Multilayer ceramic electronic component and its manufacturing method

Abstract

To provide a multilayer ceramic electronic component and a manufacturing method thereof with high capacity even under low AC voltage.SOLUTION: A multilayer ceramic electronic component 100 includes a plurality of internal electrode layers 12 facing each other, and a plurality of dielectric layers 11 that are sandwiched between the internal electrode layers 12, that contain barium zirconate titanate as a main component, contains 2 at% or more and 14 at% or less of zirconium relative to titanium, has a Curie point of less than 85°C, and has an average thickness of 1 μm or less.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a multilayer ceramic electronic component and a method for manufacturing the same. [Background technology]

[0002] Multilayer ceramic electronic components are used in high-frequency communication systems, such as mobile phones, etc. For example, multilayer ceramic capacitors are used to remove noise (see, for example, Patent Documents 1 to 5). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2007-145649 [Patent Document 2] Re-tabled publication No. 2008-105240 [Patent Document 3] Re-table No. 2010-047181 [Patent Document 4] Japanese Patent Application Laid-Open No. 2018-107413 [Patent Document 5] Japanese Patent Application Publication No. 2019-192862 Summary of the Invention [Problem to be solved by the invention]

[0004] Mobile products such as mobile phones require smaller (thinner) and larger capacity multilayer ceramic electronic components.

[0005] As various electronic devices become more energy-efficient, the AC (alternating current) input level to multilayer ceramic electronic components is decreasing. However, as the AC input level decreases, the capacitance of the multilayer ceramic electronic components also decreases. This poses the problem of reduced performance in low-voltage circuits. To efficiently remove weak noise, there is a demand for multilayer ceramic electronic components whose capacitance does not decrease under low AC driving.

[0006] The present invention has been made in view of the above-mentioned problems, and has as its object to provide a multilayer ceramic electronic component that has high capacitance even under low AC voltage, and a method for manufacturing the same. [Means for solving the problem]

[0007] A multilayer ceramic electronic component according to the present invention comprises a plurality of internal electrode layers facing each other, and a plurality of dielectric layers sandwiched between the plurality of internal electrode layers, each containing barium zirconate titanate as a main component, containing 2 at % or more and 14 at % or less of zirconium relative to titanium, having a Curie point lower than 85°C, and having an average thickness of 1 μm or less.

[0008] In the above-described multilayer ceramic electronic component, the plurality of dielectric layers may contain zirconium in an amount of 8 at % or less relative to titanium.

[0009] In the above-described multilayer ceramic electronic component, the plurality of dielectric layers may have a Curie point of 80° C. or lower.

[0010] In the above-described multilayer ceramic electronic component, the plurality of dielectric layers may have a Curie point of 50° C. or less.

[0011] The monolithic ceramic electronic component may have a capacitance at 10 mVrms greater than that at 1 Vrms under an AC voltage.

[0012] In the above-described multilayer ceramic electronic component, the plurality of dielectric layers may further contain manganese, silicon, or a rare earth element.

[0013] Another multilayer ceramic electronic component according to the present invention includes a plurality of internal electrode layers facing each other and a plurality of dielectric layers sandwiched between the plurality of internal electrode layers, the plurality of dielectric layers forming a capacitance section in a region where the plurality of internal electrodes face each other, the plurality of dielectric layers in the capacitance section being mainly composed of barium zirconate titanate, containing zirconium in a range of 2 at % to 14 at % based on the total of titanium and zirconium, the plurality of dielectric layers having a Curie point lower than 85°C and an average thickness of 1 μm, and external electrodes provided on any surface of the element body and electrically connected to some of the plurality of internal electrodes.

[0014] In the other multilayer ceramic electronic component, in the capacitive section, the plurality of dielectric layers may contain zirconium in an amount of 8 at % or less with respect to the total of titanium and zirconium.

[0015] In the other multilayer ceramic electronic component, in the capacitance section, the plurality of dielectric layers may have a Curie point of 80° C. or lower.

[0016] In the other multilayer ceramic electronic component, in the capacitive section, the plurality of dielectric layers may have a Curie point of 50° C. or lower.

[0017] The other multilayer ceramic electronic component may have a capacitance at 10 mVrms greater than that at 1 Vrms under an AC voltage.

[0018] In the other multilayer ceramic electronic component, in the capacitive section, the plurality of dielectric layers may further contain manganese, silicon, or a rare earth element.

[0019] A method for producing a multilayer ceramic electronic component according to the present invention includes the steps of: forming dielectric green sheets containing, as a main component of ceramic, barium zirconate titanate, the ceramic containing zirconium at a concentration of 2 at % or more and 14 at % or less relative to the total of titanium and zirconium; forming internal electrode patterns on the dielectric green sheets using a conductive paste; forming a laminate by stacking a plurality of the dielectric green sheets on which the internal electrode patterns have been formed; firing the laminate to form dielectric layers and internal electrode layers having an average thickness of 1 μm or less; and annealing the dielectric layers to heat treat them so that their Curie points are less than 85°C.

[0020] In the annealing step of the above manufacturing method, the heat treatment may be performed at an ambient temperature of 1100° C. to 1200° C. for 30 minutes to 3 hours.

[0021] The manufacturing method may include a step of applying a metal paste to contact the ends of the internal electrode patterns before firing the laminate. [Effects of the Invention]

[0022] According to the present invention, it is possible to provide a multilayer ceramic electronic component that has high capacitance even under low AC voltage, and a method for manufacturing the same. [Brief explanation of the drawings]

[0023] [Figure 1] FIG. 2 is a partial cross-sectional perspective view of a multilayer ceramic capacitor. [Figure 2] FIG. 2 is a cross-sectional view taken along line AA in FIG. [Figure 3] FIG. 2 is a cross-sectional view taken along line BB in FIG. [Figure 4] 1A to 1C are diagrams illustrating a flow of a method for manufacturing a multilayer ceramic capacitor. [Figure 5] 1(a) and 1(b) are diagrams illustrating the lamination process. [Figure 6] 1 shows the rate of change in AC voltage characteristics of Examples 1 to 4 and the comparative example. [Figure 7]FIG. 1 is a diagram showing the rate of change in AC voltage characteristics when the results of Example 1 are converted into average thicknesses of the dielectric layer (1 μm, 2 μm, 4 μm). DETAILED DESCRIPTION OF THE INVENTION

[0024] Hereinafter, embodiments will be described with reference to the drawings.

[0025] FIG. 1 is a partial cross-sectional perspective view of a multilayer ceramic capacitor 100 according to an embodiment. FIG. 2 is a cross-sectional view taken along line AA in FIG. 1. FIG. 3 is a cross-sectional view taken along line BB in FIG. 1. As illustrated in FIGS. 1 to 3, the multilayer ceramic capacitor 100 includes a laminated chip 10 having a substantially rectangular parallelepiped shape and external electrodes 20a, 20b provided on two opposing end faces of the laminated chip 10. Of the four faces of the laminated chip 10 other than the two end faces, the two faces other than the top and bottom faces in the stacking direction are referred to as side faces. The external electrodes 20a, 20b extend on the top, bottom and two side faces of the laminated chip 10 in the stacking direction. However, the external electrodes 20a, 20b are spaced apart from each other.

[0026] The multilayer chip 10 has a configuration in which dielectric layers 11 containing a ceramic material that functions as a dielectric and internal electrode layers 12 primarily composed of metal are alternately stacked. In other words, the multilayer chip 10 includes multiple opposing internal electrode layers 12 and dielectric layers 11 sandwiched between the multiple internal electrode layers 12. The edges of each internal electrode layer 12 are alternately exposed at the end face of the multilayer chip 10 where the external electrode 20a is provided and the end face where the external electrode 20b is provided. This allows each internal electrode layer 12 to be alternately electrically connected to the external electrode 20a and the external electrode 20b. As a result, the multilayer ceramic capacitor 100 has a configuration in which multiple dielectric layers 11 are stacked with the internal electrode layers 12 interposed therebetween. Furthermore, in a laminate of the dielectric layers 11 and the internal electrode layers 12, the internal electrode layer 12 is disposed as the outermost layer in the stacking direction, and the top and bottom surfaces of the laminate are covered with cover layers 13. The cover layers 13 are primarily composed of a ceramic material. For example, the cover layer 13 may have the same composition as the dielectric layer 11 or may have a different composition.

[0027] The size of the multilayer ceramic capacitor 100 is, for example, 0.25 mm in length, 0.125 mm in width, and 0.125 mm in height, or 0.4 mm in length, 0.2 mm in width, and 0.2 mm in height, or 0.6 mm in length, 0.3 mm in width, and 0.3 mm in height, or 0.6 mm in length, 0.3 mm in width, and 0.110 mm in height, or 1.0 mm in length, 0.5 mm in width, and 0.5 mm in height, or 1.0 mm in length, 0.5 mm in width, and 0.1 mm in height, or 3.2 mm in length, 1.6 mm in width, and 1.6 mm in height, or 4.5 mm in length, 3.2 mm in width, and 2.5 mm in height, but is not limited to these sizes.

[0028] The dielectric layer 11 is mainly composed of a ceramic material having a perovskite structure represented by the general formula ABO3. 3-α The ceramic material used is barium titanate zirconate. For example, the dielectric layer 11 contains 90 at % or more of barium titanate zirconate.

[0029] An additive may be added to the dielectric layer 11. Examples of additives to the dielectric layer 11 include oxides of magnesium (Mg), manganese (Mn), molybdenum (Mo), vanadium (V), chromium (Cr), rare earth elements (yttrium (Y), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), and ytterbium (Yb)), oxides containing cobalt (Co), nickel (Ni), lithium (Li), boron (B), sodium (Na), potassium (K), or silicon (Si), or glasses containing cobalt, nickel, lithium, boron, sodium, potassium, or silicon.

[0030] The main component of the internal electrode layers 12 may be a base metal such as nickel, or a noble metal.

[0031] 2, the region where the internal electrode layer 12 connected to the external electrode 20a and the internal electrode layer 12 connected to the external electrode 20b face each other is a region where capacitance is generated in the multilayer ceramic capacitor 100. Therefore, this region where capacitance is generated is referred to as a capacitance portion 14. In other words, the capacitance portion 14 is a region where adjacent internal electrode layers 12 connected to different external electrodes face each other.

[0032] The region where the internal electrode layers 12 connected to the external electrode 20a face each other without an internal electrode layer 12 connected to the external electrode 20b interposed therebetween is called the end margin 15. The region where the internal electrode layers 12 connected to the external electrode 20b face each other without an internal electrode layer 12 connected to the external electrode 20a interposed therebetween is also the end margin 15. In other words, the end margin 15 is the region where the internal electrode layers 12 connected to the same external electrode face each other without an internal electrode layer 12 connected to a different external electrode interposed therebetween. The end margin 15 is a region where no capacitance is generated. The end margin 15 may have the same composition as the dielectric layer 11 of the capacitive section 14, or a different composition.

[0033] As illustrated in Figure 3, in the laminated chip 10, the regions extending from the two side surfaces of the laminated chip 10 to the internal electrode layers 12 are referred to as side margins 16. In other words, the side margins 16 are regions provided to cover the ends of the multiple internal electrode layers 12 stacked in the above-mentioned laminated structure that extend to the two side surfaces. The side margins 16 are also regions that do not generate capacitance. The side margins 16 may have the same composition as the dielectric layer 11 of the capacitive section 14, or may have a different composition.

[0034] In general, the electric flux density of ferroelectrics responds nonlinearly to the electric field strength. Therefore, ferroelectrics exhibit a change in dielectric constant (AC voltage characteristics) with respect to the AC input level. When the electric field is small relative to the ferroelectric's coercive field, the ferroelectric cannot fully reverse its polarization, and it exhibits a low dielectric constant. When the electric field is about the same as the coercive field, a small electric field can reverse a large amount of polarization, and the ferroelectric exhibits its maximum dielectric constant. When the electric field is further increased, the polarization that can be reversed saturates and does not increase significantly in proportion to the increase in the electric field, and the ferroelectric exhibits a low dielectric constant. Therefore, the AC characteristics of multilayer ceramic capacitors using ferroelectric materials follow a progression of low capacitance → high capacitance → low capacitance as the voltage is increased from a low voltage, with a maximum peak.

[0035] The inventors discovered that adding Zr to the main ceramic component of the dielectric layer 11 improves the capacitance change rate at low voltages. While the reason for this is not fully understood, it is believed that when zirconium dissolves in barium titanate to form barium zirconate titanate (Ba(Ti,Zr)O3), the Curie point Tc decreases, which in turn reduces the coercive field, shifting the high capacitance peak toward lower electric fields. Therefore, a lower Curie point Tc is advantageous for improving AC characteristics. Furthermore, because the material becomes paraelectric at temperatures higher than the Curie point Tc, the dielectric constant is maximized at the low-voltage limit. Therefore, for multilayer ceramic capacitors with a guaranteed temperature of 85°C or less, it is desirable for the Curie point Tc to be less than 85°C.

[0036] From the viewpoint of sufficiently lowering the Curie point Tc of the dielectric layer 11, a lower limit is set for the amount of zirconium added relative to titanium. In this embodiment, the amount of zirconium added relative to titanium is set to 2 at% or more. The amount of zirconium added relative to titanium is preferably 3 at% or more, and more preferably 4 at% or more. The amount of zirconium added relative to the total amount of titanium and zirconium is the amount of zirconium added (at%) when the total amount of titanium and zirconium is 100 at%.

[0037] On the other hand, if the amount of zirconium in the dielectric layer 11 is too large, the relative dielectric constant of the dielectric layer 11 may decrease. Therefore, an upper limit is set on the amount of zirconium added relative to the total amount of titanium and zirconium. In this embodiment, the amount of zirconium added relative to the total amount of titanium and zirconium is set to 14 at% or less. The amount of zirconium added relative to the total amount of titanium and zirconium is preferably 10 at% or less, and more preferably 8 at% or less.

[0038] However, simply adjusting the dielectric composition is not sufficient to realize a multilayer ceramic capacitor with a capacitance higher than that at a normal AC voltage (e.g., 1 Vrms) under a low AC voltage (e.g., 10 mVrms). Therefore, the average thickness of the dielectric layers 11 of the multilayer ceramic capacitor 100 is reduced to 1 μm or less. By making the dielectric layers 11 thinner, the electric field strength applied to the dielectric layers 11 increases even when the same voltage is applied to the multilayer ceramic capacitor 100. Therefore, when the average thickness is 1 μm or less, the capacitance under normal measurement conditions (e.g., 1 Vrms) becomes low because the electric field is higher than the coercive field, and a multilayer ceramic capacitor 100 with a relatively large capacitance under a low AC voltage (e.g., 10 mVrms) can be realized.

[0039] The average thickness of the dielectric layer 11 can be measured by observing the cross section of the multilayer ceramic capacitor 100 with an SEM, measuring the thickness of the dielectric layer 11 at approximately 100 points, and deriving the average value of all the measurement points.

[0040] The average thickness of the dielectric layer 11 is preferably 0.9 μm or less, and more preferably 0.8 μm or less.

[0041] From the viewpoint of suppressing a decrease in capacity at low voltages, it is preferable that the Curie point Tc of the dielectric layer 11 is low. For example, the Curie point Tc of the dielectric layer 11 is preferably 80°C or lower, and more preferably 50°C or lower. The Curie point Tc of the dielectric layer 11 can be adjusted by the amount of zirconium added, but it can also be adjusted by the amount of other additives added in addition to zirconium. For example, the Curie point Tc can be further lowered by adding manganese, silicon, or a rare earth element such as holmium, terbium, dysprosium, yttrium, erbium, or ytterbium as an additive.

[0042] Next, a description will be given of a method for manufacturing the multilayer ceramic capacitor 100. FIG.

[0043] (raw powder production process) Barium titanate zirconate powder is prepared as the ceramic powder. Additives are added to the ceramic powder depending on the purpose. Examples of additives include oxides of magnesium (Mg), manganese (Mn), molybdenum (Mo), vanadium (V), chromium (Cr), rare earth elements (yttrium (Y), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), and ytterbium (Yb)), oxides containing cobalt (Co), nickel (Ni), lithium (Li), boron (B), sodium (Na), potassium (K), or silicon (Si), or glasses containing cobalt, nickel, lithium, boron, sodium, potassium, or silicon.

[0044] For example, a ceramic material is prepared by wet-mixing a compound containing an additive compound with a ceramic powder, followed by drying and pulverization. For example, the ceramic material obtained as described above may be pulverized as necessary to adjust the particle size, or may be combined with a classification process to adjust the particle size. A raw material powder is obtained by the above process.

[0045] (Lamination process) Next, a binder such as polyvinyl butyral (PVB) resin, an organic solvent such as ethanol or toluene, and a plasticizer are added to the obtained raw material powder and wet mixed. Using the obtained slurry, a dielectric green sheet 52 is coated on a substrate 51 by, for example, a die coater method or a doctor blade method, and then dried. The substrate 51 is, for example, a PET (polyethylene terephthalate) film.

[0046] Next, as illustrated in Fig. 5(a), internal electrode patterns 53 are formed on the dielectric green sheet 52. In Fig. 5(a), as an example, four layers of internal electrode patterns 53 are formed at predetermined intervals on the dielectric green sheet 52. The dielectric green sheet 52 on which the internal electrode patterns 53 are formed is defined as a lamination unit.

[0047] The internal electrode patterns 53 are made of a metal paste containing the main component metal of the internal electrode layers 12. The film formation method may be printing, sputtering, vapor deposition, or the like.

[0048] Next, while peeling off the dielectric green sheet 52 from the substrate 51, the lamination units are laminated as shown in FIG. 5(b).

[0049] Next, a predetermined number of cover sheets 54 (e.g., 2 to 10 layers) are laminated on top and bottom of the laminate obtained by laminating the lamination units, and are thermocompression bonded, and then cut to predetermined chip dimensions (e.g., 1.0 mm x 0.5 mm). In the example of Figure 5(b), cutting is performed along the dotted lines. The cover sheet 54 may have the same components as the dielectric green sheet 52, or may contain different additives.

[0050] (Firing process) The ceramic laminate thus obtained was subjected to binder removal treatment in an N2 atmosphere, after which a metal paste that would become the base layer of the external electrodes 20a, 20b was applied by dipping, and the ceramic laminate was heated in an atmosphere with an oxygen partial pressure of 10 -5 ~10 -8The mixture is then fired in a reducing atmosphere at 1100 to 1300° C. for 10 minutes to 2 hours at 1 atm. In this way, the multilayer ceramic capacitor 100 is obtained.

[0051] (Annealing process) After the firing step, an annealing treatment is performed at an ambient temperature of 1100°C to 1200°C for 30 minutes to 3 hours (for example, 2 hours at 1150°C). By performing the annealing treatment, it is possible to promote the solid dissolution of the additives in the dielectric layer 11 without causing large grain growth of the dielectric particles. This lowers the Curie point of the dielectric layer 11, making it possible to realize a multilayer ceramic capacitor 100 with excellent AC voltage characteristics. Note that the firing conditions for promoting the solid dissolution of the additives are not limited to these.

[0052] (Reoxidation treatment process) Thereafter, a re-oxidation treatment may be performed at 600°C to 1000°C in an N2 gas atmosphere.

[0053] (Plating process) Thereafter, the external electrodes 20a, 20b may be coated with a metal such as Cu, Ni, or Sn by plating.

[0054] Although the above embodiments have been described with reference to a multilayer ceramic capacitor as an example of a ceramic electronic component, the present invention is not limited to this. For example, the configurations of the above embodiments can be applied to other multilayer ceramic electronic components such as varistors and thermistors. [Example]

[0055] The multilayer ceramic capacitor according to the embodiment was fabricated and its characteristics were examined.

[0056] Example 1 A model chip of a 10-layer multilayer ceramic capacitor was fabricated. The main raw material, barium zirconate titanate (BaTi 0.98 Zr 0.02The Zr+Ti alloy was weighed and mixed with various additives and organic solvents at the specified ratio. The additives were 1 at% Ho (Ho2O3), 1 at% Mn (MnCO3), and 1 at% Si (SiO2) when (Zr+Ti) was 100 at%. Zirconia beads with a diameter of 0.5 mm were added and wet dispersion was performed. A binder was added to the resulting slurry, which was then coated onto a dielectric green sheet. A nickel paste containing the co-materials was then printed as an internal electrode pattern. The printed sheets were stacked, pressed, and cut. The binder was removed, and a metal paste for the external electrode underlayer was applied. The sheet was then fired in a reducing atmosphere. Annealing (at 1150°C for 2 hours) after firing promoted the solid solution of the additives without causing significant grain growth, lowering the Curie point Tc. The sheet was then re-oxidized and its characteristics were evaluated.

[0057] The average thickness of the dielectric layer was 1.99 μm. The average thickness of the dielectric layer was calculated by polishing the resin-embedded sample, observing it with a laser microscope, and using image analysis software. The AC voltage characteristics were measured with an LCR meter. The measurement frequency was 1 kHz.

[0058] Example 2 In Example 2, barium titanate zirconate (BaTi 0.96 Zr 0.04 O3) was used. Other conditions were the same as in Example 1. The average thickness of the dielectric layer was 1.98 μm.

[0059] Example 3 In Example 3, barium titanate zirconate (BaTi 0.92 Zr 0.08 O3) was used. Other conditions were the same as in Example 1. The average thickness of the dielectric layer was 2.02 μm.

[0060] Example 4 In Example 4, the main raw material barium titanate zirconate (BaTi 0.86 Zr 0.14O3) was used. Other conditions were the same as in Example 1. The average thickness of the dielectric layer was 2.03 μm.

[0061] (Comparative Example) In the comparative example, barium titanate (BaTiO3) was used instead of the main raw material barium titanate zirconate. The other conditions were the same as in Example 1. The average thickness of the dielectric layer was 2.01 μm. [Table 1]

[0062] FIG. 6 shows the rate of change in AC voltage characteristics for Examples 1 to 4 and the Comparative Example. The Comparative Example showed a tendency for the capacity to decrease with decreasing voltage. On the other hand, Examples 1 to 4 showed a capacity peak below 1 Vrms, and the capacity peak tended to shift toward a lower electric field as the zirconium content increased. Accordingly, the rate of capacity change at low voltages (10 mVrms) tended to improve. The rate of capacity change under low voltage conditions relative to normal measurement conditions (1 Vrms) was −31.1% for the Comparative Example, −25.0% for Example 1, −14.9% for Example 2, −9.5% for Example 3, and −4.6% for Example 4. The Curie point Tc was approximately 95°C for the Comparative Example, 80°C for Example 1, 65°C for Example 2, 50°C for Example 3, and approximately 25°C for Example 4. These results are thought to be due to the fact that the Curie point Tc was lowered by the solid solution of zirconium, thereby improving the AC voltage characteristics.

[0063] FIG. 7 shows the rate of change in AC voltage characteristics when the results of Example 1 are converted into average thicknesses of the dielectric layer (1 μm, 2 μm, 4 μm). The rate of change in capacitance under low voltage conditions relative to normal measurement conditions (1 Vrms) was +2.1% when converted into 1 μm, -24.2% when converted into 2 μm, and -35.8% when converted into 4 μm. These results show that the capacitance at low voltage increases as the average thickness decreases, and that at thicknesses of 1 μm or less, the capacitance at low voltage (10 mVrms) exceeds the capacitance under normal measurement conditions (1 Vrms). Similar results were obtained in Examples 2 to 4. Therefore, by using a dielectric layer that contains barium titanate zirconate as the main component, contains zirconium at 2 at% or more and 14 at% or less of the total of titanium and zirconium, has a Curie point of less than 85°C, and has an average thickness of 1 μm or less, it is possible to realize a multilayer ceramic capacitor whose capacitance at low voltage (10 mVrms) exceeds the capacitance under normal measurement conditions (1 Vrms).

[0064] On the other hand, as the amount of zirconium increases, the capacitance peak tends to shift to a lower electric field, but barium titanate zirconate with a particle size of 1 μm or less tends to have a lower dielectric constant. The barium titanate used in the comparative example had a dielectric constant of 3200, while the BaTi 0.98 Zr 0.02 The relative dielectric constant of O3 is 2900, and the BaTi 0.96 Zr 0.04 The relative dielectric constant of O3 is 2500, and the BaTi 0.92 Zr 0.08 The relative dielectric constant of O3 is 2000, and the BaTi 0.86 Zr 0.14 The relative dielectric constant of O3 was about 1600. From the viewpoint of increasing the dielectric constant and increasing the capacity at low voltage, it is clear that the amount of zirconium added relative to the total of titanium and zirconium is preferably 8 at % or less.

[0065] Although the embodiments of the present invention have been described in detail above, the present invention is not limited to such specific embodiments, and various modifications and variations are possible within the scope of the gist of the present invention as defined in the claims. [Explanation of symbols]

[0066] 10 stacked chips 11 Dielectric layer 12 Internal electrode layer 13 Cover Layer 14 Capacity part 15 End Margin 16 Side Margin 20a,20b external electrode 51 Base material 52 Dielectric green sheet 53 Internal electrode pattern 100 Multilayer ceramic capacitors

Claims

1. A plurality of internal electrode layers facing each other; a plurality of dielectric layers sandwiched between the plurality of internal electrode layers, each of which is composed mainly of barium zirconate titanate, contains 2 at % or more and 14 at % or less of zirconium with respect to the total of titanium and zirconium, has a Curie point lower than 85°C, and has an average thickness of 1 μm or less.

2. 2. The multilayer ceramic electronic component according to claim 1, wherein the plurality of dielectric layers contain zirconium in an amount of 8 at % or less with respect to the total of titanium and zirconium.

3. 3. The multilayer ceramic electronic component according to claim 1, wherein the plurality of dielectric layers have a Curie point of 80° C. or less.

4. 3. The multilayer ceramic electronic component according to claim 1, wherein the plurality of dielectric layers have a Curie point of 50[deg.] C. or less.

5. 5. The multilayer ceramic electronic component according to claim 1, wherein, under an AC voltage, the capacitance at 10 mVrms is larger than the capacitance at 1 Vrms.

6. The multilayer ceramic electronic component according to claim 1 , wherein the plurality of dielectric layers further contain manganese, silicon, or a rare earth element.

7. an element body comprising a plurality of internal electrode layers facing each other and a plurality of dielectric layers sandwiched between the plurality of internal electrode layers, the plurality of dielectric layers forming a capacitance section in a region where the plurality of internal electrodes face each other, the plurality of dielectric layers in the capacitance section being mainly composed of barium zirconate titanate, containing zirconium in an amount of 2 at % or more and 14 at % or less with respect to the total of titanium and zirconium, having a Curie point of less than 85°C and an average thickness of 1 μm; an external electrode provided on any one surface of the element body and electrically connected to some of the plurality of internal electrodes;

8. 8. The multilayer ceramic electronic component according to claim 7, wherein in the capacitance section, the plurality of dielectric layers contain zirconium in an amount of 8 at % or less with respect to the total of titanium and zirconium.

9. 9. The multilayer ceramic electronic component according to claim 7, wherein the plurality of dielectric layers in the capacitive section have a Curie point of 80[deg.] C. or lower.

10. 9. The multilayer ceramic electronic component according to claim 7, wherein the plurality of dielectric layers in the capacitive section have a Curie point of 50[deg.] C. or lower.

11. 11. The multilayer ceramic electronic component according to claim 7, wherein, under an AC voltage, the capacitance at 10 mVrms is larger than the capacitance at 1 Vrms.

12. 12. The multilayer ceramic electronic component according to claim 7, wherein in the capacitive section, the plurality of dielectric layers further contain manganese, silicon, or a rare earth element.

13. forming a dielectric green sheet containing, as a main component of ceramic, barium zirconate titanate containing zirconium at 2 at % or more and 14 at % or less relative to the total of titanium and zirconium; forming an internal electrode pattern on the dielectric green sheet using a conductive paste; forming a laminate by stacking a plurality of the dielectric green sheets on which the internal electrode patterns are formed; firing the laminate to form dielectric layers and internal electrode layers each having an average thickness of 1 μm or less; and an annealing step of heat-treating the dielectric layers so that the Curie point is less than 85°C.

14. 14. The method for producing a multilayer ceramic electronic component according to claim 13, wherein the annealing step comprises heat treatment at an atmospheric temperature of 1100° C. to 1200° C. for 30 minutes to 3 hours.

15. 15. The method for producing a multilayer ceramic electronic component according to claim 13, further comprising the step of applying a metal paste to contact edges of the internal electrode patterns before firing the laminate.

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