as) United States
`a2) Patent Application Publication io) Pub. No.: US 2011/0141655 Al
` Jeonget al. (43) Pub. Date: Jun. 16, 2011
`
`
`
`US 20110141655A1
`
`(54) MULTILAYER CERAMIC CAPACITOR
`
`(52) US. CD wees 361/303; 361/306.3; 361/313
`
`(75)
`
`Inventors:
`
`(73) Assignee:
`
`Ji Hun Jeong, Suwon (KR); Hyo
`Jung Kim, Suwon (KR); Hyo Jung
`Kim,Seoul (KR); Dong Ik Chang,
`Suwon (KR); Doo Young Kim,
`Yongin (KR)
`SAMSUNG
`ELECTRO-MECHANICS CO.,
`LID.
`
`(21) Appl. No.:
`(22)
`Filed:
`
`12/768,993
`Apr. 28, 2010
`
`(30)
`
`Foreign Application Priority Data
`
`Dec. 10, 2009
`
`(KR) woe eens 10-2009-0122195
`
`Publication Classification
`
`(51)
`
`Int. Cl.
`HOIG 4/12
`HOIG 4/005
`
`(2006.01)
`(2006.01)
`
`(57)
`
`ABSTRACT
`
`Disclosed is multilayer ceramic capacitor. The multilayer
`ceramic capacitorincludesa capacitive part including dielec-
`tric layers andfirst and secondinternal electrodes alternately
`laminated therein, wherein the dielectric layers includefirst
`ceramic particles having an averageparticle size of 0.1 um to
`0.3 um, and oneset of ends ofthefirst internal electrodes and
`one set of ends of the secondinternal electrodes are exposed
`in a lamination direction of the dielectric layers, a protective
`layer formedonat least one of top and bottom surfaces of the
`capacitive part, including second ceramic particles and hav-
`ing a porosity of 2% to 4%, wherein an average particle size
`ratio of the second ceramic particlesto the first ceramic par-
`ticles ranges from 1.1 to 1.3; and first and second external
`electrodes electrically connected to the first and secondinter-
`nal electrodes exposed in the lamination direction of the
`dielectric layers.
`
`
`
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`AVX CORPORATION
`AVX CORPORATION
`
`000001
`
`

`

`Patent Application Publication
`
`Jun. 16,2011 Sheet 1 of 2
`
`US 2011/0141655 Al
`
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`

`

`Patent Application Publication
`
`Jun. 16,2011 Sheet 2 of 2
`
`US 2011/0141655 Al
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`p
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`

`

`US 2011/0141655 Al
`
`Jun. 16, 2011
`
`MULTILAYER CERAMIC CAPACITOR
`
`CROSS-REFERENCE TO RELATED
`APPLICATIONS
`
`[0001] This application claimsthepriority ofKorean Patent
`Application No. 10-2009-0122195 filed on Dec. 10, 2009, in
`the Korean Intellectual Property Office, the disclosure of
`whichis incorporated herein by reference.
`
`capacitor. Such thermal impact and shear stress may cause
`cracks in the multilayer ceramic capacitor.
`[0012] As the multilayer ceramic capacitor has recently
`become smaller in size and higher in capacitance, many
`attempts have been made to manufacture a thinner and mul-
`tilayer ceramic body. However, as the ceramic body has
`becomethinner and multilayered, a crack occurrencerate has
`increased. Therefore, there is an increasing need for prevent-
`ing this increase in the crack occurrencerate therein.
`
`BACKGROUND OF THE INVENTION
`
`SUMMARY OF THE INVENTION
`
`1. Field of the Invention
`[0002]
`[0003] The presentinventionrelates to a multilayer ceramic
`capacitor, and more particularly,
`to a multilayer ceramic
`capacitor having a high level of reliability and a low crack
`occurrence rate by reducing stress acting on the multilayer
`ceramic capacitor.
`[0004]
`2. Description of the Related Art
`[0005]
`In general, electronic components using a ceramic
`material, such as capacitors, inductors, piezoelectric devices,
`varistors or thermistors, include a ceramic body formed of a
`ceramic material,
`internal electrodes provided inside the
`ceramic body, and external electrodesinstalled on the surface
`of the ceramic body.
`[0006] Multilayer ceramic capacitors among such ceramic
`electronic components include a plurality of laminated
`dielectric layers,
`internal electrodes interleaved with the
`dielectric layers, and external electrodes electrically con-
`nected to the internal electrodes.
`
`[0007] Multilayer ceramic capacitors are being widely used
`as a part of mobile communications devices, such as comput-
`ers, personal digital assistants (PDA) and mobile phones, due
`to their small size, high capacity and ease of mounting.
`[0008] Recently, as electronic products have become com-
`pact and multi-functional, chip components have also tended
`to become compact and highly functional. Following this
`trend, a multilayer ceramic capacitor is required to be smaller
`than ever before, but to have a high capacity.
`[0009] As for a general method of manufacturing a multi-
`layer ceramic capacitor, ceramic green sheets are manufac-
`tured and a conductive paste is printed on the ceramic green
`sheets to thereby form internal electrode layers. Tens to hun-
`dreds of such ceramic green sheets, provided with the internal
`electrode layers, are then laminated to thereby produce a
`green ceramic laminate. Thereafter, the green ceramic lami-
`nate is pressed at high pressure and high temperature and
`subsequently cut into green chips. Thereafter, the green chip
`is subjected to plasticizing, firing and polishing processes,
`and external electrodes are then formed thereon, thereby
`completing a multilayer ceramic capacitor.
`[0010] Typically, the internal electrodes, formed of metal,
`shrink and expand easily as compared to ceramic materials.
`Thus, stress caused by this difference in thermal expansion
`coefficient may act on the ceramic laminate, thereby causing
`cracks.
`
`[0011] The multilayer ceramic capacitor is used while
`mounted on a wiring board. In this case, the external elec-
`trodes of the multilayer ceramic capacitor are electrically
`connected to the wiring board by soldering and a conductive
`land on the wiring board. When the multilayer ceramic
`capacitor is mounted on the wiring board by using soldering,
`or when the wiring board mounted with the multilayer
`ceramic capacitor undergoes a cutting process,
`thermal
`impact and shearstress are applied to the multilayer ceramic
`
`[0013] An aspect of the present invention provides a mul-
`tilayer ceramic capacitor capable of achieving a high level of
`reliability and a low crack occurrencerate by reducingstress
`acting on the multilayer ceramic capacitor.
`[0014] According to an aspect of the present invention,
`there is provided a multilayer ceramic capacitor including: a
`capacitive part including dielectric layers and first and second
`internal electrodes alternately laminated therein, wherein the
`dielectric layers includefirst ceramic particles having an aver-
`age particle size of 0.1 um to 0.3 um, and oneset of ends ofthe
`first internal electrodes and one set of ends of the second
`
`internal electrodes are exposed in a lamination direction of
`the dielectric layers; a protective layer formed on at least one
`of top and bottom surfaces of the capacitive part, including
`second ceramicparticles and having a porosity of 2% to 4%,
`wherein an average particle size ratio of the second ceramic
`particles to the first ceramic particles ranges from 1.1 to 1.3;
`and first and second external electrodes electrically con-
`nected to the first and secondinternal electrodes exposed in
`the lamination direction of the dielectric layers.
`[0015]
`Thefirst ceramic particles may include barium titan-
`ate (BaTiO,)-based ceramics, lead complex perovskite-based
`ceramics, or strontium titanate (SrTiO,)-based ceramics. The
`second ceramic particles may include barium titanate (Ba-
`TiO,)-based ceramics,
`lead complex perovskite-based
`ceramics, or strontium titanate (SrTiO, )-based ceramics.
`[0016] The dielectric layers of the capacitive part may have
`a porosity of 1% orless.
`[0017] Thecapacitive part may havea thickness of 50 um to
`2000 um, and the protective layer may have a thickness of 10
`um to 100 pm.
`
`BRIEF DESCRIPTION OF THE DRAWINGS
`
`[0018] The above and other aspects, features and other
`advantages of the present invention will be more clearly
`understood from the following detailed description taken in
`conjunction with the accompanying drawings, in which:
`[0019]
`FIG. 1is a schematic perspective view illustrating a
`multilayer ceramic capacitor according to an exemplary
`embodimentof the present invention; and
`[0020]
`FIG. 2 is a schematic cross-sectional view taken
`along line I-I' of FIG. 1, illustrating the multilayer ceramic
`capacitor.
`
`DETAILED DESCRIPTION OF THE PREFERRED
`EMBODIMENT
`
`[0021] Exemplary embodiments of the present invention
`will now be described in detail with reference to the accom-
`
`panying drawings.
`[0022] The invention may, however, be embodied in many
`different forms and should not be construed as being limited
`to the embodiments set forth herein. Rather, these embodi-
`000004
`
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`

`US 2011/0141655 Al
`
`Jun. 16, 2011
`
`ments are provided so that this disclosure will be thorough
`and complete, and will fully convey the scopeofthe invention
`to those skilled in theart. In the drawings, the thicknesses of
`layers and regions are exaggerated for clarity. Like reference
`numerals in the drawings denote like elements.
`[0023]
`FIG. 1is aschematic perspective view illustrating a
`multilayer ceramic capacitor according to an exemplary
`embodimentof the present invention. FIG. 2 is a schematic
`cross-sectional view taken alongline I-I' of FIG.1, illustrat-
`ing the multilayer ceramic capacitor.
`[0024] Referring to FIGS. 1 and 2, a multilayer ceramic
`capacitor, according to this exemplary embodiment, includes
`a sintered ceramic body 110, first and second internal elec-
`trodes 130a and 1304 formed inside the sintered ceramic
`
`body 110, and first and second external electrodes 120a and
`1206 electrically connected to the first and second internal
`electrodes 130a and 1306.
`
`In FIG.2, the sintered ceramic body 110 includes a
`[0025]
`capacitive part 110A, and protective layers 110B formed on
`the top and bottom surfaces of the capacitive part 110A.
`[0026] The protective layer 110B maybe formedonatleast
`one of the top and bottom surfaces of the capacitive part
`110A. The protective layers 110B, when formed on both the
`top and bottom surfaces of the capacitive part 110A, have
`excellent influence in lowering a crack occurrencerate.
`[0027] The capacitive part 110A is obtained by laminating
`a plurality of ceramic dielectric layers 111 and thefirst and
`second internal electrodes 130a and 1306 in an alternating
`manner. The first and second internal electrodes 130a and
`
`The protective layer 110B is formed of a ceramic material,
`and contains second ceramicparticles whose averageparticle
`size ratio to the first ceramic particles 110a ranges from 1.1 to
`1.3.
`
`[0033] The second ceramic particles 1108 are not specifi-
`cally limited, provided that they have a high dielectric con-
`stant. For example,the first ceramic particles 110a mayuti-
`lize barium titanate (BaT10,)-based ceramics, lead complex
`perovskite-based ceramics,
`strontium titanate (SrTiO,)-
`based ceramics or the like.
`
`[0034] Typically, a thermal expansion coefficient of a
`ceramic material reaches approximately 8 to 9x107°/° C., and
`internal electrodes, formed of nickel, have a thermal expan-
`sion coefficient of approximately 13x10-°/° C. Thus,tensile
`and compressive stress acts on dielectric layers having a
`relatively small thermal expansion coefficient. Since thether-
`mal expansionstress due to the thermal impact hasits greatest
`influence on the interface between the protective layer 110B
`and the capacitive part 110A, a ceramic laminate having high
`brittleness may be cracked.
`[0035] According to this exemplary embodiment of the
`present invention,the protective layer 110B includesthe sec-
`ond ceramicparticles 110B having a greaterparticle size than
`the first ceramic particles 110a. The second ceramicparticles
`1105, having a greater particle size than the first ceramic
`particles 110a, are slow in shrinkage behavior as compared to
`the first ceramic particles 110a. This alleviates a stress differ-
`ence occurringat the time ofthe thermal expansionof internal
`electrodes.
`
`[0036] An average particle size ratio (D2/D1, where D1
`1306 are paired as having oppositepolarities. Thesefirst and
`denotes the average particle size of the first ceramic particles
`second internal electrodes 130a and 1306 oppose each other
`110a and D2 denotes the average particle size of the second
`in a lamination direction of the ceramic dielectric layers 111,
`ceramic particles 1105) of the second ceramicparticles 1105
`and are electrically insulated from each other by the ceramic
`to the first ceramic particles 110a ranges from 1.1 to 1.3. An
`dielectric layers 111. One set of ends of the first internal
`electrodes 130a and the other set of ends of the secondinter-
`average particle size ratio (D2/D1) of less than 1.1 fails to
`alleviate thermal impact occurring during the thermal expan-
`nal electrodes 1306 are exposedin the lamination direction of
`sion of internal electrode layers. This results in a high crack
`the ceramic dielectric layers 111. The exposed endsofthe first
`occurrence rate. An average particle size ratio exceeding 1.3
`and second internal electrodes 130a and 1306are electrically
`connectedto the first and second external electrodes 120a and
`maycause non-firing or increase a crack occurrencerate.
`1204,respectively.
`[0037]
`Furthermore, the protective layer 110B includes a
`
`[0028] Whenapredetermined voltage is appliedto thefirst plurality of pores P, and the porosity thereof ranges from 2%
`and second external electrodes 120a and 1208, electric
`to 4%. The protective layer 110B is formed by sintering a
`charges are accumulated between the opposingfirst and sec-
`slurry which is a mixture of the second ceramic particles
`ondinternal electrodes 130a and 1306. Here, the capacitance
`1104, an organic binder and a solvent. The porosity of the
`ofthe multilayer ceramic capacitor is in proportion to the area
`protective layer 110B can be controlled by controlling the
`of the opposingfirst and secondinternal electrodes 130a and
`contentofthe second ceramicparticles 1108, and the kind and
`1306.
`amountof organic binder. The content of the second ceramic
`particles 1105 may range from 15% to 40%.
`[0038] The above-mentioned porosity range may enable
`the absorption of stress generated during the thermal expan-
`sion, thereby reducing a crack occurrencerateat the interface
`between the capacitive part 110A and the protective layer
`110B.
`
`[0039] A plurality of pores also exist in the capacitive part
`110A, and the porosity ofthe capacitive part 110A may be 1%
`or less.
`
`[0029] The ceramic dielectric layers 111 of the capacitive
`part 110A contain first ceramic particles having an average
`particle size D1 of 0.1 um to 0.3 um. Thefirst ceramic par-
`ticles 110a@ are not specifically limited, provided that they
`have a high dielectric constant. For example, the first ceramic
`particles 110@ may utilize barium titanate (BaTiO,)-based
`ceramics, lead complex perovskite-based ceramics, stron-
`tium titanate (SrTiO, )-based ceramics or the like.
`[0030] The first and second internal electrodes 130a and
`130d are formed of a conductive metal, which mayutilize, for
`example, Ni or a Ni alloy. The Ni alloy may contain Mn,Cr,
`Co or Alas well as Ni.
`
`[0031] The first and second external electrodes 120a and
`1206 are formed of a conductive metal, and may contain, for
`example, copper.
`[0032] The protective layer 110B is formed on at least one
`of the top and bottom surfaces of the capacitive part 110A.
`
`[0040] The protective layer 110B may be thicker than a
`single dielectric layer within the capacitive part 110A. For
`example, the single dielectric layer 111 of the capacitive part
`110A may have a thickness of 2 um orless. As 25 or more of
`such dielectric layers 111 are laminated, the thickness of the
`capacitive part 110A mayrange from 50 um to 2000 um. The
`protective layer 110B may have a thickness of 10 um to 100
`uum.
`000005
`
`000005
`
`

`

`US 2011/0141655 Al
`
`Jun. 16, 2011
`
`are slow in termsof shrinkage behavior, a difference in stress
`caused during the thermal expansion of the internal elec-
`trodesis alleviated.
`
`tured multilayer ceramic capacitors were subjected to thermal
`impacttesting (dipping ina lead pot at 320 degrees Celsius for
`two seconds), the occurrence of cracks was evaluated using a
`microscope of 50 to 1,000 magnification.
`
`TABLE 1
`
`Average
`particle
`size ratio
`(D2/D1)
`1.1
`
`Porosity
`(%) of
`protective
`layer
`2.0
`
`1.2
`
`1.3
`
`0.8
`
`0.9
`
`1.0
`
`14
`
`1.5
`
`3.2
`
`4.0
`
`0.8
`
`1.0
`
`14
`
`5.7
`
`6.3
`
`Inventive
`example 1
`Inventive
`example 2
`Inventive
`example 3
`Comparative
`example 1
`Comparative
`example 2
`Comparative
`example 3
`Comparative
`example 4
`Comparative
`example 5
`
`
`
`Sinter-
`ability
`Sintere
`
`Sintere
`
`Sintere
`
`
`
`[0041] Hereinafter, a method ofmanufacturing a multilayer
`ceramic capacitor according to an exemplary embodimentof
`the present invention will be described.
`[0042]
`First, a plurality of ceramic green sheets, which are
`[0051] Thereafter, first and second external electrodes are
`to be laminated in a capacitance part, are prepared. The
`formedto coverthe side surfaces ofthe sintered ceramic body
`ceramic green sheets are manufactured by mixing first
`and to be electrically connectedto the first and secondinternal
`ceramic particles having an averageparticle size of 0.1 um to
`electrodes exposedto the side surfaces ofthe sintered ceramic
`0.3 um, a binder and a solvent to thereby produceaslurry and
`body.
`making this slurry into sheets having a thickness of a few
`Subsequently, the surface of those external elec-
`[0052]
`micrometers by using a doctor blade method.
`trodes maybe plated with nickel, tin orthelike.
`[0043] An internal electrodepaste (i.e., a paste for the for-
`mation of an internal electrode) is applied to the surfaces of
`[0053] Multilayer ceramic capacitors were manufactured
`under conditions shownin Table 1 below. After the manufac-
`the ceramic green sheets to thereby form first and second
`internal electrode patterns. Thefirst and secondinternalelec-
`trode patterns may be formed by using a screen printing
`method. The internalelectrode paste is obtained by dispersing
`Ni or a Ni alloy powderin an organic binder and an organic
`solvent and making it into a paste state. The Ni alloy may
`contain Mn, Cr, Co or Al as well as Ni.
`[0044] The organic binder utilized may be onethat is
`knownin the art. For example, the organic binder mayutilize,
`butis not limited to, a binder such as a cellulose-basedresin,
`an epoxy-basedresin, an aryl resin, an acryl resin, a phenol-
`formaldehyde resin, an unsaturated polyester resin, a poly-
`carbonate resin, a polyamide resin, a polyimide resin, an
`alkyderesin, a rosin esteror the like.
`[0045]
`Theutilized organic solvent mayalso be onethatis
`known in the art. For example, the organic solvent may uti-
`lize, but is not limited to, a solvent such asbutyl carbitol, butyl
`carbitol acetate,
`turpentine, a-terpineol, ethyl cellosolve,
`butyl phthalate or the like.
`[0046] Thereafter, the ceramic green sheets provided with
`the first and secondinternal electrode patterns are laminated
`and pressurized in the lamination direction. Thus, the lami-
`nated ceramic green sheets and internal electrode paste are
`pressed with each other. In such a manner, a capacitive part,
`including the alternately laminated ceramic green sheets and
`internal electrode paste, is manufactured.
`[0047]
`Subsequently, a plurality of ceramic green sheets,
`which are to be laminated on the top and bottom surfaces of
`the capacitive part, are prepared. These ceramic green sheets
`are manufactured by mixing second ceramicparticlesthat are
`1.1 to 1.3 times greater in average particle size than thefirst
`ceramic particles constituting the capacitive part, a binder and
`a solvent to thereby producea slurry, and making this slurry
`into sheets having a thickness of a few micrometers by using
`a doctor blade method. Thereafter, the ceramic green sheets
`are laminated on the capacitive part to thereby form a protec-
`tive layer. The porosity of the protective layer may be con-
`trolled by controlling the content of the second ceramic par-
`ticles and the kind and amount of organic binder, and the
`porosity of the protective layer may range from 2% to 4%.
`The content of the second ceramic particles in the ceramic
`slurry may range from 15% to 40%.
`[0048] Thereafter, a resultant ceramic laminate is cut into
`chips in units of one capacitor. At this time, the cutting is
`performed such that one set of ends of the first internal elec-
`trode patterns and the other set of ends of the secondinternal
`electrode patterns are exposedto the side surfaces thereof.
`[0049] Thereafter, the laminate chipis fired at a tempera-
`ture of 1200° C. for example, thereby manufacturing a sin-
`tered ceramic body.
`[0050] At this time, since the second ceramic particles,
`having a greater particle size than thefirst ceramic particles,
`
`Crack
`occurrence
`rate
`1/300
`
`0/300
`
`1/300
`
`17/300
`
`10/300
`
`17/300
`
`5/300
`
`15/300
`
`
`
`Sintere
`
`Sintere
`
`Sintere
`
`Sintere
`
`Non-
`sintere
`
`[0054] Referring to Table 1, comparative examples 1 to 3
`show high crack occurrencerates since they fail to alleviate
`thermal impact occurring in the thermal expansion ofinternal
`electrodes. When the average particle size ratio of second
`ceramic particles to first ceramic particles exceeds 1.3 as in
`comparative example 4 and 5, a protective layeris notfired to
`thereby experience cracking or fails to alleviate thermal
`impact, thereby resulting in a high crack occurrencerate.
`[0055]
`Inventive examples 1 to 3 show lower crack occur-
`rence rates as compared to comparative examples 1 to 5.
`[0056] Asset forth above, in the multilayer ceramic capaci-
`tor according to exemplary embodimentsofthe invention, the
`protective layer includes second ceramic particles having a
`greater particle size than first ceramic particles constituting
`the dielectric layers of the capacitive part. The second
`ceramic particles are slower in terms of shrinkage behavior
`than the first ceramic particles. Accordingly, a stress differ-
`ence causedin the thermal expansion of internalelectrodesis
`reduced. Furthermore, the porosity of the protective layer
`ranges from 2% to 4% and thus the protective layer has a
`lower density than the capacitive part.
`[0057] According to exemplary embodimentsof the inven-
`tion, the multilayer ceramic capacitor reduces thermal impact
`and shear stress applied thereto when the multilayer ceramic
`capacitor is mounted on the wiring board by using soldering
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`
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`

`US 2011/0141655 Al
`
`Jun. 16, 2011
`
`or when the wiring board mounted with the multilayer
`ceramic capacitor is cut. Thus, a crack occurrence rate can be
`lowered.
`
`[0058] While the present invention has been shown and
`described in connection with the exemplary embodiments, it
`will be apparent to those skilled in the art that modifications
`and variations can be made without departing from the spirit
`and scope ofthe invention as defined by the appended claims.
`
`Whatis claimed is:
`
`1. A multilayer ceramic capacitor comprising:
`a capacitive part including dielectric layers and first and
`second internal electrodes alternately laminatedtherein,
`wherein the dielectric layers include first ceramic par-
`ticles having an averageparticle size of0.1 um to 0.3 um,
`and oneset ofendsofthefirst internal electrodes and one
`
`set of ends of the secondinternal electrodes are exposed
`in a lamination direction ofthe dielectric layers;
`a protective layer formedonat least one of top and bottom
`surfacesofthe capacitive part, including second ceramic
`particles and having a porosity of 2% to 4%, wherein an
`
`average particle size ratio of the second ceramic par-
`ticles to thefirst ceramic particles ranges from 1.1 to 1.3;
`and
`first and second external electrodes electrically connected
`to the first and secondinternal electrodes exposed in the
`lamination direction of the dielectric layers.
`2. The multilayer ceramic capacitor of claim 1, wherein the
`first ceramic particles comprise barium titanate (BaTiO,)-
`based ceramics, lead complex perovskite-based ceramics, or
`strontium titanate (SrTiO, )-based ceramics.
`3. The multilayer ceramic capacitor of claim 1, wherein the
`second ceramic particles comprise barium titanate (BaTiO;)-
`based ceramics, lead complex perovskite-based ceramics, or
`strontium titanate (SrTiO, )-based ceramics.
`4. The multilayer ceramic capacitor of claim 1, wherein the
`dielectric layers ofthe capacitive part have a porosity of 1% or
`less.
`5. The multilayer ceramic capacitor of claim 1, wherein the
`capacitive part has a thickness of 50 um to 2000 um,and the
`protective layer has a thickness of 10 pum to 100 pm.
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