WO2015040881A1 - セラミックグリーンシート、積層セラミックコンデンサの製造方法、および積層セラミックコンデンサ - Google Patents
セラミックグリーンシート、積層セラミックコンデンサの製造方法、および積層セラミックコンデンサ Download PDFInfo
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- WO2015040881A1 WO2015040881A1 PCT/JP2014/059854 JP2014059854W WO2015040881A1 WO 2015040881 A1 WO2015040881 A1 WO 2015040881A1 JP 2014059854 W JP2014059854 W JP 2014059854W WO 2015040881 A1 WO2015040881 A1 WO 2015040881A1
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- Prior art keywords
- ceramic
- multilayer ceramic
- green sheet
- barium titanate
- ceramic capacitor
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- 239000000919 ceramic Substances 0.000 title claims abstract description 124
- 239000003985 ceramic capacitor Substances 0.000 title claims abstract description 55
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 43
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 34
- 229910002113 barium titanate Inorganic materials 0.000 claims abstract description 32
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000010304 firing Methods 0.000 claims description 14
- 238000009413 insulation Methods 0.000 abstract description 18
- 239000000654 additive Substances 0.000 abstract description 17
- 230000000996 additive effect Effects 0.000 abstract description 16
- 239000011248 coating agent Substances 0.000 abstract 2
- 238000000576 coating method Methods 0.000 abstract 2
- 230000015556 catabolic process Effects 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 abstract 1
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- 239000000843 powder Substances 0.000 description 17
- 238000004458 analytical method Methods 0.000 description 15
- 230000005684 electric field Effects 0.000 description 15
- 229910004298 SiO 2 Inorganic materials 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 238000007747 plating Methods 0.000 description 7
- 238000010298 pulverizing process Methods 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
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- 239000013078 crystal Substances 0.000 description 4
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 3
- 229910052788 barium Inorganic materials 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910052692 Dysprosium Inorganic materials 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002003 electrode paste Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 235000020985 whole grains Nutrition 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/658—Atmosphere during thermal treatment
- C04B2235/6582—Hydrogen containing atmosphere
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/658—Atmosphere during thermal treatment
- C04B2235/6583—Oxygen containing atmosphere, e.g. with changing oxygen pressures
- C04B2235/6584—Oxygen containing atmosphere, e.g. with changing oxygen pressures at an oxygen percentage below that of air
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- C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
- C04B2237/30—Composition of layers of ceramic laminates or of ceramic or metallic articles to be joined by heating, e.g. Si substrates
- C04B2237/32—Ceramic
- C04B2237/34—Oxidic
- C04B2237/345—Refractory metal oxides
- C04B2237/346—Titania or titanates
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- C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
- C04B2237/50—Processing aspects relating to ceramic laminates or to the joining of ceramic articles with other articles by heating
- C04B2237/70—Forming laminates or joined articles comprising layers of a specific, unusual thickness
- C04B2237/704—Forming laminates or joined articles comprising layers of a specific, unusual thickness of one or more of the ceramic layers or articles
Definitions
- the present invention relates to a ceramic green sheet used for manufacturing a multilayer ceramic electronic component, a method for manufacturing a multilayer ceramic capacitor using the same, and a multilayer ceramic capacitor.
- One typical ceramic electronic component is, for example, a multilayer ceramic capacitor having a structure as shown in FIG.
- this multilayer ceramic capacitor has a ceramic laminate (laminated layer) in which a plurality of internal electrodes 52 (52a, 52b) are laminated via a ceramic layer (ceramic dielectric layer) 51 that functions as a dielectric layer.
- the external electrodes 54 (54a, 54b) are arranged on both end faces 53a, 53b of the ceramic element 60 so as to be electrically connected to the internal electrodes 52 (52a, 52b).
- An increase in the capacity of the multilayer ceramic capacitor is realized by reducing the thickness of the dielectric element, but at the same time, it increases the effective area and the electric field strength applied to the element. Therefore, in order to ensure reliability with a thin layer and high electric field strength while keeping the dielectric constant of the dielectric high, for example, a small amount of additive components are dissolved in the outer periphery of ceramic particles such as barium titanate ceramic.
- a dielectric ceramic having a so-called core-shell structure is used.
- this multilayer ceramic capacitor is intended to suppress the deterioration of insulation resistance of the multilayer ceramic capacitor under high temperature and high electric field by defining the unevenness of the interface between the dielectric layer and the internal electrode layer within a predetermined range. is there.
- BaTiO 3 powder having an average particle size of 0.15 ⁇ m is used as a ceramic powder for a dielectric green sheet used in the production of a multilayer ceramic capacitor, and as a sintering aid, It is described that glass powder mainly composed of SiO 2 having an average particle diameter of 0.1 ⁇ m is used.
- glass powder mainly composed of SiO 2 having an average particle diameter of 0.1 ⁇ m is used.
- liquid phase is generated starting from glass mainly composed of SiO 2 , and Y, Mn, and Mg added to the liquid phase are taken in, so that BaTiO which is the main raw material is used. It is considered that the additive element is dissolved in 3 .
- the multilayer ceramic capacitor having the dielectric ceramic as a dielectric layer manufactured by the method of the example of Patent Document 1 is likely to cause deterioration of insulation resistance under high temperature and high electric field. .
- the present invention solves the above-mentioned problems, and when used in the production of a multilayer ceramic capacitor, a dielectric having a low ratio of grain boundaries in the grain boundary of the dielectric layer to which no additive component is present relative to all grain boundaries.
- a ceramic green that can form a layer and suppress the progress of deterioration of insulation resistance by suppressing the concentration of the electric field to a specific part of the dielectric layer even when a high electric field is applied. It is an object of the present invention to provide a sheet, a highly reliable multilayer ceramic capacitor manufactured using the ceramic green sheet, and a method for manufacturing the same.
- the ceramic green sheet of the present invention is A ceramic green sheet having barium titanate ceramic particles as a main inorganic component,
- the Si-containing component coverage which is the ratio of the Si-containing component covering the surface of the barium titanate-based ceramic particles, is 95% or more, and
- the rare earth element-containing component covering ratio of the rare earth element-containing component covering the surface of the barium titanate-based ceramic particles is 85% or more.
- Si-containing component coverage is 95% or more
- Si-containing component coverage (%) (number of points where Si element is present / number of measurement points) ⁇ 100 (1)
- the ceramic green sheet is debindered, and a scanning transmission electron microscope (STEM (Scanning Transmission Electron Microscope) is obtained. ))
- STEM Sccanning Transmission Electron Microscope
- the detection of Si relative to the total amount of detection elements excluding C and O A point having a concentration of 0.5 atomic% or more is defined as “a point where Si element is present”, and the number thereof is defined as “the number of points where Si element is present”.
- rare earth element-containing component coverage is 85% or more
- Rare earth element-containing component coverage (%) (number of rare earth elements present / number of measurement points) ⁇ 100 (2)
- the ceramic green sheet is debindered, and the raw material particles are obtained using a scanning transmission electron microscope (STEM).
- STEM scanning transmission electron microscope
- the method for manufacturing the multilayer ceramic capacitor of the present invention includes: A multilayer ceramic element comprising a plurality of dielectric layers made of a barium titanate-based ceramic, and a plurality of internal electrodes arranged to face each other with the dielectric layer interposed therebetween, and a surface of the multilayer ceramic element And a method of manufacturing a multilayer ceramic capacitor comprising an external electrode disposed so as to be electrically connected to the internal electrode,
- the ceramic green sheet according to the present invention described above is laminated with an electrode pattern imparted sheet obtained by applying the conductive paste for forming the internal electrode so as to have a predetermined pattern, and becomes an unfired ceramic element after firing. Forming a laminated structure; Firing the unfired laminated structure to form the laminated ceramic element; Forming an external electrode electrically connected to the internal electrode on the multilayer ceramic element.
- the multilayer ceramic capacitor of the present invention is A multilayer ceramic element comprising a plurality of dielectric layers made of a barium titanate-based ceramic, and a plurality of internal electrodes arranged to face each other with the dielectric layer interposed therebetween, and a surface of the multilayer ceramic element And a multilayer ceramic capacitor comprising an external electrode disposed so as to be electrically connected to the internal electrode, Of all the grain boundaries of the barium titanate-based ceramic constituting the dielectric layer, rare earth elements are present at 98% or more of grain boundaries.
- the ceramic green sheet of the present invention has a Si-containing component coverage of 95% or more, which is the ratio of the Si-containing component covering the surface of the barium titanate-based ceramic particles, and contains a rare earth element Since the component has a rare earth element-containing component coverage of 85% or more, which is the ratio of covering the surface of the barium titanate ceramic particles, the dielectric layer of the multilayer ceramic capacitor is formed using this ceramic green sheet. As a result, it is possible to reduce the ratio of the grain boundaries where no additive component is present to the total grain boundaries in the grain boundaries of the barium titanate-based ceramic constituting the dielectric layer. As a result, even when a high electric field is applied, it is possible to suppress the concentration of the electric field on a specific portion of the dielectric layer, and it is possible to suppress deterioration of the insulation resistance.
- the method for producing a multilayer ceramic capacitor of the present invention comprises laminating an electrode pattern imparting sheet provided with a conductive paste for forming an internal electrode in a predetermined pattern on the ceramic green sheet of the present invention, and firing the laminate.
- the multilayer ceramic element is provided with an external electrode that is electrically connected to the internal electrode. Therefore, it is possible to reliably manufacture a multilayer ceramic capacitor having a dielectric layer with a small proportion of the grain boundary where no additive component is present at the grain boundary of the barium titanate ceramic. be able to. In the dielectric layer, even when a high electric field is applied, the concentration of the electric field at a specific location is suppressed, so that a highly reliable multilayer ceramic capacitor with little deterioration in insulation resistance is efficiently manufactured. be able to.
- rare earth elements exist in 98% or more of the grain boundaries of the barium titanate-based ceramic constituting the dielectric layer, and the titanate constituting the dielectric layer.
- the ratio of grain boundaries that do not contain additive components (rare earth elements) to the whole grain boundary is low, and even when a high electric field is applied, the electric field applied to a specific part of the dielectric layer Therefore, it is possible to provide a highly reliable multilayer ceramic capacitor.
- this multilayer ceramic capacitor is formed on both sides of a multilayer ceramic element (ceramic body) 10 in which a plurality of internal electrodes 2 (2a, 2b) are laminated via a ceramic layer 1 which is a dielectric layer.
- An external electrode 4 (4a, 4b) is disposed on the end face 3 (3a, 3b) so as to be electrically connected to the internal electrode 2 (2a, 2b).
- the internal electrodes 2 (2a, 2b) are base metal electrodes having Ni as a conductive component.
- the external electrode 4 (4a, 4b) includes an external electrode body 11 formed by baking a conductive paste, a Ni plating film layer 12 formed on the surface of the external electrode body 11, and a surface of the Ni plating film layer 12. A multilayer structure including the formed Sn plating film layer 13 is formed.
- a dielectric layer (ceramic layer dielectric layer) 1 constituting the multilayer ceramic element (ceramic body) 10 of the multilayer ceramic capacitor is a dielectric ceramic having a perovskite structure (in this embodiment, a barium titanate ceramic). Formed from.
- BaCO 3 and TiO 2 powders were prepared and weighed so that the molar ratio of Ba and Ti was 1: 1.
- the main raw material slurry after pulverization and pulverization treatment was dried in an oven and then heat-treated at a temperature of 950 ° C. or higher to obtain a barium titanate ceramic powder having an average particle size of 0.20 ⁇ m.
- SiO 2 of the additives were prepared a plurality of kinds of SiO 2 powder having different SSA (specific surface area).
- barium titanate-based ceramic powder and each additive component (BaCO 3 , Dy 2 O 3 , MgCO 3 , MnCO 3 , SiO 2 ) are weighed, and pure water and a dispersant are added to force circulation type Was pulverized and crushed using a wet pulverizer (using PSZ media) to prepare a blended raw material slurry.
- the added amount of Dy 2 O 3 , MgCO 3 , MnCO 3 , and SiO 2 is as follows when the total content of Ti is 100 mol parts: (A) The total content (mole parts) of Dy is 4.0. (B) Mg content (mole part) is 0.25. (C) Mn content (mole part) is 0.25. (D) The Si content (mole part) is 1.5. The amount added was such that
- BaCO 3 was added at such a ratio that the ratio of Ba and Ti (Ba / Ti (molar ratio)) after firing was 1.01 after firing. Then, the slurry after pulverization and pulverization was dried in an oven to obtain each dielectric material powder.
- This ceramic slurry was formed into a sheet so that the thickness of the dielectric element after firing was 5.0 ⁇ m to obtain a rectangular ceramic green sheet.
- the sheet is formed by the doctor blade method, but the sheet forming method is not limited to this, and various known methods can be used.
- the ceramic green sheet produced as described above is subjected to a binder removal treatment by heating for 2 hours in an air atmosphere at 400 ° C., and is a barium titanate ceramic powder.
- Raw material particles were obtained.
- the surface of the raw material particles was observed with a scanning transmission electron microscope (STEM), and the abundance of Dy and Si was confirmed by point analysis using EDX.
- the shape of the raw material particles is a sphere at the position where the point analysis is performed on the raw material particles (barium titanate ceramic particles), the schematic view of the raw material particles viewed in a plane.
- the point analysis is performed by entering a point (surface of the raw material particles) that enters the inner side (center direction) of the 10 nm raw material particles 50 from the outer edge 50a of the barium titanate-based ceramic particles in FIG.
- the Si-containing component coverage was determined by the following formula (1), and the Dy (rare earth element) -containing component coverage was determined by the equation (2).
- ⁇ Si-containing component coverage (%) (number of Si elements present / number of measurement points) ⁇ 100 (1)
- the point where the detected concentration of Dy (rare earth element) and Si was 0.5 atomic% or more was judged to be the point where Dy (rare earth element) and Si were present.
- JEM-2200FS manufactured by JEOL
- the acceleration voltage is 200 kV.
- the detector EDS energy dispersive X-ray analyzer
- JED-2300T manufactured by JEOL
- SDD detector silicon drift detector
- Table 1 shows the values of the Si-containing component coverage (%) and the Dy (rare earth element) -containing component coverage (%) of the raw material particles for each sample (ceramic green sheet) obtained as described above.
- a conductive paste containing Ni powder as a conductive component is screen-printed on the ceramic green sheet produced as described above on the lower outer layer formed in the above step 1), and the inside A predetermined number (170 in this embodiment) of the electrode pattern-formed ceramic green sheets on which the electrode patterns were formed were laminated so that the internal electrode patterns were drawn out to the opposite ends facing each other.
- the unfired laminated structure obtained in the above step 4) was heated to 250 ° C. in an N 2 atmosphere to perform a binder removal treatment. Then, in a reducing atmosphere composed of H 2 —N 2 —H 2 O gas, the top temperature is 1240 to 1300 ° C. (1270 ° C. in this embodiment), the oxygen partial pressure is 10 ⁇ 9 to 10 ⁇ 10 MPa (in this embodiment) 10 -9 MPa) to obtain a fired laminated ceramic element.
- an Ni plating layer was formed so as to cover the formed Cu electrode, and an Sn plating layer was further formed so as to cover it, thereby obtaining a multilayer ceramic capacitor having a structure as shown in FIG.
- the obtained multilayer ceramic capacitor had outer dimensions of a width of 2.0 mm, a length of 1.3 mm, and a thickness of 1.3 mm.
- the thickness of the ceramic layer (dielectric layer) 1 interposed between the internal electrodes 2 was 5.0 ⁇ m.
- the grain boundary to be analyzed was selected such that the crystal interface between adjacent crystal grains was clear and the grain boundary (crystal grain boundary) was considered to be nearly perpendicular to the thin film surface.
- JEM-2200FS manufactured by JEOL
- the acceleration voltage was 200 kV.
- the detector EDS was a JED-2300T (manufactured by JEOL), a 60 mm 2 caliber SDD detector, and the EDS system was a Noran System 7.
- the thickness of the thin sample was about 100 nm.
- Concentration measurement in STEM analysis was point analysis at 30 seconds per point, and the concentration of each element was determined by the Cliff-Lorimer method.
- Point analysis was performed at the center of the selected grain boundary, and a grain boundary having a Dy detection concentration of 0.5 atomic% or more with respect to the total amount of detected elements excluding C and O was determined to be a grain boundary where Dy was present. .
- Capacitance is between 25% and 75% means that, for example, when the capacitance of 100 multilayer ceramic capacitors (samples) is measured, the capacitance is from the smaller one. Samples up to the 25th sample and samples excluding the 25th sample from the one with the largest capacitance, that is, the 26th sample to the 75th sample from the one with the smallest capacitance. .
- sample numbers marked with * are comparative samples that do not satisfy the requirements of the present invention, and other samples (sample numbers 6 to 9). ) Is a sample that satisfies the requirements of the present invention.
- a ceramic having a Si-containing component coverage determined by the above formula (1) of 95% or more and a Dy (rare earth element) -containing component coverage determined by the above formula (2) of 85% or more In the case of a sample prepared using a green sheet and having a Dy (rare earth element) abundance ratio of 98% or more in the dielectric layer (that is, the samples of sample numbers 6 to 9 having the requirements of the present invention) In a test for examining the insulation resistance, it was confirmed that a highly reliable multilayer ceramic capacitor in which the occurrence of insulation failure was not observed was obtained.
- the Si-containing component coverage determined by the above equation (1) is less than 95%, or the Dy (rare earth element) -containing component coverage determined by the above equation (2) is less than 85%.
- the Dy (rare earth element) -containing component coverage determined by the above equation (2) is less than 85%.
- the ceramic green sheet is a ceramic green sheet having a Ba / Ti ratio (Ba / Ti (molar ratio)) of 1.01 after firing.
- the (molar ratio) is not limited to this.
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Abstract
Description
そこで、誘電体の比誘電率を高く保ちながら、薄層かつ高電界強度で信頼性を確保するために、例えば、チタン酸バリウム系セラミックなどのセラミック粒子の外周部に微量の添加成分を固溶させた、いわゆるコアシェル構造を有する誘電体セラミックが用いられている。
チタン酸バリウム系セラミック粒子を主たる無機成分とするセラミックグリーンシートであって、
Si含有成分が、前記チタン酸バリウム系セラミック粒子の表面を被覆している割合であるSi含有成分被覆率が95%以上であり、かつ、
希土類元素含有成分が、前記チタン酸バリウム系セラミック粒子の表面を被覆している割合である希土類元素含有成分被覆率が85%以上であること
を特徴としている。
Si含有成分被覆率(%)=(Si元素の存在する点の数/測定点の数)×100 ……(1)
希土類元素含有成分被覆率(%)=(希土類元素の存在する点の数/測定点の数)×100 ……(2)
チタン酸バリウム系セラミックによって構成された複数の誘電体層と、前記誘電体層を介して互いに対向するように配設された複数の内部電極とを備える積層セラミック素子と、前記積層セラミック素子の表面に、前記内部電極と電気的に接続するように配設された外部電極とを具備する積層セラミックコンデンサの製造方法であって、
上述の本発明にかかるセラミックグリーンシートに、前記内部電極形成用の導電性ペーストを所定のパターンとなるように付与した電極パターン付与シートを積層し、焼成後に前記積層セラミック素子となる、未焼成の積層構造体を形成する工程と、
前記未焼成の積層構造体を焼成して、前記積層セラミック素子を形成する工程と、
前記積層セラミック素子に、前記内部電極と導通する外部電極を形成する工程と
を具備することを特徴としている。
チタン酸バリウム系セラミックによって構成された複数の誘電体層と、前記誘電体層を介して互いに対向するように配設された複数の内部電極とを備える積層セラミック素子と、前記積層セラミック素子の表面に、前記内部電極と電気的に接続するように配設された外部電極とを具備する積層セラミックコンデンサであって、
前記誘電体層を構成するチタン酸バリウム系セラミックのすべての粒界のうち、98%以上の粒界に希土類元素が存在していること
を特徴としている。
この実施形態では、本発明の実施形態にかかるセラミックグリーンシートを用いて、図1に示すような構造を有する、本発明の実施形態にかかる積層セラミックコンデンサを製造する場合を例にとって説明する。
また、外部電極4(4a,4b)は、導電性ペーストを焼き付けてなる外部電極本体11と、外部電極本体11の表面に形成されたNiめっき膜層12と、Niめっき膜層12の表面に形成されたSnめっき膜層13とを備えてなる多層構造とされている。
まず、以下の手順で、誘電体主成分原料であるチタン酸バリウム系セラミック粉末を作製した。
(a)Dyの合計含有量(モル部)が、4.0
(b)Mgの含有量(モル部)が、0.25
(c)Mnの含有量(モル部)が、0.25
(d)Siの含有量(モル部)が、1.5
となるような添加量とした。
それから、粉砕・解砕処理後のスラリーをオーブンで乾燥させ、各誘電体原料粉末を得た。
上述のようにして作製した各誘電体原料粉末に、ポリビニルブチラール系バインダーおよびエタノールなどの有機溶媒を加え、ボールミルにより湿式混合して、セラミックスラリーを作製した。
なお、この実施形態では、ドクターブレード法によりシート成形を行ったが、シート成形の方法はこれに限られるものではなく、公知の種々の方法を用いることが可能である。
まず、上述のようにして作製したセラミックグリーンシートをair雰囲気、400℃の条件下で2時間加熱することで脱バインダー処理を行い、チタン酸バリウム系セラミック粉末である原料粒子を得た。
それから、走査透過電子顕微鏡(STEM(Scanning Transmission Electron Microscope))にて原料粒子表面を観察し、Dy、Siの存在量をEDXを用いた点分析にて確認した。
すなわち、点分析は、球体状の原料粒子50を平面的に見た図2におけるチタン酸バリウム系セラミック粒子の外縁50aから10nm原料粒子50の内側(中心方向)に入った点(原料粒子の表面上の点(例えば、図2におけるP1,P2,P3など))を、1粒子につき8点(点と点の間隔は50nm以上とする)として、13個の粒子について点分析を行った。
したがって、このときの点分析の合計数は104点(8点×13粒子=104)となる。
上述のようにして得た、各試料(セラミックグリーンシート)についての、原料粒子のSi含有成分被覆率(%)およびDy(希土類元素)含有成分被覆率(%)の値を表1に示す。
1)まず、上述のようにして作製したセラミックグリーンシートを、所定の厚み(例えば100μm)を有する外層部が形成されるように所定枚数積層し、下側外層部を形成した。
得られた積層セラミック素子の端面に、導電成分としてCu粉末を含有するとともに、B2O3-Li2O3-SiO2-BaO系ガラスフリットを含有する導電性ペースト(外部電極ペースト)を塗布し、N2雰囲気中において850℃の温度で焼き付け、内部電極と電気的に接続された外部電極(Cu電極)を形成した。
また、内部電極2間に介在するセラミック層(誘電体層)1の厚みは5.0μmであった。
上述のようにして作製した積層セラミックコンデンサ(試料)を5個ずつ用意し、5個試料のそれぞれについて、長さ方向、幅方向、厚み方向のそれぞれにおける中央付近を研磨にて露出させ、該中央付近のセラミック層(誘電体層)を薄片加工した。
なお、STEM分析において、STEMはJEM-2200FS(JEOL製)を用いた。加速電圧は200kVとした。
STEM分析における濃度測定は、1点あたり30秒で点分析を行い、各元素の濃度はクリフ・ロリマー法で求めた。
その結果を、Dy存在率として表1に示す。
上記のようにして作製した積層セラミックコンデンサに対して、1kHz-1Vacにて静電容量の測定を行い、静電容量が25%値~75%値の間にあるものを評価対象となる積層セラミックコンデンサとして抽出した。
試験に供した50個の試料に対する、絶縁抵抗不良の発生した試料の個数および絶縁不良発生率を表1に併せて示す。
2(2a,2b) 内部電極
3(3a,3b) セラミック素体の端面
4(4a,4b) 外部電極
10 セラミック素体
11 外部電極本体
12 Niめっき膜層
13 Snめっき膜層
50 原料粒子
50a 原料粒子の外縁
P1,P2,P3 原料粒子の分析を行った点
Claims (3)
- チタン酸バリウム系セラミック粒子を主たる無機成分とするセラミックグリーンシートであって、
Si含有成分が、前記チタン酸バリウム系セラミック粒子の表面を被覆している割合であるSi含有成分被覆率が95%以上であり、かつ、
希土類元素含有成分が、前記チタン酸バリウム系セラミック粒子の表面を被覆している割合である希土類元素含有成分被覆率が85%以上であること
を特徴とするセラミックグリーンシート。 - チタン酸バリウム系セラミックによって構成された複数の誘電体層と、前記誘電体層を介して互いに対向するように配設された複数の内部電極とを備える積層セラミック素子と、前記積層セラミック素子の表面に、前記内部電極と電気的に接続するように配設された外部電極とを具備する積層セラミックコンデンサの製造方法であって、
請求項1記載のセラミックグリーンシートに、前記内部電極形成用の導電性ペーストを所定のパターンとなるように付与した電極パターン付与シートを積層し、焼成後に前記積層セラミック素子となる、未焼成の積層構造体を形成する工程と、
前記未焼成の積層構造体を焼成して、前記積層セラミック素子を形成する工程と、
前記積層セラミック素子に、前記内部電極と導通する外部電極を形成する工程と
を具備することを特徴とする積層セラミックコンデンサの製造方法。 - チタン酸バリウム系セラミックによって構成された複数の誘電体層と、前記誘電体層を介して互いに対向するように配設された複数の内部電極とを備える積層セラミック素子と、前記積層セラミック素子の表面に、前記内部電極と電気的に接続するように配設された外部電極とを具備する積層セラミックコンデンサであって、
前記誘電体層を構成するチタン酸バリウム系セラミックのすべての粒界のうち、98%以上の粒界に希土類元素が存在していること
を特徴とする積層セラミックコンデンサ。
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