TWI406309B - Multi-layered ceramic electronic component - Google Patents

Multi-layered ceramic electronic component Download PDF

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TWI406309B
TWI406309B TW097117399A TW97117399A TWI406309B TW I406309 B TWI406309 B TW I406309B TW 097117399 A TW097117399 A TW 097117399A TW 97117399 A TW97117399 A TW 97117399A TW I406309 B TWI406309 B TW I406309B
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ceramic
gap
mol
layer
internal electrode
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TW097117399A
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TW200908043A (en
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Koji Suzuki
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Murata Manufacturing Co
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Priority to JP2008114310A priority patent/JP4591537B2/en
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G4/00Fixed capacitors; Processes of their manufacture
    • H01G4/30Stacked capacitors
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G4/00Fixed capacitors; Processes of their manufacture
    • H01G4/002Details
    • H01G4/018Dielectrics
    • H01G4/06Solid dielectrics
    • H01G4/08Inorganic dielectrics
    • H01G4/12Ceramic dielectrics
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G4/00Fixed capacitors; Processes of their manufacture
    • H01G4/002Details
    • H01G4/228Terminals
    • H01G4/232Terminals electrically connecting two or more layers of a stacked or rolled capacitor

Abstract

The invention provides a laminated ceramic electronic component which has high reliability to wet resistance even in a miniaturization condition. In a sintered ceramic body (10) including side gap portions arranged between sides of a first internal electrode (1) and a second internal electrode (2) and first and second side surfaces (21),(22) of the sintered ceramic body and between sides of the effective layer portion (3a) and the first and second side surfaces of the sintered ceramic body, regions of the side gap portions at least adjacent to the first and second internal electrodes are Mg-rich regions MR each having a Mg concentration greater than that of the effective layer portion. In addition, the side gap portions are integrally taken as Mg-rich regions. In a side gap portion GE between the end portion of the effective layer portion and the first or second side surfaces (11), (12), the region at least adjacent to the first and second internal electrodes is taken as an Mg-rich region. Mg in the Mg-rich region is 0.5-1.0 mol% more than that in the effective layer portion.

Description

積層陶瓷電子零件Laminated ceramic electronic parts
本發明係關於一種積層陶瓷電子零件,具體而言,係關於將陶瓷層與電容形成用內部電極積層而成的積層陶瓷電子零件。The present invention relates to a laminated ceramic electronic component, and more particularly to a laminated ceramic electronic component in which a ceramic layer and an internal electrode for capacitor formation are laminated.
近年來,隨著行動電話或可攜式音樂播放器等電子機器之小型化,所裝載之電子零件之小型化亦快速發展。例如,以晶片型積層陶瓷電容器為代表之晶片型積層陶瓷電子零件中,為了確保既定特性並縮小晶片尺寸,陶瓷層之薄層化正在進展。In recent years, with the miniaturization of electronic devices such as mobile phones and portable music players, the miniaturization of electronic components mounted has also rapidly progressed. For example, in a wafer-type multilayer ceramic electronic component typified by a wafer-type multilayer ceramic capacitor, in order to secure a predetermined characteristic and to reduce the size of the wafer, thinning of the ceramic layer is progressing.
因此,因應陶瓷層之薄層化,陶瓷層之積層片數亦有增加之趨勢。通常,積層陶瓷電子零件雖具有陶瓷層與內部電極交互積層之構造,但由於內部電極並未覆蓋全部陶瓷層而僅形成至由陶瓷層之周緣部稍微後退之內側位置使內部電極從晶片側面露出,因此會在內部電極與陶瓷層之間產生段差。因此,若陶瓷層之積層片數增加時,則容易因該段差而產生剝層等構造缺陷。Therefore, in response to the thinning of the ceramic layer, the number of laminated layers of the ceramic layer also tends to increase. In general, a laminated ceramic electronic component has a structure in which a ceramic layer and an internal electrode are alternately laminated, but since the internal electrode does not cover the entire ceramic layer, it is formed only to an inner position slightly retreated from the peripheral edge portion of the ceramic layer to expose the internal electrode from the side surface of the wafer. Therefore, a step difference is generated between the internal electrode and the ceramic layer. Therefore, when the number of laminated layers of the ceramic layer is increased, structural defects such as peeling are likely to occur due to the step.
解決此種問題之對策,例如已有提案一種方法,其係將內部電極圖案印刷於陶瓷未加工片上之後,於未印刷內部電極圖案之部分印刷陶瓷膏,藉由該陶瓷膏來吸收段差(參照專利文獻1)。In order to solve such a problem, for example, a method has been proposed in which an internal electrode pattern is printed on a ceramic green sheet, and a ceramic paste is printed on a portion where the internal electrode pattern is not printed, and the ceramic paste is used to absorb the step (refer to Patent Document 1).
然而,在該方法之情況下,即使可吸收陶瓷層與內部電極間之段差,但在燒成時因內部電極與陶瓷層之燒結收 縮行為的差異,會在內部電極端部與陶瓷層之間產生微細之間隙,而有濕氣等水分滲入該間隙引起耐濕不良的問題點。However, in the case of this method, even if the difference between the absorbable ceramic layer and the internal electrode is poor, the sintering of the internal electrode and the ceramic layer is performed at the time of firing. The difference in shrinkage behavior causes a fine gap between the end of the internal electrode and the ceramic layer, and there is a problem that moisture such as moisture permeates into the gap to cause moisture resistance.
此外,與該專利文獻1相關之技術,亦有提案一種方法,其係將SiO2 添加於段差吸收用陶瓷膏,以縮小陶瓷與內部電極之燒結收縮行為的差(參照專利文獻2)。Further, in the technique related to Patent Document 1, there is also proposed a method of adding SiO 2 to the ceramic paste for step absorption to reduce the difference in sintering shrinkage behavior between the ceramic and the internal electrode (see Patent Document 2).
然而,即使是該專利文獻2之方法,要使陶瓷與內部電極兩者之燒結收縮行為完全一致係極為困難,實際上因該間隙所產生之耐濕不良問題尚未得到充分解決。However, even in the method of Patent Document 2, it is extremely difficult to completely match the sintering shrinkage behavior of both the ceramic and the internal electrode, and in fact, the problem of poor moisture resistance due to the gap has not been sufficiently solved.
又,由於段差吸收部分最接近晶片之外表面,因此在燒成步驟中熱容易傳導而易於燒結下,因SiO2 之添加使燒結溫部進一步降低,而有使側面側間隙部過度燒結容易造成電容器本體之構造缺陷或強度降低的問題點。Further, since the step absorption portion is closest to the outer surface of the wafer, heat is easily conducted in the firing step and is easily sintered, and the sintering temperature portion is further lowered by the addition of SiO 2 , and the side surface side portion is excessively sintered. The problem of structural defects or strength reduction of the capacitor body.
此外,亦有提案一種解決段差問題之方法,其係將Cu添加於段差吸收用陶瓷膏,將屬內部電極材料之Ni與陶瓷膏中之Cu合金化,以提高內部電極與段差吸收層之接合性(參照專利文獻3)。In addition, there is also proposed a method for solving the step problem, in which Cu is added to the ceramic paste for phase difference absorption, and Ni of the internal electrode material is alloyed with Cu in the ceramic paste to improve the bonding between the internal electrode and the step absorption layer. (see Patent Document 3).
然而,在該專利文獻3之方法的情況下,由於Ni與Cu之合金會因燒成環境氣氛等容易產生氧化還原反應,由於在氧化反應之體積膨脹後,會產生因還原反應之體積縮小,而在段差部產生間隙,因此實際上難以充分確保對耐濕性之可靠性。However, in the case of the method of Patent Document 3, since the alloy of Ni and Cu is likely to undergo an oxidation-reduction reaction due to a firing atmosphere or the like, the volume of the reduction reaction is reduced after the volume expansion of the oxidation reaction. On the other hand, since a gap is generated in the step portion, it is actually difficult to sufficiently ensure the reliability against moisture resistance.
專利文獻1:日本特開昭56-94719號公報專利文獻2:日本特開2004-96010號公報Patent Document 1: JP-A-56-94719 Patent Document 2: JP-A-2004-96010
專利文獻3:日本特開2005-101301號公報Patent Document 3: Japanese Laid-Open Patent Publication No. 2005-101301
本發明係用以解決上述課題,目的在於提供一種即使在小型化之情況下亦對耐濕性之可靠度高的積層陶瓷電子零件。The present invention has been made to solve the above problems, and an object of the invention is to provide a laminated ceramic electronic component having high reliability against moisture resistance even in the case of miniaturization.
為了解決上述課題,本發明(申請專利範圍第1項)之積層陶瓷電子零件,係具備:陶瓷燒結體,係複數個陶瓷層所積層而成,具有彼此相對向之第1側面及第2側面、及彼此相對向之第1端面及第2端面;第1內部電極,係形成於該陶瓷燒結體內部並引出至該第1端面且含有Ni;第2內部電極,係於該陶瓷燒結體內部形成為透過特定之該陶瓷層與該第1內部電極相對向,並引出至該第2端面且含有Ni;第1外部端子電極,係形成於該陶瓷燒結體之該第1端面,並與該第1內部電極電氣連接;以及第2外部端子電極,係形成於該陶瓷燒結體之該第2端面,並與該第2內部電極電氣連接,且連接於與該第1外部端子電極不同之電位,其特徵在於:該陶瓷燒結體包含:該陶瓷層之中挾持於該第1內部電極及該第2內部電極且有助於形成電容的有效層部;以及存在於該第1、第2內部電極之側部與該陶瓷燒結體之第1、第2側面之間、及該有效層部之側部與該陶瓷燒結體之第1、第2側面之間的側面側間隙部,使該側面側間隙部之中從與該第1、第2內部電極接觸之區域至該陶瓷燒結體側面之區域為Mg濃度高於該有效層部的富含Mg區域。In order to solve the above problem, the laminated ceramic electronic component of the invention (the first aspect of the patent application) includes a ceramic sintered body in which a plurality of ceramic layers are laminated, and have first side faces and second side faces facing each other. And the first inner surface and the second end surface facing each other; the first inner electrode is formed inside the ceramic sintered body and is led to the first end surface and contains Ni; and the second inner electrode is inside the ceramic sintered body The ceramic layer is formed to face the first internal electrode, and is led to the second end surface and contains Ni; the first external terminal electrode is formed on the first end surface of the ceramic sintered body, and The first internal electrode is electrically connected; and the second external terminal electrode is formed on the second end surface of the ceramic sintered body, and is electrically connected to the second internal electrode and connected to a potential different from the first external terminal electrode The ceramic sintered body includes: an effective layer portion of the ceramic layer sandwiched between the first internal electrode and the second internal electrode to contribute to capacitance formation; and the first and second internal portions electrode The side surface side gap portion between the side portion and the first and second side faces of the ceramic sintered body, and the side portion of the effective layer portion and the first side surface and the second side surface of the ceramic sintered body Among the portions, a region from the region in contact with the first and second internal electrodes to the side surface of the ceramic sintered body is a Mg-rich region having a Mg concentration higher than that of the effective layer portion.
又,本發明中,最好係使該側面側間隙部之中分別位於與該第1、第2內部電極相同高度之區域為該富含Mg區域。Further, in the invention, it is preferable that the region of the side-side gap portion located at the same height as the first and second internal electrodes is the Mg-rich region.
又,本發明中,最好係使該側面側間隙部整體為該富含Mg區域。Further, in the invention, it is preferable that the entire side surface side gap portion is the Mg-rich region.
又,本發明中,較佳為該陶瓷燒結體包含存在於該第1、第2內部電極之端部與該陶瓷燒結體之第1、第2端面之間、及該有效層部之端部與該陶瓷燒結體之第1或第2端面之間的端面側間隙部;使該端面側間隙部之中至少與該第1、第2內部電極鄰接之區域為Mg濃度高於該有效層部的富含Mg區域。Further, in the present invention, it is preferable that the ceramic sintered body includes an end portion of the first and second internal electrodes, and between the first end and the second end surface of the ceramic sintered body, and an end portion of the effective layer portion. An end surface side gap portion between the first or second end faces of the ceramic sintered body; wherein at least the region adjacent to the first and second internal electrodes among the end face side gap portions has a Mg concentration higher than the effective layer portion Rich in the Mg area.
又,本發明中,亦可使該第1、第2內部電極之中較最外層之內部電極外側之陶瓷層之該側面側間隙部之垂直投影區域及該端面側間隙部之垂直投影區域的至少一者為Mg濃度高於該有效層部的富含Mg區域。Further, in the present invention, the vertical projection region of the side surface side gap portion of the ceramic layer on the outer side of the inner electrode of the outermost layer of the first and second inner electrodes, and the vertical projection region of the end surface side gap portion may be At least one of them is a Mg-rich region having a Mg concentration higher than the effective layer portion.
又,本發明中,較佳為使構成該富含Mg區域之陶瓷材料之主成分為100mol%的Mg添加比例,相較於構成該有效層部之陶瓷材料之主成分為100mol%的Mg添加比例多0.5~1.0mol%。Further, in the present invention, it is preferable that the Mg addition ratio of the main component constituting the Mg-rich ceramic material is 100 mol%, and the Mg is 100 mol% of the main component of the ceramic material constituting the effective layer portion. The ratio is 0.5~1.0mol%.
又,本發明中,亦可設為該富含Mg區域中Mg濃度具有從陶瓷燒結體之外側向內側降低之濃度梯度的構成。Further, in the present invention, the Mg concentration in the Mg-rich region may have a concentration gradient which decreases from the outer side to the inner side of the ceramic sintered body.
本發明(申請專利範圍第1項)之積層陶瓷電子零件,如以上所述,係具備陶瓷燒結體、形成於陶瓷燒結體內部之第1及第2內部電極、與第1內部電極電氣連接之第1外 部端子電極、及與第2內部電極電氣連接之第2外部端子電極,由於使存在於陶瓷燒結體之第1內部電極及第2內部電極之側部與陶瓷燒結體之第1、第2側面之間、及有效層部之側部與陶瓷燒結體之第1、第2側面之間的側面側間隙部之中,從與第1、第2內部電極鄰接之區域至陶瓷燒結體側面之區域為Mg濃度高於有效層部的富含Mg區域,因此於內部電極與側面側間隙部之邊界部,生成構成內部電極之金屬之Ni與源自陶瓷之金屬元素之Mg的氧化化合物,由於藉由該氧化化合物來填充內部電極與側面側間隙部之邊界部間隙,並藉由該氧化化合物來結合內部電極與側面側間隙部,因此可提升耐濕性。此外,由於藉由因氧化化合物生成之體積膨脹,增大內部電極與側面側間隙部之邊界部之間隙的填充效果,因此該點亦可期待耐濕性之大幅提升。As described above, the laminated ceramic electronic component of the present invention (the first aspect of the invention) is provided with a ceramic sintered body, first and second internal electrodes formed inside the ceramic sintered body, and electrically connected to the first internal electrode. First outside The terminal electrode and the second external terminal electrode electrically connected to the second internal electrode are formed on the first internal electrode and the second internal electrode of the ceramic sintered body, and the first and second sides of the ceramic sintered body. Among the side surface side gap portions between the side portions of the effective layer portion and the first and second side faces of the ceramic sintered body, the region adjacent to the first and second internal electrodes to the side surface of the ceramic sintered body Since the Mg concentration is higher than the Mg-rich region of the effective layer portion, the oxidized compound of Ni constituting the metal of the internal electrode and Mg of the metal element derived from the ceramic is formed at the boundary portion between the internal electrode and the side-side gap portion. The boundary between the internal electrode and the side-side gap portion is filled with the oxidized compound, and the internal electrode and the side-side gap portion are bonded by the oxidizing compound, so that the moisture resistance can be improved. Further, since the volume expansion due to the oxidized compound increases the filling effect of the gap between the boundary portion between the internal electrode and the side surface side gap portion, the moisture resistance can be expected to be greatly improved at this point.
本發明中,關於富含Mg區域之「Mg濃度高於有效層部」,係指在有效層部含有Mg之情況下,富含Mg區域以高於有效層部之Mg含有率之比例含有Mg的概念,又,在有效層部未含Mg之情況下,係指包含有顯著程度之Mg以生成構成內部電極之金屬之Ni與Mg之氧化化合物的概念。In the present invention, the "Mg concentration is higher than the effective layer portion" in the Mg-rich region means that the Mg-rich region contains Mg in a ratio higher than the Mg content of the active layer portion when Mg is contained in the active layer portion. The concept, in the case where the effective layer portion does not contain Mg, refers to the concept of containing a significant degree of Mg to form an oxidizing compound of Ni and Mg constituting the metal of the internal electrode.
此外,在使用將MgO添加於BaTiO3 者作為耐還原性陶瓷材料的情況下,係以富含Mg區域高於該有效層部之源自MgO之Mg的含有率來含有Mg為要件。In addition, when MgO is added to BaTiO 3 as a reduction-resistant ceramic material, Mg is contained in a content ratio of Mg derived from MgO having a Mg-rich region higher than the effective layer portion.
又,本發明之積層陶瓷電子零件中,使側面側間隙部之中,分別位於與第1、第2內部電極相同高度之區域,亦 即內部電極之側邊部為富含Mg區域,藉此於內部電極之周邊部與側面側間隙部之邊界部,生成構成內部電極之金屬之Ni與源自陶瓷之金屬元素之Mg的氧化化合物,即可謀求耐濕性之提升。Further, in the multilayer ceramic electronic component of the present invention, each of the side-side gap portions is located at the same height as the first and second internal electrodes, In other words, the side portion of the internal electrode is rich in the Mg region, whereby the oxidized compound of Ni constituting the metal of the internal electrode and Mg of the metal element derived from the ceramic is formed at the boundary portion between the peripheral portion of the internal electrode and the side-side gap portion. , you can seek to improve the moisture resistance.
又,在使該側面側間隙部整體為富含Mg區域之情況下,即可防止因內部電極與側面側間隙部之間隙所造成之耐濕性的劣化,以更確實製得耐濕性優異之積層陶瓷電子零件。In addition, when the entire side surface side gap portion is rich in the Mg region, deterioration of moisture resistance due to the gap between the internal electrode and the side surface side gap portion can be prevented, and the moisture resistance can be more reliably obtained. Laminated ceramic electronic parts.
又,使存在於有效層部之端部與陶瓷燒結體之第1或第2端面之間之端面側間隙部之中,至少與第1、第2內部電極鄰接之區域為富含Mg區域,藉此亦可抑制、防止水分從端面滲入,以進一步提升耐濕性。Further, among the end surface side gap portions existing between the end portion of the effective layer portion and the first or second end surface of the ceramic sintered body, at least the region adjacent to the first and second internal electrodes is rich in the Mg region. Thereby, it is also possible to suppress and prevent moisture from penetrating from the end surface to further improve moisture resistance.
此外,由於在端面亦形成外部端子電極,而藉由外部端子電極獲得抑制水分滲入之效果,因此不須特別設置富含Mg區域於端面側之情形亦不少,但藉由將富含Mg區域亦設於端面側,則可進一步提升耐濕可靠性。In addition, since the external terminal electrode is formed on the end surface, and the effect of suppressing the penetration of moisture is obtained by the external terminal electrode, it is not necessary to particularly provide the Mg-rich region on the end surface side, but the Mg-rich region is rich. Also provided on the end face side, the moisture resistance reliability can be further improved.
又,本發明中,亦可使第1、第2內部電極之中較設置於最外層之內部電極外側之陶瓷層之側面側間隙部之垂直投影區域及端面側間隙部之垂直投影區域的至少一者為Mg濃度高於有效層部的富含Mg區域,在該情況下,可更確實製得耐濕性優異之積層陶瓷電子零件。Further, in the present invention, at least one of the vertical projection area of the side surface side gap portion of the ceramic layer provided outside the internal electrode of the outermost layer and the vertical projection area of the end surface side gap portion may be provided in the first and second internal electrodes. One is a Mg-rich region having a Mg concentration higher than that of the effective layer portion, and in this case, a laminated ceramic electronic component excellent in moisture resistance can be more reliably produced.
又,使構成富含Mg區域之陶瓷材料之主成分為100mol%的Mg添加比例,相較於構成有效層部之陶瓷材料之主成分為100mol%的Mg添加比例多0.5~1.0mol%,藉 此可更確實提高耐濕可靠性,使本發明更具實效。In addition, the Mg addition ratio of the main component constituting the Mg-rich ceramic material is 100 mol%, and the Mg addition ratio is 0.5 to 1.0 mol%, which is 100 mol% of the main component of the ceramic material constituting the active layer portion. This makes it more practical to improve the moisture resistance reliability and make the invention more effective.
又,本發明中,在富含Mg區域中使Mg濃度具有從陶瓷燒結體之外側向內側降低的濃度梯度之構成的情況下,亦可製得耐濕性優異之積層陶瓷電子零件。Further, in the present invention, in the case where the Mg concentration has a concentration gradient which decreases from the outer side to the inner side of the ceramic sintered body in the Mg-rich region, the laminated ceramic electronic component excellent in moisture resistance can be obtained.
此外,使Mg濃度具有從陶瓷燒結體之外側向內側降低的濃度梯度之構成的方法,係例示將燒成前之原始晶片浸漬於含有Mg之黏結劑,在含浸Mg後將原始晶片加以燒成之方法等。Further, a method of constituting a composition in which the concentration of Mg has a concentration gradient from the outer side to the inner side of the ceramic sintered body is exemplified by immersing the original wafer before firing in a binder containing Mg, and firing the original wafer after impregnating Mg. Method and so on.
以下,表示本發明之實施形態並進一步詳細說明本發明特徵之處。Hereinafter, embodiments of the present invention will be described and the features of the present invention will be described in further detail.
[實施形態1][Embodiment 1]
圖1係表示本發明一實施形態之積層陶瓷電子零件(本實施形態中係積層陶瓷電容器)之構成的立體圖,圖2係圖1之A-A線截面圖,圖3係圖1之B-B線截面圖,圖4係用以說明本發明實施形態1之積層陶瓷電容器之構成的圖。1 is a perspective view showing a configuration of a laminated ceramic electronic component according to an embodiment of the present invention (a laminated ceramic capacitor in the embodiment), FIG. 2 is a cross-sectional view taken along line AA of FIG. 1, and FIG. 3 is a cross-sectional view taken along line BB of FIG. FIG. 4 is a view for explaining the configuration of the multilayer ceramic capacitor according to the first embodiment of the present invention.
本實施形態1之積層陶瓷電容器,如圖1~4所示,係具備複數個陶瓷層3所積層之陶瓷燒結體10、以交互引出至相反側之方式配置於其內部的第1及第2內部電極1,2、及以與第1及第2內部電極1,2之引出部導通之方式配設於陶瓷燒結體10彼此相對向之第1端面11與第2端面12的第1及第2外部端子電極31,32。As shown in FIGS. 1 to 4, the multilayer ceramic capacitor of the first embodiment has the ceramic sintered body 10 in which a plurality of ceramic layers 3 are laminated, and the first and second portions which are disposed in the opposite side so as to be alternately drawn to the opposite side. The internal electrodes 1 and 2 are disposed so as to be electrically connected to the lead portions of the first and second internal electrodes 1 and 2 so that the first and second end faces 11 and 12 of the ceramic sintered body 10 face each other. 2 external terminal electrodes 31, 32.
若進一步詳細說明,陶瓷燒結體10具有彼此相對向之 第1側面21及第2側面22(圖1、圖3)、與彼此相對向之第1端面11及第2端面12(圖1、圖2),於內部則如圖2、圖3所示,配置有引出至第1端面11且含有Ni之第1內部電極1、及透過既定陶瓷層(有助於形成電容之介電體層)3,於陶瓷燒結體10內部設置成與第1內部電極1相對向,並引出至第2端面12且含有Ni之第2內部電極2。As described in further detail, the ceramic sintered bodies 10 have opposite one another The first side surface 21 and the second side surface 22 ( FIGS. 1 and 3 ) and the first end surface 11 and the second end surface 12 ( FIG. 1 and FIG. 2 ) facing each other are shown in FIG. 2 and FIG. 3 . The first internal electrode 1 that is led to the first end surface 11 and contains Ni, and the first ceramic electrode that penetrates a predetermined ceramic layer (which contributes to the formation of a capacitor) 3 are disposed inside the ceramic sintered body 10 and the first internal electrode. 1 is opposed to the second internal electrode 2 including Ni to the second end face 12.
又,於陶瓷燒結體10之第1端面11,如圖1、圖2所示,配置有與第1內部電極1電氣連接的第1外部端子電極31,於陶瓷燒結體10之第2端面12,配置有與第2內部電極2電氣連接且連接於與第1外部端子電極31不同電位的第2外部端子電極32。Further, as shown in FIGS. 1 and 2, the first external terminal electrode 31 electrically connected to the first internal electrode 1 is disposed on the first end surface 11 of the ceramic sintered body 10, and the second end surface 12 of the ceramic sintered body 10 is disposed. The second external terminal electrode 32 is electrically connected to the second internal electrode 2 and connected to a potential different from that of the first external terminal electrode 31.
又,此積層陶瓷電容器中,陶瓷燒結體10,如圖3、圖4所示,包含陶瓷層3之中挾持於第1內部電極1及第2內部電極2且有助於形成電容的有效層部3a、存在於第1內部電極1及第2內部電極2之側部與陶瓷燒結體10之第1、第2側面21,22之間、及有效層部3a之側部與陶瓷燒結體10之第1、第2側面21,22之間的側面側間隙部GS 、存在於第1內部電極1及第2內部電極2之端部與陶瓷燒結體10之第1、第2端面11,12之間、及有效層部3a之端部與陶瓷燒結體10之第1或第2端面11,12之間的端面側間隙部GEFurther, in the multilayer ceramic capacitor, as shown in FIGS. 3 and 4, the ceramic sintered body 10 includes an effective layer which is held by the first internal electrode 1 and the second internal electrode 2 in the ceramic layer 3 and contributes to formation of a capacitance. The portion 3a, the side portion of the first internal electrode 1 and the second internal electrode 2, and the first and second side faces 21 and 22 of the ceramic sintered body 10, and the side portion of the effective layer portion 3a and the ceramic sintered body 10 The side surface side gap portion G S between the first and second side faces 21 and 22 and the end portions of the first inner electrode 1 and the second inner electrode 2 and the first and second end faces 11 of the ceramic sintered body 10 are The end surface side gap portion G E between the end portions of the 12 and the effective layer portion 3a and the first or second end faces 11 and 12 of the ceramic sintered body 10.
此外,陶瓷燒結體10,如圖3所示,係於較最上層之內部電極1(2)及最下層之內部電極1(2)的外側,具備有與形成電容無關之陶瓷層的外層3b。Further, as shown in FIG. 3, the ceramic sintered body 10 is provided on the outer side of the inner electrode 1 (2) of the uppermost layer and the inner electrode 1 (2) of the lowermost layer, and is provided with an outer layer 3b of a ceramic layer which is independent of the capacitance. .
接著,該側面側間隙部Gs 及端面側間隙部GE 之中,與第1、第2內部電極1,2鄰接之區域GS1 (圖3、圖4)、GE1 (圖4),係設成Mg濃度較有效層部3a高之富含Mg區域MR ,且Mg係擴及間隙部整體大致均勻分布。Subsequently, the gap in the side surface and the end portions G s side gap portion G E, and the first and second internal electrodes 1 area of the adjacent G S1 (FIG. 3, FIG. 4), G E1 (FIG. 4), The Mg-rich region M R having a higher Mg concentration than the effective layer portion 3a is provided, and the Mg-based diffusion and the entire gap portion are substantially uniformly distributed.
此外,本實施形態1中,雖使Mg擴及間隙部整體大致均勻分布,但Mg並無須一定擴及間隙部整體大致均勻分布,只要Mg存在於間隙部之內部電極附近部分即可。又,Mg亦可如本實施形態1之情形,以到達陶瓷燒結體側面之方式分布於間隙部整體,或以偏折至間隙部之內部電極附近部分的方式分布。Further, in the first embodiment, the Mg diffusion and the entire gap portion are substantially uniformly distributed, but the Mg does not necessarily have to be uniformly distributed over the entire gap portion as long as Mg is present in the vicinity of the internal electrode of the gap portion. Further, in the case of the first embodiment, Mg may be distributed to the entire gap portion so as to reach the side surface of the ceramic sintered body, or may be distributed so as to be offset to the vicinity of the internal electrode of the gap portion.
此外,本實施形態1中,構成有效層部3a之陶瓷材料係使用不含Mg之材料,構成富含Mg區域MR 之材料,係使用相對於構成有效層部3a之陶瓷材料其主要成分為100mol%、在0.5~1.0mol%之範圍添加Mg之陶瓷材料。Further, in the first embodiment, the ceramic material constituting the effective layer portion 3a is made of a material containing no Mg, and a material rich in the Mg region M R is used as the main component of the ceramic material constituting the effective layer portion 3a. A ceramic material of Mg is added in a range of 100 mol% in the range of 0.5 to 1.0 mol%.
本實施形態1之積層陶瓷電容器中,如以上所述,由於在側面側間隙部GS 及端面側間隙部GE 之中,將與第1、第2內部電極1,2鄰接之區域GS1 、GE1 ,設成Mg濃度較有效層部3a高之富含Mg區域MR ,因此在第1、第2內部電極1,2與由與其鄰接之陶瓷構成之區域GS1 及GE1 的邊界部,會生成構成內部電極1,2之金屬之Ni與源自陶瓷之金屬元素之Mg的氧化化合物,藉由該氧化化合物來填充內部電極1,2與區域GS1 及GE1 之邊界部的間隙C(參照圖5),且藉由該氧化化合物來結合內部電極1,2與區域GS1 及GE1 ,因此可製得具備高耐濕性且即使在小型化之情況下亦 對耐濕性之可靠度高的積層陶瓷電容器。In the multilayer ceramic capacitor of the first embodiment, the region G S1 adjacent to the first and second internal electrodes 1 and 2 is formed in the side surface side gap portion G S and the end surface side gap portion G E as described above. , G E1, Mg concentration is set to more effective high layer portion 3a of the Mg-rich regions M R, and therefore the boundary between the first, the second region of the internal electrode 2 composed of a ceramic adjoining G S1 and the G E1 In the portion, an oxidizing compound of Ni constituting the metal of the internal electrodes 1, 2 and Mg derived from the metal element of the ceramic is generated, and the oxidized compound fills the boundary between the internal electrode 1, 2 and the regions G S1 and G E1 . The gap C (refer to FIG. 5), and the internal electrodes 1, 2 and the regions G S1 and G E1 are bonded by the oxidizing compound, so that it is possible to have high moisture resistance and to be wet even in the case of miniaturization Multilayer ceramic capacitors with high reliability.
其次,針對該積層陶瓷電容器之製造方法作說明。Next, a description will be given of a method of manufacturing the laminated ceramic capacitor.
(1)首先,準備以介電體陶瓷為主要成分之陶瓷未加工片、含有Ni粉末作為導電材料之內部電極用導電性膏、及外部端子電極用導電性膏。(1) First, a ceramic green sheet containing a dielectric ceramic as a main component, a conductive paste for an internal electrode containing Ni powder as a conductive material, and a conductive paste for an external terminal electrode are prepared.
於陶瓷未加工片或各種導電性膏雖包含黏結劑及溶劑,但可使用公知之有機黏結劑或有機溶劑。Although the ceramic raw sheet or various conductive pastes contain a binder and a solvent, a known organic binder or an organic solvent can be used.
(2)接著,如圖6(a)所示,於陶瓷未加工片41上,藉由例如網版印刷等將導電性膏42印刷成島狀,以形成內部電極圖案42p。(2) Next, as shown in FIG. 6(a), the conductive paste 42 is printed on an island shape by, for example, screen printing on the ceramic green sheet 41 to form the internal electrode pattern 42p.
(3)接著,如圖6(b)所示,於陶瓷未加工片41上未形成內部電極圖案42p之部分,印刷側面側間隙部GS 及端面側間隙部GE 用之陶瓷膏43。(3) Next, as shown in Fig. 6 (b), the ceramic paste 43 for the side surface side gap portion G S and the end surface side gap portion G E is printed on the portion of the ceramic green sheet 41 where the internal electrode pattern 42p is not formed.
構成該陶瓷膏之陶瓷材料,係使用採用Mg之含有率較構成作為基底之陶瓷未加工片41之陶瓷材料高的陶瓷材料者。The ceramic material constituting the ceramic paste is a ceramic material having a higher content ratio of Mg than a ceramic material constituting the ceramic green sheet 41 as a base.
此外,在使Mg傾斜分布於間隙部之情況下,可使用例如準備Mg含有率不同之複數種陶瓷膏,相鄰接依序印刷之方法等。Further, when Mg is obliquely distributed in the gap portion, for example, a plurality of types of ceramic pastes having different Mg contents may be prepared, and a method of printing adjacent to each other may be used.
(4)其次,如圖6(b)所示,將陶瓷未加工片41一邊沿長度方向交互錯開既定距離一邊加以積層,以製作母塊。此外,於最外層係積層未形成內部電極圖案之外層用未加工片。(4) Next, as shown in Fig. 6(b), the ceramic green sheets 41 are laminated while being shifted by a predetermined distance in the longitudinal direction to form a mother block. Further, a raw sheet for a layer other than the internal electrode pattern was not formed on the outermost layer.
此外,母塊可視須要藉由均壓法等方法沿積層方向壓 接。In addition, the mother block may need to be pressed in the direction of the laminate by means of a pressure equalization method or the like. Pick up.
(5)其次,沿既定切割線L將母塊切割成既定尺寸以切取原始晶片(參照圖6(c))。此外,圖6(c)中,為了方便係取出1片陶瓷未加工片來表示切割線L。此外,視須要亦可以滾筒磨光等方法來研磨原始晶片,使原始晶片之稜線部及角部帶圓角。(5) Next, the mother block is cut to a predetermined size along a predetermined cutting line L to cut the original wafer (refer to Fig. 6(c)). Further, in Fig. 6(c), the cutting line L is shown for convenience in order to take out one ceramic unprocessed sheet. In addition, the original wafer may be ground by a method such as barrel polishing, such that the ridge line and the corner portion of the original wafer are rounded.
(6)其次,將原始晶片(原始陶瓷積層體)加以燒成。燒成溫度以900~1300℃較佳。燒成環境氣氛可適當分別使用大氣、N2 等環境氣氛。(6) Next, the original wafer (original ceramic laminate) is fired. The firing temperature is preferably 900 to 1300 °C. In the firing atmosphere, an atmosphere such as the atmosphere or N 2 may be used as appropriate.
(7)其次,將導電性膏塗布於經燒成之陶瓷積層體的兩端面,加以焙烤以形成外部端子電極。焙烤溫度以700~900℃較佳。焙烤環境氣氛可適當分別使用大氣、N2 等環境氣氛。(7) Next, a conductive paste is applied to both end faces of the fired ceramic laminate, and baked to form an external terminal electrode. The baking temperature is preferably from 700 to 900 °C. The atmosphere of the baking environment may be appropriately used in an atmosphere such as the atmosphere or N 2 .
此外,視須要亦可於外部端子電極表面,形成以提升電氣連接可靠性或提升焊料附著性為目的之鍍鍍敷膜。In addition, a plating film for the purpose of improving electrical connection reliability or improving solder adhesion may be formed on the surface of the external terminal electrode as needed.
藉此,即可製得具有如圖1~4所示構成之積層陶瓷電容器。Thereby, a multilayer ceramic capacitor having the structure shown in Figs. 1 to 4 can be obtained.
在本實施形態1之積層陶瓷電容器之情況下,由於不使用構成陶瓷未加工片41之材料而使用Mg含有率較高之材料,以作為側面側間隙部GS 及端面側間隙部GE 用之陶瓷膏,因此如圖3、圖4所示,側面側間隙部GS 、端面側間隙部GE 之中,位於與第1及第2內部電極1,2相同高度位置之區域所含之Mg的濃度係高於其他陶瓷部分(有效層部3a等)所含之Mg的濃度,藉由構成內部電極1,2之Ni 與該Mg之氧化化合物來填充內部電極1,2與區域GS1 及GE1 之邊界部的間隙C(參照圖5),且藉由該氧化化合物來結合內部電極1,2與區域GS1 及GE1 ,因此可製得具備高耐濕性的積層陶瓷電容器。In the case of the multilayer ceramic capacitor of the first embodiment, a material having a high Mg content is used without using a material constituting the ceramic green sheet 41, and the surface side gap portion G S and the end surface side gap portion G E are used. As shown in FIG. 3 and FIG. 4, the side surface side gap portion G S and the end surface side gap portion G E are located in the same height position as the first and second internal electrodes 1 and 2, respectively. The concentration of Mg is higher than the concentration of Mg contained in the other ceramic portions (the effective layer portion 3a, etc.), and the internal electrodes 1, 2 and the region G S1 are filled by Ni which constitutes the internal electrodes 1, 2 and the oxidized compound of the Mg. And the gap C (see FIG. 5) at the boundary of G E1 , and the internal electrodes 1, 2 and the regions G S1 and G E1 are bonded by the oxidizing compound, so that a multilayer ceramic capacitor having high moisture resistance can be obtained.
此外,由於在陶瓷層彼此間可產生構成成分之若干擴散,因此側面側間隙部GS 、端面側間隙部GE 之中富含Mg區域MR 之區域GS1 彼此、區域GE1 彼此所挾持之部分,Mg濃度亦可能稍微變高。In addition, since a certain amount of diffusion of the constituent components can be generated between the ceramic layers, the regions G S1 rich in the Mg region M R and the regions G E1 among the side-side gap portions G S and the end-face-side gap portions G E are held by each other. In part, the Mg concentration may also become slightly higher.
又,陶瓷中之Mg雖能以MgO等之形態存在,亦可以其他Mg氧化物等之化合物的狀態存在。然而,玻璃成分之Mg則不佳。此係因若側面側間隙部GS 、端面側間隙部GE 中之玻璃量增加時,則側面側間隙部GS 、端面側間隙部GE 之燒結溫度會降低,由於原來熱即容易傳導至位於晶片外表面附近之側面側間隙部GS 、端面側間隙部GE ,因此側面側間隙部GS 、端面側間隙部GE 會變成過度燒結,而有導致電容器本體之構造缺陷或強度降低的顧慮。Further, although Mg in the ceramic may exist in the form of MgO or the like, it may exist in the state of a compound such as other Mg oxide. However, the Mg of the glass component is not good. This was due when the side surface side gap portion G S, increases the amount of glass end face side gap portion G E in the, the side surface side gap portion G S, sintered end surface side gap portion G E the temperature decreases, since the original heat that is easily conducted to a position of the wafer surface in the vicinity of the outer surface of the side gap portion G S, the end face side gap portion G E, and therefore the side surface side gap portion G S, the end face side gap portion G E becomes excessive sintering, which can result in configuration of the capacitor body of a defect or strength Reduced concerns.
此外,富含Mg區域MR 之Mg含有率,如以上所述,具體而言,以相對於陶瓷材料之主要成分為100mol%,Mg之添加比例以較有效層部3a多0.5~1.0mol%較佳。Further, the Mg content of the Mg-rich region M R is as described above, specifically, 100 mol% with respect to the main component of the ceramic material, and the addition ratio of Mg is 0.5 to 1.0 mol% more than the effective layer portion 3a. Preferably.
有關本發明之構成,雖亦可考慮將構成電容器本體之陶瓷整體所含之Mg濃度普遍提高,但若變更有效層部之組成時,由於有無法獲得所須之電容器特性(介電係數、溫度特性等)的顧慮,因此最好如本發明般使側面側間隙部GS 、端面側間隙部GE 含有更多之Mg。In the configuration of the present invention, it is conceivable that the Mg concentration of the entire ceramic constituting the capacitor body is generally improved. However, when the composition of the effective layer portion is changed, the required capacitor characteristics (dielectric coefficient, temperature) cannot be obtained. Therefore, it is preferable that the side-side gap portion G S and the end surface-side gap portion G E contain more Mg as in the present invention.
此外,本發明之積層陶瓷電子零件中,陶瓷層可使用以BaTiO3 、CaTiO3 、SrTiO3 、及CaZrO3 等為主成分之介電體陶瓷。又,亦可使用將Mn化合物、Fe化合物、Cr化合物、Co化合物、及Ni化合物等副成分添加於該等主成分者。Further, in the multilayer ceramic electronic component of the present invention, a dielectric ceramic containing BaTiO 3 , CaTiO 3 , SrTiO 3 , and CaZrO 3 as a main component can be used as the ceramic layer. Further, an auxiliary component such as a Mn compound, an Fe compound, a Cr compound, a Co compound, or a Ni compound may be added to the main components.
又,本發明之積層陶瓷電子零件中,陶瓷層之厚度以1~10μm較佳。Further, in the laminated ceramic electronic component of the present invention, the thickness of the ceramic layer is preferably 1 to 10 μm.
又,本發明中,係以內部電極包含Ni為要件。具體而言,係以包含金屬之Ni、NiO等之Ni化合物、或Ni合金等為要件。內部電極之厚度以1~10μm較佳。Further, in the present invention, the internal electrode contains Ni as a requirement. Specifically, a Ni compound such as Ni or NiO containing a metal, or a Ni alloy or the like is used as a requirement. The thickness of the internal electrode is preferably 1 to 10 μm.
又,本發明中,係以將外部端子電極設為具備基底電極與於其上形成鍍敷層之複數層構造較佳。外部端子電極通常雖係以從端面繞入主面及側面之方式所形成,但只要至少形成於端面亦可。Further, in the present invention, it is preferable that the external terminal electrode has a plurality of layers including a base electrode and a plating layer formed thereon. The external terminal electrode is usually formed so as to be wound around the main surface and the side surface from the end surface, but it may be formed at least at the end surface.
構成外部端子電極之基底電極,可使用Cu、Ni、Ag、及Ag-Pd等金屬。基底電極以含玻璃較佳。As the base electrode constituting the external terminal electrode, a metal such as Cu, Ni, Ag, or Ag-Pd can be used. The base electrode is preferably glass-containing.
外部端子電極之鍍敷層,在積層陶瓷電子零件為焊接構裝之情況下,以採用鍍Ni層、鍍Sn層之2層構造較佳。在藉由導電性接著劑或打線構裝之積層陶瓷電子零件的情況下,以採用鍍Ni層、鍍Au層之2層構造較佳。又,在電容器為埋入樹脂基板的情況下,較佳為以鍍Cu層來構成最外層。敷鍍層並無須一定為2層,1層或3層以上皆可。又,鍍敷層每一層之厚度以1~10μm較佳。又,在基底電極與鍍敷層之間,亦可形成緩和應力用之樹脂層。In the case where the laminated ceramic electronic component is soldered, the plating layer of the external terminal electrode is preferably a two-layer structure in which a Ni plating layer or a Sn plating layer is used. In the case of a laminated ceramic electronic component which is formed by a conductive adhesive or wire bonding, a two-layer structure in which a Ni plating layer or an Au plating layer is used is preferable. Further, when the capacitor is embedded in the resin substrate, it is preferable to form the outermost layer by plating a Cu layer. The plating layer does not have to be two layers, and one layer or three layers or more may be used. Further, the thickness of each layer of the plating layer is preferably 1 to 10 μm. Further, a resin layer for relieving stress may be formed between the base electrode and the plating layer.
此外,本發明係著重於內部電極所含之Ni與陶瓷所含 之Mg之反應的發明,只要是可設為本發明特有之構成,且可期待作用效果者,則不限於積層陶瓷電容器,亦可應用於積層熱敏電阻、及積層電感器等。In addition, the present invention focuses on the inclusion of Ni and ceramic contained in the internal electrodes. The invention of the reaction of the Mg is not limited to the laminated ceramic capacitor, and may be applied to a laminated thermistor, a laminated inductor, or the like as long as it is a structure peculiar to the present invention and can be expected to have an effect.
[實施形態2][Embodiment 2]
圖7係表示本發明其他實施形態(實施形態2)之積層陶瓷電子零件(本實施形態中係積層陶瓷電容器)之要部構成的截面圖,係相當於實施形態1之B-B線截面圖的圖,圖8係用以說明本發明實施形態2之積層陶瓷電容器之構成的圖。Fig. 7 is a cross-sectional view showing a configuration of a main part of a laminated ceramic electronic component (a laminated ceramic capacitor in the present embodiment) according to another embodiment (the second embodiment) of the present invention, and corresponds to a cross-sectional view taken along line BB of the first embodiment. Fig. 8 is a view for explaining the configuration of a multilayer ceramic capacitor in accordance with a second embodiment of the present invention.
本實施形態2之積層陶瓷電容器,如圖7及圖8所示,係將側面側間隙部GS 設為富含Mg區域MR ,且亦將內部電極之中較最外層之內部電極外側之陶瓷層(外層)3b之側面側間隙部GS 的垂直投影區域13b設為富含Mg區域MRAs shown in FIGS. 7 and 8, the multilayer ceramic capacitor of the second embodiment has the side-side gap portion G S as the Mg-rich region M R and the outer electrode of the innermost electrode among the internal electrodes. The vertical projection region 13b of the side surface side gap portion G S of the ceramic layer (outer layer) 3b is set to be rich in the Mg region M R .
此外,本實施形態2之積層陶瓷電容器之情形,富含Mg區域MR 中,Mg濃度係具有從陶瓷燒結體之外側向內側降低的濃度梯度。Further, in the case of the multilayer ceramic capacitor of the second embodiment, in the Mg-rich region M R , the Mg concentration has a concentration gradient which decreases from the outer side to the inner side of the ceramic sintered body.
亦即,本實施形態2之積層陶瓷電容器,在下述諸點構成係與該實施形態1之情形不同,亦即:在內部電極之中較最外層之內部電極外側之陶瓷層(外層)3b之側面側間隙部GS 的垂直投影區域13b亦形成富含Mg區域MR 、在端面側間隙部GE 未形成富含Mg區域MR 、及富含Mg區域MR 中,Mg濃度具有從陶瓷燒結體之外側向內側降低的濃度梯度。In other words, the multilayer ceramic capacitor of the second embodiment differs from the first embodiment in that the ceramic layer (outer layer) 3b outside the internal electrode of the outermost layer among the internal electrodes is used. vertically projected area of the side surface 13b side gap portion G S Mg-rich region is also formed of M R, the end face side gap portion is not formed G E Mg-rich region M R, M R, and the Mg-rich region, Mg having a concentration of from ceramic A concentration gradient that decreases laterally to the inside of the sintered body.
此外,其他構成則與該實施形態1之情形相同。Further, other configurations are the same as those in the first embodiment.
即使本實施形態2之構成的情形,由於側面側間隙部GS 及側面側間隙部GS 之垂直投影區域13b係設為富含Mg區域,內部電極之側部與陶瓷層之間隙係藉由Ni與Mg之氧化化合物來填充,且內部電極之側部與陶瓷層係藉由Ni與Mg之氧化化合物更確實結合,因此與該實施形態1之情形同樣地,可製得具備高耐濕性且即使在小型化之情況下亦對耐濕性之可靠度高的積層陶瓷電容器。In the case of the configuration of the second embodiment, since the vertical projection region 13b of the side surface side gap portion G S and the side surface side gap portion G S is rich in the Mg region, the gap between the side portion of the internal electrode and the ceramic layer is The Ni and Mg oxidizing compounds are filled, and the side portions of the internal electrode and the ceramic layer are more reliably bonded by the oxidizing compound of Ni and Mg. Therefore, in the same manner as in the first embodiment, high moisture resistance can be obtained. Moreover, even in the case of miniaturization, a multilayer ceramic capacitor having high reliability against moisture resistance.
其次,針對該積層陶瓷電容器之製造方法作說明。Next, a description will be given of a method of manufacturing the laminated ceramic capacitor.
當製造本實施形態2之積層陶瓷電容器時,在實施形態1之積層陶瓷電容器之製造方法的步驟(3)中,於陶瓷未加工片上之內部電極圖案的周邊區域(未形成內部電極圖案之部分),塗布陶瓷膏,該陶瓷膏係使用與構成陶瓷未加工片(作為基底)之陶瓷材料相同的陶瓷材料。When the multilayer ceramic capacitor of the second embodiment is manufactured, in the step (3) of the method for manufacturing a multilayer ceramic capacitor according to the first embodiment, the peripheral portion of the internal electrode pattern on the ceramic green sheet (the portion where the internal electrode pattern is not formed) The ceramic paste is coated with the same ceramic material as the ceramic material constituting the ceramic green sheet (as a substrate).
接著,與實施形態1之情形同樣地,一邊將陶瓷未加工片沿長度方向交互錯開既定距離一邊加以積層,以製作母塊。此外,將未形成內部電極圖案之外層用未加工片積層於最外層。Then, in the same manner as in the first embodiment, the ceramic green sheets are laminated while being shifted by a predetermined distance in the longitudinal direction to form a mother block. Further, the outer layer in which the inner electrode pattern is not formed is laminated on the outermost layer with the unprocessed sheet.
接著,可視須要藉由均壓法等方法將母塊沿積層方向壓接。Then, it may be necessary to press the mother block in the lamination direction by a method such as a pressure equalization method.
之後,與實施形態1之情形同樣地,沿既定切割線將母塊切割成既定尺寸以切取原始晶片。此外,視須要亦可以滾筒研磨等方法來研磨原始晶片,使原始晶片之稜線部及角部帶圓角。Thereafter, as in the case of the first embodiment, the mother block is cut into a predetermined size along a predetermined cutting line to cut the original wafer. In addition, the original wafer may be ground by a method such as barrel polishing as needed, so that the ridge line and the corner portion of the original wafer are rounded.
接著,將製得之原始晶片的兩側面,浸漬於以1mol/L 之比例含有MgO之有機黏結劑溶液,使原始晶片含浸Mg分後加以乾燥。Next, the two sides of the obtained original wafer were immersed at 1 mol/L. The ratio of the organic binder solution containing MgO is such that the original wafer is impregnated with Mg and dried.
之後,以與實施形態1之情形同樣的方法,藉由進行燒成、外部端子電極之形成,而製得如圖7及8所示要部之在陶瓷燒結體10之富含Mg區域MR 中,Mg濃度具有從陶瓷燒結體10之外側向內側降低之濃度梯度的積層陶瓷電容器。Thereafter, in the same manner as in the first embodiment, by firing and external terminal electrodes, the Mg-rich region M R of the ceramic sintered body 10 as shown in Figs. 7 and 8 is obtained. Among them, the Mg concentration has a multilayer ceramic capacitor having a concentration gradient which decreases from the outer side to the inner side of the ceramic sintered body 10.
此外,本實施形態2中,雖將原始晶片之一對側面,浸漬於含有MgO之有機黏結劑溶液,但視情況亦可設為將原始晶片整體浸漬於含有MgO之有機黏結劑溶液的構成。Further, in the second embodiment, one of the original wafers is immersed in the organic binder solution containing MgO, but it may be configured to immerse the entire original wafer in an organic binder solution containing MgO.
[實施形態3][Embodiment 3]
圖9係表示本發明其他實施形態(實施形態3)之積層陶瓷電子零件(本實施形態中係積層陶瓷電容器)之要部構成的截面圖,係相當於實施形態1之圖1之B-B線截面圖,圖10係用以說明本發明實施形態3之積層陶瓷電容器之構成的圖。FIG. 9 is a cross-sectional view showing a configuration of a main part of a laminated ceramic electronic component (a laminated ceramic capacitor in the present embodiment) according to another embodiment (Embodiment 3) of the present invention, and corresponds to a cross section taken along line BB of FIG. 1 of the first embodiment. Fig. 10 is a view for explaining the configuration of a multilayer ceramic capacitor according to a third embodiment of the present invention.
本實施形態3之積層陶瓷電容器,如圖9及圖10所示,係於側面側間隙部GS 形成富含Mg區域MR ,且亦於內部電極之中較最外層之內部電極外側之陶瓷層(外層)3b之側面側間隙部GS 的垂直投影區域13b形成富含Mg區域MREmbodiment 3 of the present product ceramic capacitor, as shown in FIG. 9 and FIG. 10, based on the side surface side gap portion formed Mg-rich region G S M R, in the ceramic to the outside of the inner electrode Qieyi than the outermost internal electrodes The vertical projection region 13b of the side-side gap portion G S of the layer (outer layer) 3b forms a Mg-rich region M R .
另一方面,如圖10所示,於端面側間隙部GE 則未形成富含Mg區域。On the other hand, as shown in FIG. 10, the Mg-rich region is not formed in the end surface side gap portion G E .
亦即,本實施形態3之積層陶瓷電容器,在下述諸點構成係與該實施形態1之情形不同,亦即:在內部電極之 中較最外層之內部電極外側之陶瓷層(外層)3b之側面側間隙部GS 的垂直投影區域13b亦形成富含Mg區域MR 、及在端面側間隙部GE 未形成富含Mg區域MRIn other words, the laminated ceramic capacitor of the third embodiment differs from the first embodiment in that the ceramic layer (outer layer) 3b outside the internal electrode of the outermost layer among the internal electrodes is used. vertically projected area of the side surface 13b side gap portion G S Mg-rich region is also formed of M R, M R, and Mg-rich region at the end face of the gap G E portion is not formed.
其他構成則與該實施形態1之情形相同。此外,本實施形態3中,雖使Mg大致均勻分布擴及間隙部整體,但Mg並無須均勻分布擴及間隙部整體,只要Mg存在於間隙部之內部電極的附近部分即可。又,Mg亦可如實施形態3之情形般以到達陶瓷燒結體之側面的方式分布於間隙部整體,或以偏折至間隙部之內部電極的附近部分之形態存在。The other configuration is the same as that in the first embodiment. Further, in the third embodiment, Mg is uniformly distributed and spread over the entire gap portion, but Mg does not have to be uniformly distributed and spread over the entire gap portion, and Mg may be present in the vicinity of the internal electrode of the gap portion. Further, in the case of the third embodiment, Mg may be distributed over the entire gap portion so as to reach the side surface of the ceramic sintered body, or may exist in the vicinity of the internal electrode which is deflected to the gap portion.
本實施形態3之構成之情形下,亦可製得具備高耐濕性且即使在小型化之情況下亦對耐濕性之可靠度高的積層陶瓷電容器。In the case of the configuration of the third embodiment, a multilayer ceramic capacitor having high moisture resistance and high reliability against moisture resistance even in the case of miniaturization can be obtained.
其次,針對該積層陶瓷電容器之製造方法作說明。Next, a description will be given of a method of manufacturing the laminated ceramic capacitor.
如圖11(a)所示,於陶瓷未加工片41上藉由例如網版印刷等將導電性膏42印刷成帶狀,以形成內部電極圖案42p。As shown in Fig. 11 (a), the conductive paste 42 is printed on a ceramic green sheet 41 by, for example, screen printing or the like to form an internal electrode pattern 42p.
其次,一邊將陶瓷未加工片41沿寬度方向交互錯開既定距離一邊加以積層,以製作母塊。此外,將未形成內部電極圖案之外層用未加工片積層於最外層。Next, the ceramic green sheets 41 are laminated while being shifted by a predetermined distance in the width direction to form a mother block. Further, the outer layer in which the inner electrode pattern is not formed is laminated on the outermost layer with the unprocessed sheet.
此外,母塊可視須要藉由均壓法等方法沿積層方向壓接。In addition, the mother block may need to be crimped in the lamination direction by a method such as a pressure equalization method.
接著,沿既定切割線L將母塊切割成既定尺寸以切取原始晶片(參照圖11(b))。此外,圖11(b)中,為了方便係取出1片陶瓷未加工片來表示切割線L。Next, the mother block is cut to a predetermined size along a predetermined cutting line L to cut out the original wafer (refer to FIG. 11(b)). Further, in Fig. 11(b), the cut line L is indicated for convenience in order to take out one piece of the ceramic green sheet.
此外,該原始晶片,在內部電極圖案不僅是露出於一 側端面而係於兩側面均露出之構造之點,構成係與實施形態1及2之原始晶片有所不同。In addition, the original wafer, the internal electrode pattern is not only exposed to one The side end surface is formed at a point where both sides are exposed, and the configuration is different from the original wafers of Embodiments 1 and 2.
其次,於原始晶片之兩側面,以既定厚度塗布使用Mg含有率高於構成陶瓷未加工片之陶瓷的陶瓷膏,並加以乾燥。Next, on both sides of the original wafer, a ceramic paste having a Mg content higher than that of the ceramic constituting the ceramic green sheet is applied at a predetermined thickness and dried.
此外,在使Mg傾斜分布於間隙部之情況下,可使用例如準備Mg含有率不同之複數種陶瓷膏,依序進行塗布、乾燥重複塗布之方法等。Further, when Mg is obliquely distributed in the gap portion, for example, a plurality of ceramic pastes having different Mg contents may be prepared, and a method of coating, drying and repeating coating may be sequentially performed.
藉此,於原始晶片之兩側面,即形成相當於側面側間隙部之富含Mg區域(參照圖9)。Thereby, on the both side faces of the original wafer, the Mg-rich region corresponding to the side-side gap portion is formed (see FIG. 9).
又,此方法之情形下,亦在內部電極之中較最外層之內部電極外側之陶瓷層之側面側間隙部的垂直投影區域形成富含Mg區域。Further, in the case of this method, the Mg-rich region is also formed in the vertical projection region of the side-side gap portion of the ceramic layer outside the inner electrode of the outermost layer among the internal electrodes.
之後,視須要亦可以滾筒研磨等方法來研磨原始晶片,使原始晶片之稜線部及角部帶圓角。然而,當塗布陶瓷膏時,在使用將原始晶片之側面浸漬於陶瓷膏浴之浸漬方法的情況下,由於依據陶瓷膏之塗布形狀,原始晶片之稜線部及角部會帶圓角,因此有時不須滾筒研磨。Thereafter, the original wafer may be ground by a method such as barrel polishing as needed, so that the ridge line portion and the corner portion of the original wafer are rounded. However, when the ceramic paste is applied, in the case of using the immersion method of immersing the side surface of the original wafer in the ceramic paste bath, since the ridge line portion and the corner portion of the original wafer are rounded according to the coating shape of the ceramic paste, there is No need to grind the drum.
其他步驟則與實施形態1相同。The other steps are the same as those in the first embodiment.
實施例Example
[實施例1][Example 1]
首先,使用以耐還原性之鈦酸鋇系陶瓷粉末為主體之陶瓷漿液,使厚度為2.0μm之矩形陶瓷未加工片成形。該耐還原性之鈦酸鋇系陶瓷粉末,亦即有效層部用陶瓷材 料,本實施例中,係使用以99mol%之比例含有BaTiO3 ,1mol%之比例含有Y2 O3 ,但不含MgO之材料(MgO添加量:0mol%)。First, a ceramic slurry mainly composed of a barium titanate-based ceramic powder resistant to reduction was used to form a rectangular ceramic green sheet having a thickness of 2.0 μm. The reduction-resistant barium titanate-based ceramic powder, that is, the ceramic material for the effective layer portion, in the present embodiment, contains BaTiO 3 in a ratio of 99 mol%, and the ratio of 1 mol% contains Y 2 O 3 , but does not contain Material of MgO (addition amount of MgO: 0 mol%).
接著,於該陶瓷未加工片上,將摻和有平均粒徑為0.3μm之鎳粉末100重量份與有機黏結劑3.0重量份的導電性膏作為內部電極形成用導電性膏,以網版印刷成短邊寬度為800μm,形成內部電極圖案。Next, on the ceramic green sheet, 100 parts by weight of nickel powder having an average particle diameter of 0.3 μm and 3.0 parts by weight of a conductive paste of an organic binder were used as a conductive paste for forming an internal electrode, and screen-printed. The short side width was 800 μm to form an internal electrode pattern.
接著,將摻合陶瓷材料(構成間隙部之陶瓷材料,MgO添加比例較該有效層部用陶瓷材料多0.5mol%之陶瓷材料)100重量份與有機黏結劑3.0重量份的陶瓷膏,以網版印刷於內部電極圖案之周圍,以消除內部電極圖案與其周圍之段差,其中,相對於以99mol%之比例含有BaTiO3 ,1mol%之比例含有Y2 O3 的主成分100mol%,該陶瓷材料係以0.5mol%之比例摻合MgO作為添加物。Next, a ceramic material (ceramic material constituting the gap portion, a ceramic material having a MgO addition ratio of 0.5 mol% more than the ceramic material for the effective layer portion) is blended with 100 parts by weight of the organic paste and 3.0 parts by weight of the ceramic paste. The plate is printed around the internal electrode pattern to eliminate the step difference between the internal electrode pattern and the periphery thereof, wherein the ceramic composition is 100 mol% of the main component containing Y 2 O 3 in a ratio of 1 mol% to Ba mol 3 in a ratio of 99 mol%. MgO was blended as an additive at a ratio of 0.5 mol%.
接著,將240片印刷有該導電性膏及陶瓷膏之陶瓷未加工片加以積層,並進一步將各70片以上述方式成形且未形成內部電極圖案之陶瓷未加工片(外層用陶瓷未加工片)積層於其上下兩面側,藉由沿厚度方向加壓並予以切割,而製得長度2.0mm×寬度1.0mm×厚度1.0mm之原始晶片(未燒成之陶瓷燒結體)。Next, 240 pieces of ceramic green sheets on which the conductive paste and the ceramic paste were printed were laminated, and 70 pieces of ceramic unprocessed sheets which were formed in the above manner and which did not form internal electrode patterns (ceramic unprocessed sheets for outer layers) were further laminated. The laminate was laminated on the upper and lower sides thereof, and pressed and cut in the thickness direction to obtain an original wafer (unfired ceramic sintered body) having a length of 2.0 mm, a width of 1.0 mm, and a thickness of 1.0 mm.
以1300℃之溫度將該原始晶片加以燒成,而製得長度1.6mm×寬度0.8mm×厚度0.8mm之陶瓷燒結體。The original wafer was fired at a temperature of 1300 ° C to obtain a ceramic sintered body having a length of 1.6 mm × a width of 0.8 mm × a thickness of 0.8 mm.
於所製得之陶瓷燒結體之內部電極之露出面的兩端面,塗布導電性膏並加以焙烤,藉此形成外部端子電極, 而製得積層陶瓷電容器A(試料A)。Applying a conductive paste to both end faces of the exposed surface of the internal electrode of the obtained ceramic sintered body, and baking the same, thereby forming an external terminal electrode. A multilayer ceramic capacitor A (sample A) was produced.
又,構成間隙部之陶瓷材料,相對於以99mol%之比例含有BaTiO3 ,1mol%之比例含有Y2 O3 的主成分為100mol%,係使用以0.75mol%之比例摻合MgO作為添加物之陶瓷材料(MgO之添加比例較該有效層部用陶瓷材料多0.75mol%之材料),其他則以與該積層陶瓷電容器A之情形相同條件,製作積層陶瓷電容器B(試料B)。In addition, the ceramic material constituting the gap portion contains BaTiO 3 in a ratio of 99 mol%, and the main component containing Y 2 O 3 in a ratio of 1 mol% is 100 mol%, and MgO is blended in an amount of 0.75 mol% as an additive. In the ceramic material (the amount of addition of MgO is 0.75 mol% more than the ceramic material for the active layer portion), the laminated ceramic capacitor B (sample B) was produced under the same conditions as in the case of the multilayer ceramic capacitor A.
又,構成間隙部之陶瓷材料,相對於以99mol%之比例含有BaTiO3 ,1mol%之比例含有Y2 O3 的主成分為100mol%,係使用以1mol%之比例摻合MgO作為添加物的陶瓷材料(較該有效層部用陶瓷材料多1mol%之陶瓷材料),其他則以與該積層陶瓷電容器A之情形相同條件,製作積層陶瓷電容器C(試料C)。In addition, the ceramic material constituting the gap portion contains BaTiO 3 in a ratio of 99 mol%, and the main component containing Y 2 O 3 in a ratio of 1 mol% is 100 mol%, and MgO is blended at a ratio of 1 mol% as an additive. A ceramic material (ceramic material having 1 mol% more than the ceramic material for the effective layer portion) was used, and a multilayer ceramic capacitor C (sample C) was produced under the same conditions as in the case of the multilayer ceramic capacitor A.
又,構成間隙部之陶瓷材料,相對於以99mol%之比例含有BaTiO3 ,1mol%之比例含有Y2 O3 的主成分為100mol%,係使用以1.5mol%之比例摻合MgO作為添加物的陶瓷材料(較該有效層部用陶瓷材料多1.5mol%之陶瓷材料),其他則以與該積層陶瓷電容器A之情形相同條件,製作積層陶瓷電容器D(試料D)。In addition, the ceramic material constituting the gap portion contains BaTiO 3 in a ratio of 99 mol%, and the main component containing Y 2 O 3 in a ratio of 1 mol% is 100 mol%, and MgO is blended in an amount of 1.5 mol% as an additive. A ceramic material (a ceramic material having 1.5 mol% more than the ceramic material for the effective layer portion) was used, and a multilayer ceramic capacitor D (sample D) was produced under the same conditions as in the case of the multilayer ceramic capacitor A.
又,為了比較,該陶瓷膏係使用未添加MgO且將使用與陶瓷未加工片相同陶瓷粉末之陶瓷膏,以網版印刷於內部電極圖案周圍的陶瓷未加工片,以相同方式製作作為比較例1之積層陶瓷電容器E(試料E)。Further, for comparison, the ceramic paste was produced in the same manner as a comparative example by using a ceramic paste in which no ceramic material was added and using the same ceramic powder as the ceramic green sheet, and screen-printed on the ceramic electrode pattern around the internal electrode pattern. 1 multilayer ceramic capacitor E (sample E).
接著,針對該實施例1之積層陶瓷電容器(試料)A、B、 C、D及比較例1之積層陶瓷電容器(試料)E,進行施加0.5V直流電壓之測試,並以電阻值在1.0×10E6Ω以下之積層陶瓷電容器為不良品,其他則為良品來進行選別。Next, the multilayer ceramic capacitors (samples) A and B of the first embodiment were used. C, D, and the multilayer ceramic capacitor (sample) E of Comparative Example 1 were subjected to a test for applying a DC voltage of 0.5 V, and a multilayer ceramic capacitor having a resistance value of 1.0 × 10 E6 Ω or less was used as a defective product, and the others were selected as good products.
接著,針對選別後之良品進行耐濕測試以確認耐濕性。Next, the moisture resistance test was performed on the selected good product to confirm the moisture resistance.
測試條件係以溫度為125℃、濕度為95%RH、施加5V直流電壓、保持時間144小時,於測試後以常溫施加10V之直流電壓,並將電阻值在1.0×10E6Ω以下者判定為耐濕不良。The test conditions were as follows: temperature was 125 ° C, humidity was 95% RH, 5 V DC voltage was applied, and the holding time was 144 hours. After the test, a DC voltage of 10 V was applied at room temperature, and the resistance value was determined to be moisture resistance at 1.0×10 E6 Ω or less. bad.
表1係表示針對實施例1之積層陶瓷電容器(試料)A、B、C、D及比較例1之積層陶瓷電容器(試料)E各500個,所調查之耐濕測試前的選別不良率、及選別後之良品各500個所調查之耐濕測試不良率的測量結果。Table 1 shows 500 layers of the multilayer ceramic capacitors (samples) A, B, C, and D of the first embodiment and the multilayer ceramic capacitors (samples) E of the comparative example 1, and the rate of selection failure before the moisture resistance test, And the results of the moisture resistance test failure rate surveyed by each of the 500 good products after the selection.
如表1所示,已確認實施例1之積層陶瓷電容器(試料)A、B、C、D及比較例1之積層陶瓷電容器(試料)E之耐濕測試前的不良率雖為同等,但針對耐濕測試不良率實施例1之試料A、B、C、D係大幅低於比較例1之試料)E。特別是試料B,C中耐濕測試不良率為0%。As shown in Table 1, it was confirmed that the multilayer ceramic capacitors (samples) A, B, C, and D of the first embodiment and the multilayer ceramic capacitor (sample) E of the comparative example 1 had the same defect rate before the moisture resistance test, but The samples A, B, C, and D of Example 1 were significantly lower than the samples of Comparative Example 1 for the moisture resistance test failure rate. In particular, in the samples B and C, the moisture resistance test failure rate was 0%.
又,比較例1之試料E中,觀察到諸多即使是耐濕測試後被判定為良品者,測試後之電阻值已較測試前降低。Further, in the sample E of Comparative Example 1, it was observed that many of the resistance values after the test were determined to be good after the moisture resistance test, and the resistance value after the test was lower than before the test.
又,在實施例1之試料B、C中,於內部電極之端部完全無法檢測出間隙,在試料A、D亦僅於積層方向中央部之內部電極的端部觀察到些微間隙。由此可推測,係因實施例1之積層陶瓷電容器中,可抑制水分滲入內部電極之端部與周圍之間隙,而抑制了耐濕測試之不良的產生。Further, in the samples B and C of the first embodiment, the gap was not detected at the end portion of the internal electrode, and the samples A and D were observed only at the end portions of the internal electrodes in the central portion in the stacking direction. Therefore, in the multilayer ceramic capacitor of the first embodiment, it is possible to suppress the penetration of moisture into the gap between the end portion of the internal electrode and the periphery, thereby suppressing the occurrence of defects in the moisture resistance test.
[實施例2][Embodiment 2]
首先,使用以耐還原性之鈦酸鋇系陶瓷粉末為主體之陶瓷漿液,使厚度為2.0μm之矩形陶瓷未加工片成形。該耐還原性之鈦酸鋇系陶瓷粉末,具體而言,係使用以99mol%之比例含有BaTiO3 ,1mol%之比例含有Y2 O3 ,但不含MgO之材料(MgO添加量:0 mol%)。First, a ceramic slurry mainly composed of a barium titanate-based ceramic powder resistant to reduction was used to form a rectangular ceramic green sheet having a thickness of 2.0 μm. The reduction-resistant barium titanate-based ceramic powder is specifically a material containing BaTiO 3 in a ratio of 99 mol%, and Y 2 O 3 in a ratio of 1 mol%, but not containing MgO (addition amount of MgO: 0 mol) %).
接著,於該陶瓷未加工片上,將摻和有平均粒徑為0.3μm之鎳粉末100重量份與有機黏結劑3.0重量份的導電性膏作為內部電極形成用導電性膏,以網版印刷成短邊寬度為800μm,形成內部電極圖案。Next, on the ceramic green sheet, 100 parts by weight of nickel powder having an average particle diameter of 0.3 μm and 3.0 parts by weight of a conductive paste of an organic binder were used as a conductive paste for forming an internal electrode, and screen-printed. The short side width was 800 μm to form an internal electrode pattern.
接著,將摻合與用來使該陶瓷未加工片成形之陶瓷漿液所含之陶瓷粉末相同的陶瓷粉末(未添加MgO)100重量份與有機黏結劑3.0重量份的陶瓷膏,以網版印刷於內部電極圖案之周圍,以消除內部電極圖案與其周圍之段差。Next, 100 parts by weight of the ceramic powder (without adding MgO) and the ceramic paste of 3.0 parts by weight of the organic binder, which are the same as the ceramic powder contained in the ceramic slurry for forming the ceramic green sheet, are blended and screen-printed. Around the internal electrode pattern to eliminate the difference between the internal electrode pattern and its surroundings.
接著,將240片印刷有該導電性膏及陶瓷膏之陶瓷未加工片加以積層,並進一步將各70片以上述方式形成且未形成內部電極圖案之陶瓷未加工片(外層用陶瓷未加工片)積層於其上下兩面側,藉由沿厚度方向加壓並予以切割,而製得長度2.0mm×寬度1.0mm×厚度1.0mm之原始晶片(未燒成之陶瓷燒結體)。Next, 240 pieces of ceramic green sheets on which the conductive paste and the ceramic paste were printed were laminated, and 70 pieces of ceramic unprocessed sheets which were formed in the above manner and which did not form internal electrode patterns (ceramic unprocessed sheets for outer layers) were further laminated. The laminate was laminated on the upper and lower sides thereof, and pressed and cut in the thickness direction to obtain an original wafer (unfired ceramic sintered body) having a length of 2.0 mm, a width of 1.0 mm, and a thickness of 1.0 mm.
接著,將所製得之原始晶片的一側面,浸漬於以1mol/L之比例含有MgO之有機黏結劑溶液並予以乾燥後,另一側面亦加以浸漬,使兩側面含浸Mg。Next, one side of the obtained original wafer was immersed in an organic binder solution containing MgO at a ratio of 1 mol/L and dried, and the other side was also immersed so that both sides were impregnated with Mg.
使該原始晶片乾燥後,再以1300℃之溫度加以燒成,而製得長度1.6mm×寬度0.8mm×厚度0.8mm之陶瓷燒結體。After the original wafer was dried, it was fired at a temperature of 1300 ° C to obtain a ceramic sintered body having a length of 1.6 mm, a width of 0.8 mm, and a thickness of 0.8 mm.
接著,於所製得之陶瓷燒結體之內部電極之露出面的兩端面,塗布導電性膏並加以焙烤,藉此形成外部端子電極,而製得積層陶瓷電容器F(試料F)。Then, a conductive paste was applied to both end faces of the exposed surface of the internal electrode of the obtained ceramic sintered body, and baked to form an external terminal electrode, thereby producing a multilayer ceramic capacitor F (sample F).
此外,該積層陶瓷電容器F(試料F),係相當於具有該實施形態2所說明之構成之積層陶瓷電容器的積層陶瓷電容器,且係陶瓷燒結體之兩側面側為富含Mg區域,富含Mg區域中Mg濃度具有從陶瓷燒結體之外側向內側降低之濃度梯度的積層陶瓷電容器(參照圖7、圖8)。In addition, the multilayer ceramic capacitor F (sample F) is a multilayer ceramic capacitor corresponding to the multilayer ceramic capacitor having the configuration described in the second embodiment, and the side faces of the ceramic sintered body are rich in Mg regions, and are rich. The Mg concentration in the Mg region has a multilayer ceramic capacitor having a concentration gradient which decreases from the outer side to the inner side of the ceramic sintered body (see FIGS. 7 and 8).
又,以同樣方式使用以3.0mol/L之比例含有MgO之有 機黏結劑溶液,並藉由相同步驟製得積層陶瓷電容器G(試料G)。Also, in the same manner, the use of MgO in a ratio of 3.0 mol/L is used. The binder solution was prepared, and a multilayer ceramic capacitor G (sample G) was produced by the same procedure.
又,為了比較,以與該實施例1所說明之比較例1之情形相同方法,製作作為比較例2之積層陶瓷電容器H(試料H)。此外,該比較例2之試料H雖係以與該比較例1相同方法所製造,但製造批號與比較例1不同。Further, for comparison, a multilayer ceramic capacitor H (sample H) as Comparative Example 2 was produced in the same manner as in the case of Comparative Example 1 described in the first embodiment. Further, the sample H of Comparative Example 2 was produced in the same manner as in Comparative Example 1, but the manufacturing lot number was different from that of Comparative Example 1.
接著,針對本實施例2之積層陶瓷電容器F、G與比較例2之積層陶瓷電容器H,以與該實施例1之情形相同方法,進行耐濕測試前之選別、及針對選別後之良品的耐濕測試。Next, the multilayer ceramic capacitors F and G of the second embodiment and the multilayer ceramic capacitor H of the comparative example 2 were subjected to the selection before the moisture resistance test and the good after the selection in the same manner as in the first embodiment. Moisture resistance test.
將其結果表示於表2。The results are shown in Table 2.
如表2所示,本實施例2之積層陶瓷電容器F、G與比較例2之積層陶瓷電容器H,如表2所示,可獲得與該實施例1及比較例1大致相同之評估結果。As shown in Table 2, as shown in Table 2, the multilayer ceramic capacitors F and G of the second embodiment and the multilayer ceramic capacitor H of the comparative example 2 were obtained in substantially the same evaluation results as those of the first and the first comparative examples.
亦即,如表2所示,已確認實施例2之積層陶瓷電容器F、G及比較例2之積層陶瓷電容器H之耐濕測試前的不良率雖為同等,但耐濕測試的不良率方面,實施例2之試料的積層陶瓷電容器F、G係大幅低於比較例2之積層陶瓷電容器H。特別是,試料G中耐濕測試不良率為0%。In other words, as shown in Table 2, it has been confirmed that the multilayer ceramic capacitors F and G of the second embodiment and the multilayer ceramic capacitors of the second embodiment have the same defect rate before the moisture resistance test, but the defect rate of the moisture resistance test is The multilayer ceramic capacitors F and G of the sample of Example 2 were significantly lower than the multilayer ceramic capacitor H of Comparative Example 2. In particular, the moisture resistance test rate in the sample G was 0%.
又,比較例2之積層陶瓷電容器H中,觀察到諸多即使是耐濕測試後被判定為良品者,測試後之電阻值已較測試前降低。Further, in the multilayer ceramic capacitor H of Comparative Example 2, it was observed that many of the resistance values after the test were determined to be good after the moisture resistance test, and the resistance value after the test was lower than before the test.
又,從實施例2之積層陶瓷電容器G,於內部電極之端部完全無法檢測出間隙,在比較例2之積層陶瓷電容器F亦僅於積層方向中央部之內部電極的端部觀察到些微間隙。Further, in the multilayer ceramic capacitor G of the second embodiment, the gap was not detected at the end portion of the internal electrode, and the multilayer ceramic capacitor F of Comparative Example 2 was observed only at the end of the internal electrode at the center portion in the stacking direction. .
[實施例3][Example 3]
首先,使用以耐還原性之鈦酸鋇系陶瓷粉末為主體之陶瓷漿液,使厚度為2.0μm之矩形陶瓷未加工片成形。First, a ceramic slurry mainly composed of a barium titanate-based ceramic powder resistant to reduction was used to form a rectangular ceramic green sheet having a thickness of 2.0 μm.
該耐還原性之鈦酸鋇系陶瓷粉末,亦即有效層部用陶瓷材料,本實施例3中,相對於以99mol%之比例含有BaTiO3 ,1mol%之比例含有Y2 O3 的主成分為100mol%,係使用以1mol%之比例摻合MgO之材料。The reduction-resistant barium titanate-based ceramic powder, that is, the ceramic material for the effective layer portion, contains the main component of Y 2 O 3 in a ratio of 99 mol% to BaTiO 3 and 1 mol% in the present embodiment 3. For 100 mol%, a material in which MgO is blended in a ratio of 1 mol% is used.
接著,於該陶瓷未加工片上,將摻和有平均粒徑為0.3μm之鎳粉末100重量份與有機黏結劑3.0重量份的導電性 膏作為內部電極形成用導電性膏,以網版印刷成短邊寬度為800μm,形成內部電極圖案。Next, on the ceramic green sheet, 100 parts by weight of nickel powder having an average particle diameter of 0.3 μm and 3.0 parts by weight of an organic binder were added. The paste was used as a conductive paste for forming an internal electrode, and screen-printed to have a short side width of 800 μm to form an internal electrode pattern.
接著,將摻合陶瓷材料(構成間隙部之陶瓷材料,MgO添加比例較該有效層部用陶瓷材料多0.5mol%之陶瓷材料)100重量份與有機黏結劑3.0重量份的陶瓷膏,以網版印刷於內部電極圖案之周圍,以消除內部電極圖案與其周圍之段差,其中,相對於以99mol%之比例含有BaTiO3 ,1mol%之比例含有Y2 O3 的主成分為100mol%,該陶瓷材料係以0.5mol%之比例摻合MgO作為添加物。Next, a ceramic material (ceramic material constituting the gap portion, a ceramic material having a MgO addition ratio of 0.5 mol% more than the ceramic material for the effective layer portion) is blended with 100 parts by weight of the organic paste and 3.0 parts by weight of the ceramic paste. The plate is printed around the internal electrode pattern to eliminate the step difference between the internal electrode pattern and the periphery thereof, wherein the main component containing Y 2 O 3 in a proportion of 1 mol% is 100 mol% with respect to the content of BaTiO 3 in a ratio of 99 mol%, the ceramic The material was blended with MgO as an additive at a ratio of 0.5 mol%.
接著,將240片印刷有該導電性膏及陶瓷膏之陶瓷未加工片加以積層,並進一步將各70片以上述方式形成且未形成內部電極圖案之陶瓷未加工片(外層用陶瓷未加工片)積層於其上下兩面側,藉由沿厚度方向加壓並予以切割,而製得長度2.0mm×寬度1.0mm×厚度1.0mm之原始晶片(未燒成之陶瓷燒結體)。Next, 240 pieces of ceramic green sheets on which the conductive paste and the ceramic paste were printed were laminated, and 70 pieces of ceramic unprocessed sheets which were formed in the above manner and which did not form internal electrode patterns (ceramic unprocessed sheets for outer layers) were further laminated. The laminate was laminated on the upper and lower sides thereof, and pressed and cut in the thickness direction to obtain an original wafer (unfired ceramic sintered body) having a length of 2.0 mm, a width of 1.0 mm, and a thickness of 1.0 mm.
以1300℃之溫度將該原始晶片加以燒成,而製得長度1.6mm×寬度0.8mm×厚度0.8mm之陶瓷燒結體。The original wafer was fired at a temperature of 1300 ° C to obtain a ceramic sintered body having a length of 1.6 mm × a width of 0.8 mm × a thickness of 0.8 mm.
於所製得之陶瓷燒結體之內部電極之露出面的兩端面,塗布導電性膏並加以焙烤,藉此形成外部端子電極,而製得積層陶瓷電容器I(試料I)。A conductive paste was applied to both end faces of the exposed surface of the internal electrode of the obtained ceramic sintered body, and baked to form an external terminal electrode, thereby producing a multilayer ceramic capacitor I (Sample I).
又,構成間隙部之陶瓷材料,相對於以99mol%之比例含有BaTiO3 ,1mol%之比例含有Y2 O3 的主成分為100mol%,係使用以1.75mol%之比例摻合MgO作為添加物的陶瓷材料(MgO添加比例較該有效層部用陶瓷材料多 0.75mol%之材料),其他則以與該積層陶瓷電容器I之情形相同條件,製作積層陶瓷電容器J(試料J)。In addition, the ceramic material constituting the gap portion contains BaTiO 3 in a ratio of 99 mol%, and the main component containing Y 2 O 3 in a ratio of 1 mol% is 100 mol%, and MgO is blended as an additive at a ratio of 1.75 mol%. A ceramic material (a material having a MgO addition ratio of 0.75 mol% more than the ceramic material for the effective layer portion) was used, and a multilayer ceramic capacitor J (sample J) was produced under the same conditions as in the case of the multilayer ceramic capacitor 1.
又,構成間隙部之陶瓷材料,相對於以99mol%之比例含有BaTiO3 ,1mol%之比例含有Y2 O3 的主成分為100mol%,係使用以2mol%之比例摻合MgO作為添加物的陶瓷材料(MgO添加比例較該有效層部用陶瓷材料多1mol%之材料),其他則以與該積層陶瓷電容器I之情形相同條件,製作積層陶瓷電容器K(試料K)。In addition, the ceramic material constituting the gap portion contains BaTiO 3 in a ratio of 99 mol%, and the main component containing Y 2 O 3 in a ratio of 1 mol% is 100 mol%, and MgO is blended as an additive at a ratio of 2 mol%. A ceramic material (a material having a MgO addition ratio of 1 mol% more than the ceramic material for the effective layer portion) was used, and a multilayer ceramic capacitor K (sample K) was produced under the same conditions as in the case of the multilayer ceramic capacitor 1.
又,構成間隙部之陶瓷材料,相對於以99mol%之比例含有BaTiO3 ,1mol%之比例含有Y2 O3 的主成分為100mol%,係使用以2.5mol%之比例摻合MgO作為添加物的陶瓷材料(MgO添加比例較該有效層部用陶瓷材料多1.5mol%之陶瓷材料),其他則以與該積層陶瓷電容器I之情形相同條件,製作積層陶瓷電容器L(試料L)。In addition, the ceramic material constituting the gap portion contains BaTiO 3 in a ratio of 99 mol%, and the main component containing Y 2 O 3 in a ratio of 1 mol% is 100 mol%, and MgO is blended in an amount of 2.5 mol% as an additive. A ceramic material (a ceramic material having a MgO addition ratio of 1.5 mol% more than the ceramic material for the effective layer portion) was used, and a multilayer ceramic capacitor L (sample L) was produced under the same conditions as in the case of the multilayer ceramic capacitor 1.
又,為了比較,構成間隙部之陶瓷材料,相對於以99mol%之比例含有BaTiO3 ,1mol%之比例含有Y2 O3 的主成分為100mol%,係使用以1mol%之比例摻合MgO作為添加物的陶瓷材料(與該有效層部用陶瓷材料相同之材料),其他則以與該積層陶瓷電容器I之情形相同條件,製作積層陶瓷電容器M(試料M)。Moreover, for comparison, the ceramic material constituting the gap portion contains BaTiO 3 in a ratio of 99 mol%, and the main component containing Y 2 O 3 in a ratio of 1 mol% is 100 mol%, and MgO is blended at a ratio of 1 mol%. The ceramic material of the additive (the same material as the ceramic material for the effective layer portion) was used, and the laminated ceramic capacitor M (sample M) was produced under the same conditions as in the case of the multilayer ceramic capacitor 1.
接著,針對該實施例3之積層陶瓷電容器(試料)I、J、K、L及比較例3之積層陶瓷電容器(試料)M,進行施加0.5V直流電壓之測試,以電阻值在1.0×10E6Ω以下之積層陶瓷電容器為不良品,其他則為良品進行選別。Next, a multilayer ceramic capacitor (sample) I, J, K, L of the third embodiment and a multilayer ceramic capacitor (sample) M of Comparative Example 3 were subjected to a test for applying a DC voltage of 0.5 V to have a resistance value of 1.0 × 10 E6 Ω. The following laminated ceramic capacitors are defective products, and others are good for sorting.
接著,針對選別後之良品進行耐濕測試以確認耐濕性。Next, the moisture resistance test was performed on the selected good product to confirm the moisture resistance.
測試條件係以溫度為125℃、濕度為95%RH、施加5V直流電壓、保持時間144小時,於測試後施加10V之直流電壓,將電阻值在1.0×10E6Ω以下者判定為耐濕不良。The test conditions were such that the temperature was 125 ° C, the humidity was 95% RH, a direct current voltage of 5 V was applied, and the holding time was 144 hours. A DC voltage of 10 V was applied after the test, and a resistance value of 1.0 × 10 E6 Ω or less was judged to be moisture-resistant.
表3係表示針對實施例3之積層陶瓷電容器(試料)I、J、K、L及比較例3之積層陶瓷電容器(試料)M各500個,所調查之耐濕測試前的選別不良率、及選別後之良品各500個所調查之耐濕測試不良率的測量結果。Table 3 shows the number of the multilayer ceramic capacitors (samples) I, J, K, and L of the third embodiment, and the number of the multilayer ceramic capacitors (samples) M of Comparative Example 3, 500, and the poorness rate before the moisture resistance test, And the results of the moisture resistance test failure rate surveyed by each of the 500 good products after the selection.
如表3所示,已確認實施例3之積層陶瓷電容器(試料)I、K、L及比較例3之積層陶瓷電容器(試料)M之耐濕測試前的不良率雖大致同等,但耐濕測試不良率方面實施例3之試料I、K、L則大幅低於比較例3之試料M。As shown in Table 3, it was confirmed that the multilayer ceramic capacitors (samples) I, K, and L of the third embodiment and the multilayer ceramic capacitor (sample) M of Comparative Example 3 had substantially the same defect rate before the moisture resistance test, but were resistant to moisture. The samples I, K, and L of Example 3 in terms of the test failure rate were significantly lower than the sample M of Comparative Example 3.
又,MgO之添加量為1.75mol%之實施例之試料J的情形,耐濕測試前之不良率為0%,耐濕測試後之不良率亦為0%。Further, in the case of the sample J of the example in which the amount of MgO added was 1.75 mol%, the defect rate before the moisture resistance test was 0%, and the defect rate after the moisture resistance test was also 0%.
又,MgO之添加量為1.5mol%之實施例之試料I的情形,耐濕測試前之不良率雖為0.20%,但耐濕測試後之不良率亦為0%,MgO之添加量為2mol%之實施例之試料K的情形,耐濕測試前之不良率雖為0.40%,但耐濕測試後之不良率亦為0%。Further, in the case of the sample I of the example in which the amount of MgO added was 1.5 mol%, the defect rate before the moisture resistance test was 0.20%, but the defect rate after the moisture resistance test was also 0%, and the amount of MgO added was 2 mol. In the case of the sample K of the example, the defect rate before the moisture resistance test was 0.40%, but the defect rate after the moisture resistance test was also 0%.
另一方面,已確認MgO之添加量為2.5mol%之實施例之試料L的情形,耐濕測試前之不良率雖為0.40%,但耐濕測試之不良率為8%,雖大幅低於比較例3之試料M,若相較於滿足本發明之要件之其他試料I、J、K,則耐濕測試不良率變高。On the other hand, in the case of the sample L of the example in which the amount of MgO added was 2.5 mol%, the defect rate before the moisture resistance test was 0.40%, but the defect rate of the moisture resistance test was 8%, which was significantly lower than In the sample M of Comparative Example 3, the moisture resistance test failure rate was higher than the other samples I, J, and K satisfying the requirements of the present invention.
又,比較例3之試料M中,觀察到諸多即使是耐濕測試後被判定為良品者,測試後之電阻值已較測試前降低。Further, in the sample M of Comparative Example 3, it was observed that even if it was judged to be a good product after the moisture resistance test, the resistance value after the test was lower than that before the test.
上述各實施形態及實施例1、2中,雖以構成有效層部之陶瓷未含Mg之情形為例作說明,比較例3中則以構成有效層部之陶瓷含有Mg之情形為例作說明,但與構成有效層部之陶瓷是否含有Mg無關,藉由使富含Mg層之Mg含有 率在本發明既定範圍內高於有效層部之Mg含有率,即可得到本發明之基本效果。In each of the above-described embodiments and the first and second embodiments, the case where the ceramic constituting the effective layer portion does not contain Mg will be described as an example, and in the comparative example 3, the case where the ceramic constituting the effective layer portion contains Mg will be described as an example. However, regardless of whether or not the ceramic constituting the effective layer portion contains Mg, the Mg-rich layer contains Mg. The basic effect of the present invention can be obtained by setting the Mg content of the effective layer portion within the predetermined range of the present invention.
此外,上述實施形態及實施例中,雖以積層陶瓷電容.器為例作說明,但本發明並不限於積層陶瓷電容器,亦可廣泛應用於具備含有Ni之內部電極例如積層熱敏電阻或積層電感器等各種積層陶瓷電子零件。Further, in the above-described embodiments and examples, a multilayer ceramic capacitor is described as an example. However, the present invention is not limited to a multilayer ceramic capacitor, and can be widely applied to an internal electrode including Ni, such as a laminated thermistor or a laminate. Various laminated ceramic electronic parts such as inductors.
本發明進一步在其他之點亦不限於上述實施例,有關陶瓷層與內部電極之積層形態或積層數、構成有效層部或側面側、端面側間隙部之陶瓷材料的種類、及含有Ni之內部電極材料的組成等,在本發明之範圍內可作各種應用、或加以變形。Further, the present invention is not limited to the above embodiment, and the laminated form or the number of layers of the ceramic layer and the internal electrode, the type of the ceramic material constituting the effective layer portion, the side surface side, the end surface side gap portion, and the interior containing Ni The composition and the like of the electrode material can be variously applied or modified within the scope of the invention.
如以上所述,根據本發明即能提供可提升具有將內部電極透過陶瓷層設置於陶瓷燒結體中之構造之積層陶瓷電子零件的耐濕可靠性,即使在小型化之情況下亦對耐濕性之可靠度高的積層陶瓷電子零件。As described above, according to the present invention, it is possible to provide moisture resistance reliability of a laminated ceramic electronic component having a structure in which an internal electrode is transmitted through a ceramic layer in a ceramic sintered body, and is resistant to moisture even in the case of miniaturization. Multilayer ceramic electronic parts with high reliability.
因此,本發明適合利用在使用於各種用途之積層陶瓷電容器、積層熱敏電阻、積層電感器等各種積層陶瓷電子零件。Therefore, the present invention is suitable for use in various laminated ceramic electronic parts such as multilayer ceramic capacitors, laminated thermistors, and laminated inductors used in various applications.
1‧‧‧第1內部電極1‧‧‧1st internal electrode
2‧‧‧第2內部電極2‧‧‧2nd internal electrode
3‧‧‧陶瓷層3‧‧‧Ceramic layer
3a‧‧‧有效層部3a‧‧‧ Effective Layer
3b‧‧‧外層3b‧‧‧ outer layer
10‧‧‧陶瓷燒結體10‧‧‧ceramic sintered body
11‧‧‧陶瓷燒結體之第1端面11‧‧‧The first end of the ceramic sintered body
12‧‧‧陶瓷燒結體之第2端面12‧‧‧The second end of the ceramic sintered body
13b‧‧‧垂直投影區域13b‧‧‧Vertical projection area
21‧‧‧陶瓷燒結體之第1側面21‧‧‧The first side of the ceramic sintered body
22‧‧‧陶瓷燒結體之第2側面22‧‧‧The second side of the ceramic sintered body
31‧‧‧第1外部端子電極31‧‧‧1st external terminal electrode
32‧‧‧第2外部端子電極32‧‧‧2nd external terminal electrode
41‧‧‧陶瓷未加工片41‧‧‧Ceramic unprocessed tablets
42‧‧‧導電性膏42‧‧‧ Conductive paste
42p‧‧‧內部電極圖案42p‧‧‧ internal electrode pattern
43‧‧‧陶瓷膏43‧‧‧Ceramic paste
GE ‧‧‧端面側間隙部G E ‧‧‧End face clearance
GE1 ‧‧‧端面側間隙部與第1、第2內部電極鄰接之區域G E1 ‧‧‧A region adjacent to the first and second internal electrodes
GS ‧‧‧側面側間隙部G S ‧‧‧ side side gap
GS1 ‧‧‧側面側間隙部與第1、第2內部電極鄰接之區域G S1 ‧‧‧A region adjacent to the first and second internal electrodes
L‧‧‧切割線L‧‧‧ cutting line
MR ‧‧‧富含Mg區域M R ‧‧‧rich in Mg area
圖1係表示本發明實施形態1之積層陶瓷電子零件(積層陶瓷電容器)的立體圖。Fig. 1 is a perspective view showing a laminated ceramic electronic component (multilayer ceramic capacitor) according to the first embodiment of the present invention.
圖2係圖1之A-A線截面圖。Figure 2 is a cross-sectional view taken along line A-A of Figure 1.
圖3係圖1之B-B線截面圖。Figure 3 is a cross-sectional view taken along line B-B of Figure 1.
圖4係用以說明本發明實施形態1之積層陶瓷電容器 之構成的圖。Figure 4 is a view showing a multilayer ceramic capacitor according to Embodiment 1 of the present invention; The composition of the figure.
圖5係用以說明本發明實施形態1之積層陶瓷電容器之作用的要部截面圖。Fig. 5 is a cross-sectional view of an essential part for explaining the action of the multilayer ceramic capacitor according to the first embodiment of the present invention.
圖6(a)、(b)、(c)係表示本發明實施形態1之積層陶瓷電容器之製造方法的圖。(a), (b), and (c) of FIG. 6 are views showing a method of manufacturing a multilayer ceramic capacitor according to the first embodiment of the present invention.
圖7係表示本發明實施形態2之積層陶瓷電容器之構成的側面截面圖。Fig. 7 is a side cross-sectional view showing the configuration of a multilayer ceramic capacitor in accordance with a second embodiment of the present invention.
圖8係用以說明本發明實施形態2之積層陶瓷電容器之構成的圖。Fig. 8 is a view for explaining the configuration of a multilayer ceramic capacitor in accordance with a second embodiment of the present invention.
圖9係表示本發明實施形態3之積層陶瓷電容器之構成的側面截面圖。Fig. 9 is a side cross-sectional view showing the configuration of a multilayer ceramic capacitor in accordance with a third embodiment of the present invention.
圖10係用以說明本發明實施形態3之積層陶瓷電容器之構成的圖。Fig. 10 is a view for explaining the configuration of a multilayer ceramic capacitor in accordance with a third embodiment of the present invention.
圖11(a)、(b)係表示本發明實施形態3之積層陶瓷電容器之製造方法的圖。(a) and (b) of FIG. 11 are views showing a method of manufacturing a multilayer ceramic capacitor according to a third embodiment of the present invention.
1‧‧‧第1內部電極1‧‧‧1st internal electrode
2‧‧‧第2內部電極2‧‧‧2nd internal electrode
3‧‧‧陶瓷層3‧‧‧Ceramic layer
3a‧‧‧有效層部3a‧‧‧ Effective Layer
3b‧‧‧外層3b‧‧‧ outer layer
10‧‧‧陶瓷燒結體10‧‧‧ceramic sintered body
21‧‧‧陶瓷燒結體之第1側面21‧‧‧The first side of the ceramic sintered body
22‧‧‧陶瓷燒結體之第2側面22‧‧‧The second side of the ceramic sintered body
GS ‧‧‧側面側間隙部G S ‧‧‧ side side gap
GS1 ‧‧‧側面側間隙部與第1、第2內部電極鄰接之區域G S1 ‧‧‧A region adjacent to the first and second internal electrodes
MR ‧‧‧富含Mg區域M R ‧‧‧rich in Mg area

Claims (14)

  1. 一種積層陶瓷電子零件,具備:陶瓷燒結體,係複數個陶瓷層所積層而成,具有彼此相對向之第1側面及第2側面、及彼此相對向之第1端面及第2端面;第1內部電極,係形成於該陶瓷燒結體內部並引出至該第1端面,且含有Ni;第2內部電極,係於該陶瓷燒結體內部形成為透過特定之該陶瓷層與該第1內部電極相對向,並引出至該第2端面,且含有Ni;第1外部端子電極,係形成於該陶瓷燒結體之該第1端面,並與該第1內部電極電氣連接;以及第2外部端子電極,係形成於該陶瓷燒結體之該第2端面,並與該第2內部電極電氣連接,且連接於與該第1外部端子電極不同之電位,其特徵在於:該陶瓷燒結體包含:該陶瓷層之中挾持於該第1內部電極及該第2內部電極且有助於形成電容的有效層部;以及存在於該第1、第2內部電極之側部與該陶瓷燒結體之第1、第2側面之間、及該有效層部之側部與該陶瓷燒結體之第1、第2側面之間的側面側間隙部;使該側面側間隙部之中從與該第1、第2內部電極接觸之區域至該陶瓷燒結體側面之區域為Mg濃度高於該有效層部的富含Mg區域。 A laminated ceramic electronic component comprising: a ceramic sintered body formed by stacking a plurality of ceramic layers, having a first side surface and a second side surface facing each other, and a first end surface and a second end surface facing each other; The internal electrode is formed inside the ceramic sintered body and led to the first end surface and contains Ni. The second internal electrode is formed in the ceramic sintered body so that the ceramic layer is transparent to the first internal electrode. And leading to the second end surface and containing Ni; the first external terminal electrode is formed on the first end surface of the ceramic sintered body, and is electrically connected to the first internal electrode; and the second external terminal electrode Formed on the second end surface of the ceramic sintered body, electrically connected to the second internal electrode, and connected to a potential different from the first external terminal electrode, wherein the ceramic sintered body includes: the ceramic layer The first inner electrode and the second inner electrode are supported by the first inner electrode and the second inner electrode to form an effective layer portion of the capacitor; and the side portions of the first and second inner electrodes and the first and second ceramic sintered bodies are present. 2 between the sides And a side surface side gap portion between the side portion of the effective layer portion and the first and second side faces of the ceramic sintered body; and a region of the side surface side gap portion that is in contact with the first and second internal electrodes The region on the side of the ceramic sintered body is a Mg-rich region having a Mg concentration higher than that of the effective layer portion.
  2. 如申請專利範圍第1項之積層陶瓷電子零件,其中,使該側面側間隙部中分別位於與該第1、第2內部電極相同高度之區域為該富含Mg區域。 The laminated ceramic electronic component according to the first aspect of the invention, wherein the region of the side-side gap portion located at the same height as the first and second internal electrodes is the Mg-rich region.
  3. 如申請專利範圍第1項之積層陶瓷電子零件,其中,使該側面側間隙部整體為該富含Mg區域。 The laminated ceramic electronic component according to the first aspect of the invention, wherein the side side gap portion as a whole is the Mg-rich region.
  4. 如申請專利範圍第1至3項中任一項之積層陶瓷電子零件,其中,該陶瓷燒結體包含存在於該第1、第2內部電極之端部與該陶瓷燒結體之第1、第2端面之間、及該有效層部之端部與該陶瓷燒結體之第1或第2端面之間的端面側間隙部;使該端面側間隙部之中至少與該第1、第2內部電極鄰接之區域為Mg濃度高於該有效層部的富含Mg區域。 The multilayer ceramic electronic component according to any one of claims 1 to 3, wherein the ceramic sintered body includes the first and second ends of the first and second internal electrodes and the first and second ceramic sintered bodies. An end surface side gap portion between the end faces and an end portion of the effective layer portion and the first or second end faces of the ceramic sintered body; and at least the first and second internal electrodes are included in the end face side gap portions The adjacent region is a Mg-rich region having a Mg concentration higher than that of the active layer portion.
  5. 如申請專利範圍第1至3項中任一項之積層陶瓷電子零件,其中,使該第1、第2內部電極中較最外層之內部電極外側之陶瓷層之該側面側間隙部之垂直投影區域、及該端面側間隙部之垂直投影區域的至少一者,為Mg濃度高於該有效層部的富含Mg區域。 The laminated ceramic electronic component according to any one of claims 1 to 3, wherein the vertical projection of the side surface side gap portion of the ceramic layer outside the internal electrode of the outermost layer of the first and second internal electrodes At least one of the region and the vertical projection region of the end face side gap portion is a Mg-rich region having a Mg concentration higher than the effective layer portion.
  6. 如申請專利範圍第4項之積層陶瓷電子零件,其中,使該第1、第2內部電極中較最外層之內部電極外側之陶瓷層之該側面側間隙部之垂直投影區域、及該端面側間隙部之垂直投影區域的至少一者,為Mg濃度高於該有效層部的富含Mg區域。 The laminated ceramic electronic component according to the fourth aspect of the invention, wherein the vertical projection region of the side surface side gap portion of the ceramic layer outside the internal electrode of the outermost layer of the first and second internal electrodes, and the end surface side At least one of the vertical projection regions of the gap portion is a Mg-rich region having a Mg concentration higher than the effective layer portion.
  7. 如申請專利範圍第1至3項中任一項之積層陶瓷電子零件,其中,使構成該富含Mg區域之陶瓷材料之主成分 為100mol%的Mg添加比例,相較於構成該有效層部之陶瓷材料之主成分為100mol%的Mg添加比例多0.5~1.0mol%。 The laminated ceramic electronic component according to any one of claims 1 to 3, wherein the main component of the ceramic material constituting the Mg-rich region is made The addition ratio of 100 mol% of Mg is 0.5 to 1.0 mol% more than the Mg addition ratio of 100 mol% of the main component of the ceramic material constituting the effective layer portion.
  8. 如申請專利範圍第4項之積層陶瓷電子零件,其中,使構成該富含Mg區域之陶瓷材料之主成分為100mol%的Mg添加比例,相較於構成該有效層部之陶瓷材料之主成分為100mol%的Mg添加比例多0.5~1.0mol%。 The multilayer ceramic electronic component according to the fourth aspect of the invention, wherein the Mg addition ratio of the main component constituting the Mg-rich ceramic material is 100 mol%, compared to the main component of the ceramic material constituting the effective layer portion. The proportion of addition of 100 mol% of Mg is 0.5 to 1.0 mol%.
  9. 如申請專利範圍第5項之積層陶瓷電子零件,其中,使構成該富含Mg區域之陶瓷材料之主成分為100mol%的Mg添加比例,相較於構成該有效層部之陶瓷材料之主成分為100mol%的Mg添加比例多0.5~1.0mol%。 The multilayer ceramic electronic component according to the fifth aspect of the invention, wherein the Mg addition ratio of the main component constituting the Mg-rich ceramic material is 100 mol%, compared to the main component of the ceramic material constituting the effective layer portion. The proportion of addition of 100 mol% of Mg is 0.5 to 1.0 mol%.
  10. 如申請專利範圍第6項之積層陶瓷電子零件,其中,使構成該富含Mg區域之陶瓷材料之主成分為100mol%的Mg添加比例,相較於構成該有效層部之陶瓷材料之主成分為100mol%的Mg添加比例多0.5~1.0mol%。 The multilayer ceramic electronic component according to claim 6, wherein the Mg addition ratio of the main component constituting the Mg-rich ceramic material is 100 mol%, compared to the main component of the ceramic material constituting the effective layer portion. The proportion of addition of 100 mol% of Mg is 0.5 to 1.0 mol%.
  11. 如申請專利範圍第1至3項中任一項之積層陶瓷電子零件,其中,該富含Mg區域中Mg濃度具有從陶瓷燒結體之外側向內側降低的濃度梯度。 The laminated ceramic electronic component according to any one of claims 1 to 3, wherein the Mg concentration in the Mg-rich region has a concentration gradient which decreases from the outer side to the inner side of the ceramic sintered body.
  12. 如申請專利範圍第4項之積層陶瓷電子零件,其中,該富含Mg區域中Mg濃度具有從陶瓷燒結體之外側向內側降低的濃度梯度。 The multilayer ceramic electronic component of claim 4, wherein the Mg concentration in the Mg-rich region has a concentration gradient that decreases from the outer side to the inner side of the ceramic sintered body.
  13. 如申請專利範圍第5項之積層陶瓷電子零件,其中,該富含Mg區域中Mg濃度具有從陶瓷燒結體之外側向內側降低的濃度梯度。 The multilayer ceramic electronic component of claim 5, wherein the Mg concentration in the Mg-rich region has a concentration gradient that decreases from the outer side to the inner side of the ceramic sintered body.
  14. 如申請專利範圍第6項之積層陶瓷電子零件,其 中,該富含Mg區域中Mg濃度具有從陶瓷燒結體之外側向內側降低的濃度梯度。 Such as the laminated ceramic electronic component of claim 6 of the patent scope, In the Mg-rich region, the concentration of Mg has a concentration gradient that decreases from the outside to the inside of the ceramic sintered body.
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