formed from the conductive paste cannot be improved, and the thinning of the electrode film cannot be supported. doing.

  Accordingly, in order to solve such problems, the present invention aims to provide a conductive paste capable of suppressing variation in capacitance and reducing dielectric loss, and a multilayer ceramic capacitor using the conductive paste. Is.

That is, the invention according to claim 1 of the present application is a conductive paste for a multilayer ceramic electronic component comprising at least a ceramic powder and a conductive metal powder,
The ceramic powder has 1) an average particle diameter of 0.01 to 0.1 μm, 2) a lattice constant ratio (c / a) of c-axis length to a-axis length of crystal lattice of 1.0020 or more, and 3) barium. And the titanium molar ratio (Ba / Ti) is 0.995 or more and 1.000 or less, 4) the particle size variation coefficient CV is 35% or less, and 5) the major axis to minor axis ratio (aspect ratio) is 1.15. The following barium titanate powder,
The conductive metal powder is 1) a nickel powder having an average particle diameter larger than the average particle diameter of the ceramic powder and an average particle diameter of 0.4 μm or less, and 2) a carbon content of 0.06 wt% or less. This is a conductive paste for ceramic electronic components.

  The invention according to claim 2 of the present application is characterized in that the ceramic powder is 3 to 25 parts by weight when the weight of the conductive metal powder is 100 parts by weight. This is a conductive paste for ceramic electronic components.

The invention described in claim 3 has a film density of 5.3 g / cm 3 or more obtained by printing and drying the conductive paste for multilayer ceramic electronic component according to claim 1 or 2, and a maximum protrusion height. It is a dry film of 1.5 μm or less.

  A fourth aspect of the present invention is a multilayer ceramic capacitor in which the thickness of the internal electrode layer using the dried film according to the third aspect is 1.5 μm or less.

  The conductive paste according to the present invention is suitable for use in a small and thin multilayer ceramic electronic component, particularly a multilayer ceramic capacitor, and suppresses variations in capacitance and dielectric breakdown voltage to reduce dielectric loss. This has the effect of reducing the size. Furthermore, an electronic component such as a multilayer ceramic capacitor can be obtained at a low cost without requiring a special manufacturing process or equipment.

  The dried film obtained by drying the conductive paste of the present invention is used as an internal electrode of a multilayer ceramic capacitor, so that there is no risk of loss of capacitance, and variation in capacitance and dielectric breakdown voltage is suppressed. The loss is reduced.

  The multilayer ceramic capacitor according to the present invention has small variations in capacitance and dielectric breakdown voltage, and can be easily reduced in size and thickness.

  The conductive paste of the present invention is obtained by dispersing nickel powder and ceramic powder of conductive powder in a vehicle in which a resin binder is dissolved in an organic solvent, and the details of the configuration will be described below.

[Conductive powder (nickel powder)]
Nickel powder, which is a conductive powder, may contain carbon depending on its production method, and this carbon deteriorates the sinterability between nickel powders, so that the content can be suppressed to 0.06 wt% or less. desirable.
If the content exceeds 0.06 wt%, the reason is not clear, but it affects the dry film density of the dried film obtained by drying the conductive paste, and as a result, an electrode film having a desired film thickness and effective electrode area. This is because cannot be obtained.

In order to reduce the carbon content in the nickel powder to 0.06 wt% or less, in a liquid phase reduction method in which a nickel salt aqueous solution is reduced with a reducing agent to precipitate the nickel powder, particle size control of the obtained powder is performed. In order to prevent agglomeration, an organic dispersion material such as a surfactant is added to the reaction solution for synthesis. In this case, the added organic substance is considered to remain at the grain boundaries inside the nickel powder produced by the reaction. The carbon content in the nickel powder is lowered by not adding an organic dispersant such as a surfactant to the reaction solution, or by suppressing the amount added.
The analysis of the amount of carbon contained in the nickel powder is measured by the high frequency combustion infrared absorption wave method.

  Next, the average particle diameter of the nickel powder is larger than the average particle diameter of the ceramic powder and not more than 0.4 μm. First, the nickel powder may produce coarse particles due to aggregation, and the average particle diameter is When the particle diameter exceeds 0.4 μm, the particle size of the coarse particles (D100) exceeds 1.5 μm. As a result, the maximum protrusion height of the dry film (electrode film) formed by drying the conductive paste is 1.5 μm. Therefore, it is difficult to reduce the thickness of the dielectric layer.

  Second, when trying to form a dry film (electrode film) having a film thickness of 1.5 μm or less with nickel powder having an average particle diameter of 0.4 μm or less, the nickel powder particles are insufficiently filled, This is because the dry film density cannot be secured, the dry film (electrode film) having excellent continuity cannot be obtained, the dry film (electrode film) is interrupted, and the capacitance of the multilayer ceramic capacitor is reduced. .

  Third, if the average particle size is smaller than the average particle of the ceramic powder, the conductivity after the electrode film is formed is remarkably lowered, and the electrode film does not function.

  In the present invention, the particle diameter of the nickel powder is expressed by a particle diameter obtained by calculating the specific surface area based on the BET method unless otherwise specified.

In Equation 1, S Ni is the specific surface area (m 2 / g) of nickel powder, and ρ is the true density of nickel, which is 8.9.
The particle size distribution of the nickel powder can be measured using a known particle size analyzer.

In the present invention, the method for producing the nickel powder to be used is not particularly limited, and the nickel powder is produced by controlling the carbon content and the average particle size.
For example, a liquid phase reduction method in which an aqueous nickel salt solution is reduced with a reducing agent to precipitate nickel powder, a vapor phase reduction method in which chloride vapor is directly deposited from a gas phase in hydrogen gas, an aqueous nickel solution at a high temperature, for example, 600 Nickel powder having a carbon content of 0.06 wt% or less, an average particle size larger than the average particle size of the ceramic powder, and 0.4 μm or less, as appropriate, such as a spray pyrolysis method in which spraying is performed at a temperature of 0 ° C. Manufacturing.

[Ceramic powder (barium titanate powder)]
The ceramic powder added to the conductive paste of the present invention can be selected from BaTiO 3 which is usually a perovskite type oxide, and those obtained by adding various additives thereto, and the dielectric powder of the multilayer ceramic capacitor. The same composition as the ceramic powder used as the main component of the green sheet forming the layer or a similar composition is also preferred.

  There are various methods for producing a ceramic powder, such as a solid phase method, a hydrothermal synthesis method, an alkoxide method, a sol-gel method, and the hydrothermal synthesis method is used in the present invention because a fine and sharp particle size distribution can be obtained. The ceramic powder is preferable.

  The average particle size of the ceramic powder in the present invention is preferably in the range of 0.01 μm to 0.1 μm. When the average particle diameter exceeds 0.1 μm, the gap between the contact points of the substantially spherical nickel powder particles is filled in the dry film because the ceramic powder is filled in the gap formed by stacking the substantially spherical nickel powder particles. First, the desired dry film density cannot be obtained, that is, the dry film density is lowered. Second, the effect of delaying the sintering start temperature of the conductive paste to the sintering start temperature of the ceramic layer is weakened.

On the other hand, if the particle size of the ceramic powder is less than 0.01 μm, the sintering delay effect of the conductive paste cannot be obtained, and structural defects such as delamination and cracks are likely to occur. In addition, the maximum protrusion height is 1.5 μm or more due to the reduced dry film density and the agglomerated powder of the ceramic powder, making it difficult to reduce the thickness of the dielectric layer. Problems related to reliability, such as rising, occur.
In the present invention, the particle size of the ceramic powder is represented by the particle size of the specific surface area calculated based on the BET method unless otherwise specified. Formula 2 when using barium titanate powder as the ceramic powder is shown in Equation 2.

In Equation 2, S BT specific surface area (m 2 / g) of barium titanate powder, [rho BT is 6.1 true density of the barium titanate powder.

The lattice constant ratio (c / a) between the c-axis length and the a-axis length of the crystal lattice of the ceramic powder is 1.0020 or more, preferably 1.0040 or more and 1.0100 or less.
In the tetragonal barium titanate powder, if its c / a ratio is smaller than 1.0020, ferroelectricity cannot be obtained. In addition, barium titanate powder has a c / a variation in the range of 1.000 to 1.0100 due to phase transition accompanying temperature change, and the sintering temperature increases as c / a increases. If the c / a of the barium powder is less than 1.0020, the co-material in the internal electrode layer is released into the dielectric layer molded body during firing, and the added fine co-material is involved in the sintering of the dielectric layer. If the c / a is larger than 1.0020, the grain loss of the common material in the ceramic powder layer and the internal electrode layer is suppressed, and the dielectric loss of the multilayer ceramic capacitor is reduced. In addition, the insulation resistance can be increased.

  The measurement of the lattice constant (c / a) is performed using a powder X-ray diffractometer (for example, RAD-IIA manufactured by Rigaku Corporation), and XRD profile data for Rietveld analysis is in a range where 2θ is 10 to 120 °. The lattice constant ratio (c / a) is calculated using Rietveld analysis.

The barium / titanium molar ratio (Ba / Ti) of the barium titanate powder is preferably 0.995 to 1.000. By controlling the molar ratio (Ba / Ti) of the barium titanate powder within the above range, it is possible to produce a powder with less variation in particle size distribution and less aggregate formation.
On the other hand, when the molar ratio (Ba / Ti) is outside the above range, the dispersion of the particle size distribution becomes large, and when the molar ratio (Ba / Ti) exceeds 1.000, it exists in the crystal lattice of the barium titanate powder. As the hydroxyl group increases, the loss on ignition increases, so the c / a ratio decreases, causing deterioration of dielectric properties such as insulation resistance and dielectric loss, and further causing a decrease in capacitance and variations.

  The molar ratio (Ba / Ti) is measured using a fluorescent X-ray analyzer (for example, Simultix 12 manufactured by Rigaku Corporation).

  In addition, when the molar ratio (Ba / Ti) of the barium titanate powder synthesized by a wet method such as hydrothermal synthesis exceeds 1.000, the c / a ratio is lowered. Residual hydroxyl groups can be removed and the c / a ratio can be increased by a method of re-heat-treating the hydroxyl groups incorporated in the air in the atmosphere. However, in this method, voids are formed in the part where the hydroxyl group was present in the particle, so that the volume ratio that does not contribute to the dielectric constant increases and the dielectric constant is lowered. Therefore, the molar ratio (Ba / Ti ) Is preferably 1.000 or less.

Next, the coefficient of variation CV indicating the spread of the particle size of the ceramic powder is desirably 35% or less. More desirably, it is 25% or less.
If the coefficient of variation CV value of the ceramic powder exceeds 35%, the spread of the particle size distribution becomes large and it cannot be said that the particle size distribution is sharp. Therefore, when the average particle size is small, the gap between the substantially spherical nickel powder particles When the average particle size is larger than that, it becomes difficult to enter uniformly between the contact points of approximately spherical nickel powder particles, and the conductive paste is sintered. The problem arises that the effect of delaying the starting temperature to the sintering start temperature of the ceramic layer is weakened.

  On the other hand, when the coefficient of variation CV value of the ceramic powder is 35% or less, it becomes easy to enter between the contact points of the substantially spherical nickel powder particles, a high dry film density is obtained, and the sintering start temperature of the conductive paste is further set to the ceramic layer. The effect of delaying to the sintering start temperature becomes stronger. For this reason, the continuity of the internal electrodes is improved, and variations in capacitance can be suppressed.

  The coefficient of variation CV value is measured using a known particle size analyzer (for example, “Microtrack” manufactured by Nikkiso Co., Ltd.), and the standard deviation is defined as a measure of the distribution width of the measured particle size distribution. , From the calculation formula shown in Equation 3.

Here, d 86% is the particle size (μm) at the point where the cumulative curve is 86%, and d 16% is the particle size (μm) at the point where the cumulative curve is 16%.

The aspect ratio, which is the ratio of the major axis diameter to the minor axis diameter of the ceramic powder, is desirably 1.15 or less.
If the aspect ratio is larger than 1.15, it is difficult to increase the dry film density of the dry film of the conductive paste because it is difficult to enter the space between the substantially spherical nickel powder particles when the average particle diameter is small. The amount of powder added cannot be minimized, and as a result, the sintering of the nickel powder during firing cannot be delayed, making it difficult to reduce the thickness of the internal electrode layer.

  The aspect ratio is obtained by measuring the particle diameter from 100 particles in a photograph (magnification: 50,000 times) observed using a scanning electron microscope (manufactured by Hitachi, SEM S-4800).

  The content of the ceramic powder is desirably 3 to 25 parts by weight with respect to 100 parts by weight of the conductive metal powder. More desirably, it is 5 to 15 parts by weight.

If the content of the ceramic powder is less than 3 parts by weight, for example, the sintering of the nickel powder cannot be controlled, the mismatch of the sintering shrinkage behavior of the internal electrode layer and the dielectric layer becomes significant, and the internal electrode is further sintered. Since it starts at a low temperature and the difference in sintering temperature between the internal electrode layer and the dielectric layer becomes large, firing cracks are generated.
On the other hand, if the content of the ceramic powder exceeds 25 parts by weight, for example, the thickness of the dielectric layer expands due to sintering with the ceramic particles in the dielectric layer from the internal electrode layer, resulting in a composition shift. It adversely affects electrical characteristics such as a decrease in rate.

[Organic solvent]
The organic solvent used in the conductive paste of the present invention is a component that dissolves the resin component and has a function of stably dispersing inorganic components such as conductive metal powder in the paste. When applied (printed) onto a circuit board or the like, these powders are spread evenly and have a function of dissipating into the atmosphere by firing.

  Such organic solvents include terpineol (α, β, γ and mixtures thereof), dihydroterpineol, octanol, decanol, tridecanol, dibutyl phthalate, butyl acetate, butyl carbitol, butyl carbitol acetate, dipropylene glycol monomethyl Ether or the like can be used.

[binder]
As the binder resin for the conductive paste, one or more organic resins such as ethyl cellulose, ethyl cellulose, nitrocellulose, acrylic and polyvinyl butyral are selected and used.
The molecular weight is based on the premise that the molecular weight is dissolved in the organic solvent to be used, but a resin having a molecular weight of 20,000 to 200,000 is preferably used. The amount of resin in the paste is desirably 1.0 to 5.0 wt%, and more preferably 2.0 to 4.0 wt%. If it is less than 1.0 wt%, it is difficult to obtain a viscosity suitable for screen printing, and if it exceeds 5.0 wt%, the amount of residual carbon increases at the time of binder removal, which causes delamination of the laminated chip, which is not preferable.

  In order to further adjust the viscosity, aromatic hydrocarbons and aliphatic hydrocarbons are used as diluents. For example, an aliphatic hydrocarbon such as decane, nonane, heptane, etc., a melting point of 190 to 350 ° C., preferably an aliphatic higher alcohol having 8 to 20 carbon atoms, such as decanol, octanol, etc., or an aromatic hydrocarbon such as benzene Toluene or the like can be used alone or in combination, and functions to adjust the drying speed after printing the conductive paste or to impart appropriate viscosity characteristics to the conductive paste.

  Moreover, you may add a well-known additive with conductive paste, such as an antifoamer, a dispersing agent, a plasticizer, surfactant, a thickener, to an electrically conductive paste as needed.

  For producing the conductive paste, a known method such as a three-roll mill or a ball mill can be used, and the conductive paste is printed (applied) by a known screen printing.

[Dry film]
Usually, a conductive paste is applied to a green sheet or the like by screen printing and dried by heating to remove the organic solvent and the binder, thereby forming a dry film for internal electrodes having a predetermined pattern. The dry film thickness is controlled by controlling the thickness of the screen pattern. Furthermore, excessive carbon remaining in the electrode film, that is, residual carbon derived from organic solvents and binders deteriorates electrical characteristics after firing, such as capacitance, dielectric loss, and dielectric breakdown voltage, and thus dry. The amount of residual carbon in the film is also controlled.

In the present invention, the dry film density of the conductive paste is preferably 5.3 g / cm 3 or more, and more preferably 5.5 g / cm 3 or more.
Although the dry film density is desirably high, the true density of metallic nickel cannot be exceeded. When the dry film density is lower than 5.3 g / cm 3 , a dense electrode film cannot be obtained at the time of firing, causing problems such as capacity loss.

The dry film density is measured by printing a nickel powder paste on a PET film so as to have a film thickness of 30 μm in an area of 5 × 10 cm and then drying in air at 120 ° C. for 40 minutes. The dried nickel powder paste dry film is cut into 1 × 1 cm, the thickness and weight are measured, and the dry film density is calculated by the calculation formula shown in Equation 4.
The number of measurements was performed at 30 locations, and the average value of the obtained film densities was taken as the film density of the conductive paste.

The dry film density is measured by printing a conductive paste on a PET film. Of course, the same characteristics can be exhibited even when the conductive paste of the present invention is printed on a dielectric layer green sheet. .
Here, the dry film density is the density after the conductive paste is dried.

In the present invention, the average surface roughness and the maximum protrusion height are measured by applying a nickel paste on a glass substrate using an applicator (gap thickness 5 μm), and then drying in air at 120 ° C. for 5 minutes. A dry film of about 3 μm is obtained. Next, the protrusion on the surface of the dried film is measured by an optical method, that is, a phase shift interference method.
Specifically, the sample and the reference mirror are irradiated with light from a light source limited to a specific wavelength region, and the surface state is observed by interference fringes of the light irradiated on the sample and the reference mirror. More specifically, the surface state is observed from the interference fringes of the light by moving the sample in the direction in which the light is irradiated every quarter wavelength. For example, the maximum protrusion height of the dry film is measured using an optical interference type surface shape measuring device (NT-1100 manufactured by WYCO).

The maximum protrusion height is measured by applying the conductive paste of the present invention to a glass substrate, but the same characteristics are exhibited even when the conductive paste of the present invention is printed on a dielectric layer green sheet. Of course.
The maximum protrusion height of the present invention is the sum of the maximum value of the peak height of the contour curve and the maximum value of the valley depth in an arbitrary measurement area, that is, not the R max value, but the peak height of the contour curve in an arbitrary measurement area. The value indicates the maximum value.

[Examples and Comparative Examples]
Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. The scope of the present invention is not limited by the examples.

  Conductive paste is manufactured by three rolls, and the dry film density and maximum protrusion height of this paste are evaluated as the dry film, and the capacitance variation (CV value; standard of capacitance) of the multilayer ceramic capacitor as the electrical property evaluation. Deviation / average capacitance) and dielectric loss were measured.

(1) Production of Conductive Paste The component composition of the conductive paste was 45 wt% of nickel powder (average particle size 0.4 μm and 0.2 μm), and the ceramic powder shown in Table 1 (average particle size 0.12 μm, 0.1 μm). 07 μm, 0.05 μm, 0.04 μm, 0.02 μm) was 9.0 wt% or 4.5 wt%, the vehicle was 2.8 wt%, and the organic solvent was 43.2 wt% or 47.7 wt%.
The vehicle was made of ethyl cellulose (molecular weight 70000): 13 wt% as a resin component and terpineol: 87 wt% as an organic solvent and heated to 60 ° C.
The carbon content of the nickel powder was 0.04% in all cases.

(2) Production of Multilayer Ceramic Capacitor A multilayer ceramic capacitor was produced using the conductive paste produced in (1), and the electrical characteristics of capacitance and dielectric loss were evaluated.
A conductive paste was printed on a raw dielectric green sheet having a thickness of 3 μm, dried, and then 20 layers were stacked, pressure-bonded and cut to produce a chip of 3.2 × 1.6 mm size. After debinding the chip, the chip was baked at 1260 ° C. in a weak reducing atmosphere. After firing, 50 multilayer ceramic capacitors in which terminal electrodes were applied to the chip were produced.
The electrical characteristics of the capacitance C and dielectric loss tan δ were evaluated using the produced multilayer ceramic capacitor. The measurement results are shown in Table 2.
The internal electrode thickness after chip firing was 1.3 μm, and the dielectric layer thickness was 2 μm.

  The capacitance C (unit: μF) was measured at 25 ° C. with a digital LCR meter (4278A manufactured by YHP) under the conditions of applying a frequency of 1 kHz and a measurement voltage of 1 Vrms. The case where the variation (CV value) of the capacitance C was 2.5% or less was regarded as good.

  The dielectric loss tan δ (unit:%) was measured at 25 ° C. using a digital LCR meter (4278A manufactured by YHP) under the conditions of applying a frequency of 1 kHz and a measurement voltage of 1 Vrms. A case where the dielectric loss tan δ was 3.5% or less was regarded as good.

Table 1 shows the characteristics of various ceramic powders having different average particle sizes, lattice constant ratios (tetragonal) (c / a), molar ratios (Ba / Ti), coefficient of variation CV values, and aspect ratios.
Ceramic powders A, B, C, and D in Table 1 satisfy the scope of the present invention, but ceramic powders E, F, G, H, and I have some characteristics outside the scope of the present invention. is there.

  As is apparent from Table 2, it can be seen that the present invention example 1 to the present invention example 4 that satisfy all the scope of the present invention are excellent in dry film evaluation and multilayer ceramic capacitor electrical characteristics.

  On the other hand, in Comparative Example 1, although the influence of the carbon content on the dry film density is unknown, the carbon content of the nickel powder used is 0.09 wt%, greatly exceeding the range of 0.06% of the present invention. Therefore, compared with Example 4 using the same ceramic powder D, the dry film density is greatly reduced, and further, the variation in capacitance due to residual carbon remaining in the electrode film after firing It can be seen that the dielectric loss has also deteriorated.

In Comparative Example 2, since the average particle size of the ceramic powder used is as large as 0.12 μm, it becomes difficult to enter between the contact points of the substantially spherical nickel powder particles, and the dry film density is greatly reduced to 4.8 g / cm 3. It has been. In addition, the maximum protrusion height is 2.0 μm due to a decrease in dry film density and an agglomerated powder of ceramic powder, and as a result, variations in capacitance and dielectric loss are worsened.

  In Comparative Example 3, since the lattice constant ratio (c / a) of the ceramic powder to be used is as small as 1.0018, the co-material in the internal electrode layer is released into the dielectric layer molded body during firing, and the added fine particles This co-material is involved in the sintering of the dielectric layer, and the dielectric loss is increased.

  In Comparative Example 4, the molar ratio Ba / Ti of the ceramic powder used is as large as 1.042, the dispersion of the particle size distribution (CV value) is increased, and the hydroxyl groups existing in the crystal lattice of barium titanate are increased. For this reason, the loss on ignition is increased, so that the lattice constant ratio (c / a) is decreased, and the dielectric loss and the variation in capacitance are worsened.

  In Comparative Example 5, since the coefficient of variation CV value of the ceramic powder used is as large as 40%, it becomes difficult to enter the gaps between the substantially spherical nickel powder particles, resulting in a decrease in the dry film density and the firing of the conductive paste. The effect of delaying the sintering start temperature to the sintering start temperature of the ceramic layer is weakened, and the variations in dielectric loss and capacitance are exacerbated.

  In Comparative Example 6, since the aspect ratio of the ceramic powder to be used is larger than 1.21 and 1.15, it is difficult for the ceramic powder to enter the gaps between the substantially spherical nickel powder particles, and the dry film of the dry film of the conductive paste It is difficult to increase the density, and the function of delaying the sintering of the nickel powder during firing is weakened, and the dielectric loss and the variation in capacitance are worsened.

  From Table 2, the dispersion of the capacitance (CV value) regardless of the lack of particle size, lattice constant ratio (c / a), molar ratio Ba / Ti, variation coefficient CV value, aspect ratio of ceramic powder used It can be seen that the dielectric loss cannot be controlled within the specification range of the present invention.

Claims (4)

  1. A conductive paste for multilayer ceramic electronic parts comprising at least ceramic powder and conductive metal powder,
    The ceramic powder has 1) an average particle diameter of 0.01 to 0.1 μm, 2) a lattice constant ratio (c / a) of c-axis length to a-axis length of crystal lattice of 1.0020 or more, and 3) barium. And the titanium molar ratio (Ba / Ti) is 0.995 or more and 1.000 or less, 4) the particle size variation coefficient CV is 35% or less, and 5) the major axis to minor axis ratio (aspect ratio) is 1.15. The following barium titanate powder,
    The conductive metal powder is 1) a nickel powder having an average particle diameter larger than the average particle diameter of the ceramic powder and an average particle diameter of 0.4 μm or less, and 2) a carbon content of 0.06 wt% or less. Conductive paste for ceramic electronic parts.
  2.   2. The conductive paste for multilayer ceramic electronic components according to claim 1, wherein the ceramic powder is 3 to 25 parts by weight when the weight of the conductive metal powder is 100 parts by weight.
  3. A dry film having a film density of 5.3 g / cm 3 or more and a maximum protrusion height of 1.5 μm or less obtained by printing and drying the conductive paste for multilayer ceramic electronic components according to claim 1 or 2.
  4.   A multilayer ceramic capacitor having a thickness of an internal electrode layer using the dry film according to claim 3 of 1.5 μm or less.
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CN102379017A (en) 2010-04-06 2012-03-14 Nec东金株式会社 Electricity accumulator device
KR101218979B1 (en) * 2010-12-10 2013-01-04 삼성전기주식회사 A manufacturing method of perovskite powder, perovskite powder and laminated ceramic electronic part manufactured by the same
KR20120066942A (en) * 2010-12-15 2012-06-25 삼성전기주식회사 Conductive paste composition for inner electrode, multilayer ceramic capacitor using the same and a manufacturing method thereof
KR20130005518A (en) * 2011-07-06 2013-01-16 삼성전기주식회사 Conductive paste composition for internal electrode and multilayer ceramic electronic component
KR101952843B1 (en) * 2011-07-07 2019-02-27 삼성전기주식회사 Conductive paste composition for internal electrode and multilayer ceramic electronic component
KR101813284B1 (en) * 2011-09-08 2017-12-29 삼성전기주식회사 Conductive paste and multi-layer ceramic electronic parts fabricated by using the same
KR101823160B1 (en) * 2012-04-26 2018-01-29 삼성전기주식회사 Laminated ceramic electronic parts and manufacturing method thereof
JP5566434B2 (en) * 2012-09-25 2014-08-06 太陽誘電株式会社 Multilayer ceramic capacitor
KR102029616B1 (en) * 2019-02-19 2019-10-08 삼성전기주식회사 Conductive paste composition for internal electrode and multilayer ceramic electronic component

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