JP2005101302A - Laminated ceramic electronic component and method of manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing laminated ceramic electronic component by which the occurrence of delamination is prevented in a thin highly-laminated ceramic electronic component, even when conductor layers formed by the thin film forming method are used by improving the degreasing properties of the conductor layers at baking time, and a laminated ceramic electronic component manufactured by the method. <P>SOLUTION: The method of manufacturing laminated ceramic electronic component includes steps of: baking a molded laminate provided with the conductor patterns in a green laminate constituted by laminating the ceramic green sheets containing at least ceramic powder and an organic binder upon another; and forming the main body of an electronic component having ceramic layers and conductor layers respectively formed from a plurality of ceramic green sheets and conductor patterns formed by the thin film forming method. The ceramic green sheets contain the organic binder at a rate of 5-12 pts. mass to 100 pts. mass ceramic powder. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a method for producing a multilayer ceramic electronic component and a multilayer ceramic electronic component, and in particular, a ceramic layer and a conductor layer are thin layers, multilayer multilayer ceramic substrates, multilayer inductors, multilayer piezoelectric elements, and multilayer ceramic capacitors. The present invention relates to a method for manufacturing a multilayer ceramic electronic component and a multilayer ceramic electronic component manufactured by the method.

In recent years, multilayer ceramic capacitors, which are representative examples of multilayer ceramic electronic components, have been made thinner in order to reduce the size and increase the capacity of ceramic layers and conductor layers, and in particular, vapor deposition as conductor layers. Alternatively, a metal film obtained by a thin film forming method such as a plating method and having a lamination number of 250 or more has been developed (for example, Patent Document 1). Usually, in a ceramic green sheet for forming such a multilayer ceramic electronic component, according to the following Patent Document 2, in order to increase the adhesion of the laminate, a large amount of organic binder is used with respect to 100 parts by mass of the ceramic powder. Is used.
JP 2000-243650 A JP-A-1-226130

  However, as in Patent Document 1, when the number of ceramic layers is increased and a metal film having a higher coverage on the ceramic layer than the conductor paste is used as the conductor layer, the ceramic green sheet used is If many binders are included as in Patent Document 2, it is difficult to degrease the binder in the ceramic green sheet in the firing process, and such residual carbon causes delamination inside the multilayer ceramic capacitor. There was a problem that it became easier.

  Accordingly, the present invention provides a multilayer ceramic electronic component that can improve degreasing properties during firing and prevent delamination even when a conductor layer obtained by a thin film forming method is used in a multilayer ceramic electronic component having a thin layer and a highly laminated layer. It is an object of the present invention to provide a method for manufacturing a component and a multilayer ceramic electronic component manufactured using the method.

  In order to achieve the above object, a method for producing a multilayer ceramic electronic component according to the present invention includes a conductor produced by thin film formation in a green laminate formed by laminating a plurality of ceramic green sheets containing at least ceramic powder and an organic binder. Firing a multilayer molded body having a pattern, and forming an electronic component body having a ceramic layer and a conductor layer formed from the ceramic green sheet and the conductor pattern, respectively. In the ceramic green sheet, the amount of the organic binder with respect to 100 parts by mass of the ceramic powder is 5 to 11 parts by mass.

  In the multilayer green body in the method for producing the multilayer ceramic electronic component, the ceramic green sheet is formed by applying a ceramic slurry on a support on which a conductor pattern is formed, and drying the ceramic slurry. It is desirable to form a conductive pattern embedded sheet body formed so as to be embedded in, and to laminate a plurality of the conductive pattern embedded sheets formed by peeling the support from the conductive pattern embedded sheet body, In particular, the laminated molded body includes (a) a step of preparing a ceramic green sheet having no conductive pattern, and (b) a step of bonding the conductive pattern side of the conductive pattern embedded sheet on the ceramic green sheet; (C) a step of peeling the support from the conductor pattern-embedded sheet, and (d) (b), The step c) repeatedly stacked several times, the uppermost layer, further the ceramic green laminating the sheets, it is desirable that formation of.

  In the method for producing a multilayer ceramic electronic component, the conductor pattern is produced by at least one thin film forming method selected from the group consisting of sputtering, vapor deposition, and plating, the thickness is 1.0 μm or less, and the ceramic layer is coated. It is desirable that the rate is 60% or more, the thickness of the ceramic layer is 3 μm or less, and the number of layers is 100 or more.

  Furthermore, the organic binder used for the manufacturing method of the multilayer ceramic electronic component is a mixture of a first binder having a polymerization degree of 300 or less and a second binder having a polymerization degree of 1000 or more, and the first binder ( It is desirable that the mass ratio between B1) and the second binder (B2) satisfies the relationship B1 / B2 ≧ 1.0.

  The multilayer ceramic electronic component manufactured by the manufacturing method of the present invention is connected to an electronic component body in which ceramic layers and conductor layers are alternately stacked, and the conductor layer led to the end face of the electronic component body. A multilayer ceramic electronic component comprising external electrodes, wherein the electronic component body is formed by the above-described method for manufacturing a multilayer ceramic electronic component.

  According to such a manufacturing method, the amount of carbon remaining in the degreasing step is reduced by reducing the binder amount to 5 to 11 parts by mass with respect to 100 parts by mass of the ceramic powder of the organic binder in the ceramic green sheet. And delamination due to residual carbon in the firing step can be suppressed.

  In particular, in the present invention, as the organic binder constituting the ceramic green sheet, two types of organic binders having different degrees of polymerization are mixed, that is, the first binder having a low degree of polymerization increases the plasticity and adhesiveness. On the other hand, by improving the shape retention by the second binder having a high degree of polymerization, it is possible to improve the degreasing property as well as the flexibility of the laminated molded body, thereby reducing the amount of the binder between the conductor pattern and the ceramic green sheet. Delamination due to poor adhesion can be suppressed.

Hereinafter, a method for producing a multilayer ceramic electronic component of the present invention and a multilayer ceramic electronic component obtained by using the method will be described in detail by taking a multilayer ceramic capacitor as an example. First, a flexible support, for example, on a PET film In addition, a plurality of rectangular conductor patterns are formed by at least one thin film forming method selected from the group consisting of electroplating, electroless plating, vapor deposition, and sputtering. As the thin film forming method in this case, an electroplating method is preferable because it can be formed in a large area at a low cost. In addition, as the metal species of the conductor pattern, for example, at least one metal selected from the group of Ni, Cu, Ag, Ag—Pd, and the like is preferable. Base metals are preferable in terms of enabling firing and low cost, and Ni is more preferable. The conductor pattern at this time may be formed by previously forming a conductor pattern on a metal substrate by, for example, electroplating and transferring it onto a PET film.

Next, for example, a ceramic slurry is prepared by mixing BaTiO ₃ based ceramic powder, various sintering aids, an organic binder, and a solvent.

  Here, the organic binder used in the present invention is a mixture of a first binder having a polymerization degree of 300 or less and a second binder having a polymerization degree of 1000 or more, and the first binder (B1) and the second binder. It is desirable that the mass ratio with (B2) be in the relationship of B1 / B2 ≧ 1.0, particularly the B1 / B2 ratio is in the range of 3 to 4.5. The average particle size of the ceramic powder is preferably submicron or less, preferably 0.5 μm or less, for the reason of thinning the ceramic green sheet.

  Next, the ceramic slurry is coated on the support on which the conductor pattern is formed, and a conductor pattern embedded sheet body is formed in which the conductor pattern is embedded in a ceramic green sheet formed by drying the ceramic slurry. To do.

  Here, the ceramic green sheet used for forming the multilayer ceramic electronic component of the present invention is 100 parts by mass of ceramic powder because it improves adhesion when the ceramic green sheets are laminated and increases the degreasing property of the organic binder. On the other hand, it is important that the amount of the organic binder is 5 to 11 parts by mass, particularly 8 to 9 parts by mass.

  Further, the conductor pattern has a thickness of 1 μm or less, particularly 0.7 μm or less, and a coverage ratio of 60% or more and 80% or more with respect to the ceramic green sheet in the shape of the electronic component main body of the present invention formed after firing. It is desirable.

  Next, a laminated molded body is formed using the conductor pattern-embedded sheet body of the present invention.

  First, a predetermined number of ceramic green sheets having no conductor pattern are laminated as an outer cover sheet on the lower layer side. Next, after adhering the conductor pattern side of the conductor pattern embedded sheet body to the upper surface, the PET film as a support is peeled from the conductor pattern embedded sheet body. This process of laminating the conductive pattern embedded sheet body and peeling the support body was repeated a predetermined number of times.Next, on the upper surface side of the laminated body, again, as an external cover sheet, a ceramic green sheet having no conductive pattern was placed on the lower layer side The same number of sheets are laminated and heated under pressure to form the laminated molded body of the present invention.

  Next, this laminated molded body is cut at a predetermined position to form an electronic component body molded body, and then degreased and fired at a predetermined temperature condition to form the electronic component body of the present invention.

Here, the number of stacked layers in the present invention is preferably 100 layers or more, particularly preferably 200 layers or more, and more preferably 300 layers or more.

  Moreover, the degreasing conditions of the electronic component body molded body in the production method of the present invention are as follows: the atmosphere is air, the temperature is 200 to 400 ° C., and the heating rate is 5 ° C./h or more. In the case where Ni is used, the temperature is in the range of 1200 to 1300 ° C.

  The thickness of the ceramic layer constituting the electronic component main body thus fabricated, here, the thickness of the ceramic layer in the region in contact with the conductor layer is preferably 3 μm or less, particularly 2 μm or less. Next, an external electrode paste is attached and baked on the end surface from which the conductor layer of the electronic component main body is derived to obtain a multilayer ceramic capacitor provided with external electrodes. That is, in the multilayer ceramic electronic component of the present invention, the external electrode 3 is formed on the end surface of the electronic component body 1. The electronic component body 1 is configured by alternately laminating ceramic layers 5 and conductor layers 7. Here, the conductor layers 7 are alternately led out to the end face of the electronic component main body 1.

  Next, examples of the present invention are shown below.

  First, on a flexible PET film having a thickness of 38 μm or less, a conductor pattern mainly composed of Ni having a rectangular shape and a predetermined dimension was formed by electroplating. The thickness of this conductor pattern was 0.5 μm, and the coverage in the electronic component body after firing was 80%.

Next, BaTiO ₃ powder having an average particle size of 0.3 μm is used as the ceramic powder for the ceramic slurry for the ceramic green sheet of the present invention, and SiO ₂ having an average particle size of 0.6 μm is used as a sintering aid. Glass powder as a main component was used.

  Here, a mixed solvent in which toluene and ethanol were mixed at a weight ratio of 1: 1 was used as a solvent for the ceramic slurry. The organic binder is polyvinyl butyral, and a first binder having a polymerization degree of 300 and a second binder having a polymerization degree of 1700 are prepared so as to have a ratio shown in Table 1, and the ceramic powder and the solvent are mixed with a predetermined amount. A ceramic slurry was prepared by mixing at a ratio of

  Next, the above-mentioned ceramic slurry is applied on a PET film on which a conductor pattern is formed by a doctor blade method, and a conductor pattern-embedded sheet body having ceramic green sheets with thicknesses of 2 μm, 3 μm, and 4 μm in contact with the conductor pattern Was made.

  Next, the conductive pattern embedded sheet was passed between metal rolls heated to 40 ° C. to 50 ° C., and calendered.

  Next, the conductive pattern-embedded sheet body is laminated, then the carrier film is peeled off, 300 layers are laminated, and 20 layers of outer cover sheets are laminated on the upper and lower surfaces thereof to form the laminated molded body of the present invention. Produced.

  Next, the laminated molded body is cut to produce an electronic component main body molded body, degreased under conditions of atmospheric air, 300 ° C., and heating rate of 7 ° C./h, and fired in a reducing atmosphere at a temperature of 1260 ° C. To obtain an electronic component body.

  Next, an external electrode paste was applied to both end faces of the capacitor body and baked to form external electrodes, thereby producing a multilayer ceramic capacitor having a size of 3.2 mm in length and 2.5 mm in width.

  For evaluation of structural defects, the delamination occurrence rate was determined for 100 multilayer ceramic capacitors after firing, and cracks were generated by performing a solder thermal shock test at 280 ° C. on the same number of samples with no defects after firing. Rate was evaluated.

On the other hand, as a comparative example, a sample using a ceramic green sheet having an organic binder content outside the range of the present invention was produced with the same configuration as the sample of the present invention, and the same evaluation as the present invention was performed. These results are shown in Table 1.

  As is clear from the results in Table 1, the sample No. of the present invention in which the binder amount was 5 to 11 parts by mass with respect to 100 parts by mass of the ceramic powder. 1 to 11, the occurrence rate of delamination after firing was 5% or less, and the occurrence rate of cracks after the solder thermal shock test was 3% or less. In particular, the sample No. 1 was adjusted so that the binder content was 8 to 8 parts by mass and the ratio B1 / B2 between the first binder (B1) and the second binder (B2) constituting the binder was in the range of 3 to 4.5. 5 to 10, the delamination after firing was 1% or less, and 0% in the thermal shock resistance test.

  On the other hand, sample No. In Nos. 12 and 13, delamination occurred frequently after firing and after the thermal shock test.

It is a schematic sectional drawing which shows the multilayer ceramic capacitor of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Effective dielectric part 3 External cover dielectric layer 5 External electrode 7 Dielectric ceramic layer 9 Internal electrode layer

Claims (9)

In a green laminate formed by laminating a plurality of ceramic green sheets containing at least ceramic powder and an organic binder, a laminate molded body having a conductor pattern produced by a thin film forming method is fired, and the ceramic green sheet and the conductor are fired. In the method for producing a multilayer ceramic electronic component comprising a step of forming an electronic component body having a ceramic layer and a conductor layer, each formed from a pattern, the ceramic green sheet has an amount of the organic binder with respect to 100 parts by mass of the ceramic powder. The manufacturing method of the multilayer ceramic electronic component characterized by being 5-11 mass parts. The multilayer molded body is a ceramic green formed by forming a conductor pattern on the surface of a support, applying a ceramic slurry on the support on which the conductor pattern is formed, and drying the ceramic slurry. Forming a conductive pattern embedded sheet formed to be embedded in the sheet, and laminating a plurality of the conductive pattern embedded sheets formed by peeling the support from the conductive pattern embedded sheet; The method for producing a multilayer ceramic electronic component according to claim 1. Laminated molded body is
(A) preparing a ceramic green sheet having no conductor pattern;
(B) adhering the conductor pattern side of the conductor pattern-embedded sheet on the ceramic green sheet;
(C) a step of peeling the support from the conductive pattern embedded sheet;
(D) The steps of (b) and (c) are repeated a plurality of times, and the ceramic green sheet is further laminated on the uppermost layer. Manufacturing method for ceramic electronic components. 4. The method for producing a multilayer ceramic electronic component according to claim 1, wherein the conductor pattern is produced by at least one thin film forming method selected from the group consisting of sputtering, vapor deposition, and plating. 5. The method for producing a multilayer ceramic electronic component according to claim 1, wherein the thickness of the conductor pattern is 1.0 μm or less and the coverage of the ceramic layer is 60% or more. 6. The method for producing a multilayer ceramic electronic component according to claim 1, wherein the thickness of the ceramic layer is 3 [mu] m or less. The method for producing a multilayer ceramic electronic component according to claim 1, wherein the number of layers is 100 or more. The organic binder is a mixture of a first binder having a degree of polymerization of 300 or less and a second binder having a degree of polymerization of 1000 or more, and the mass ratio of the first binder (B1) and the second binder (B2). Satisfies the relationship of B1 / B2 ≧ 1.0. The method for producing a multilayer ceramic electronic component according to any one of claims 1 to 7, wherein: A multilayer ceramic electronic component comprising: an electronic component body in which ceramic layers and conductor layers are alternately stacked; and an external electrode connected to the conductor layer led to an end surface of the electronic component body, A multilayer ceramic electronic component, wherein the electronic component main body is formed by the method for producing a multilayer ceramic electronic component according to any one of claims 1 to 8.

Images