TW559841B - Ceramic-material, ceramic several-layers-component with said ceramic-material and method to produce the component - Google Patents

Ceramic-material, ceramic several-layers-component with said ceramic-material and method to produce the component Download PDF

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TW559841B
TW559841B TW91111667A TW91111667A TW559841B TW 559841 B TW559841 B TW 559841B TW 91111667 A TW91111667 A TW 91111667A TW 91111667 A TW91111667 A TW 91111667A TW 559841 B TW559841 B TW 559841B
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ceramic
ceramic material
layer
patent application
component
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Guenther Pfeiler
Christl Mead
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Epcos Ag
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
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Abstract

This invention relates to a ceramic-material on the basis of BaTi4O9, which includes additionally 0.1-0.5 wt% Mn2O3 and Nd2O3. In addition, this invention relates to a ceramic several-layers component. Through the addition of Mn2O3 to barium-titanate, it can be attained that the ceramic material has a small dielectric-constant, this will make the production of several-layers-capacitors with small capacities easier.

Description

559841 五、發明說明(1 ) 本發明涉及陶瓷材料,其含有鈦酸鋇。本發明亦涉及 一種含有陶瓷材料之陶瓷多層組件及其製造方法。 陶瓷材料已爲人所知,其適合用來製造多層電容器且 具有大約是50或更大之介電常數ε。這些陶瓷材料之缺 點是:由於較大之介電常數,則製造電容値很小之多層 電容是困難的。 由 Mhaisalkar,S.G.;Ready, D.W;Akbar,S.A·;等人所 寫之文件”Mic rowave Dielectric Properties of Doped BaTi409”;J.Am· Ceram. Soc.74[8]( 1 99 1 ) 1 894- 1 898 中已 知一些陶瓷材料,其具有低的介電常數ε = 35且除了 BaTi4〇9之外仍含有Μη02或BaCo3。這些陶瓷材料之缺 點是:其必須在大於120(TC之很高之燒結溫度中進行燒 結且因此不可使用銀成份較高之內電極,此乃因純銀之 熔點是1 0 8 3 °C。在以這些習知之陶瓷材料來製造多層式 電容器時各內電極所需之材料成本會較高,內電極通常 是由銀及鉛所構成之混合物,其中Ag/Pt之混合比(ratio) 是5 0/5 0。但鈿是昂貴的,因此成本很高。 本發明之目的是提供一種陶瓷材料’其具有較低之介 電常數。 本發明中此目的以申請專利範圍第1項之陶瓷材料來 達成。本發明有利之其它形式,具有本發明之陶瓷材料 之陶瓷多層組件及其製造方法描述在申請專利範圍各附 屬項中。 559841 五、發明說明(2) 本發明中之陶瓷組件含有鈦酸鋇(BaTi4〇9)及另外含有 0.1至0.5重量百分比之Μη203 ° 藉由添加Μη203,則以鈦酸鋇爲主之陶瓷材料即具有 較低之介電常數(其介於3 5和3 8之間)。因此,在製造 多層式電容器時可輕易地設定較小之電容値,就此種電 容器之厚度(有效之介電質)及其面積(決定該有效之電容 器板之面積)而言所使用之各層不必遵守一種很精確之 尺寸精確度。 在本發明有利之實施形式中,陶瓷材料另含有一種 Nd2〇3成份,其未超過〇·2重量百分比。 藉由添加Nd203,則可達成之優點是:本發明之陶瓷材 料具有所謂”COG特性”。 本發明亦提供一種陶瓷多層組件,其層堆疊是由交替 地重疊配置之電極層及介電質層所構成且介電質層含有 本發明之陶瓷材料。此種陶瓷多層組件例如可以是多層 電容器,其中各介電質層形成介電質。各電極層即爲電 容器板。藉由適當地配置各外電極(其是與電極層相接 觸),則可使多個單一電容器並聯。 若陶瓷材料含有0.2至1 ·5重量百分比之Ag20成 份,則這樣是有利的。藉由陶瓷材料以銀來作適當之摻 雜,則銀由本發明之多層陶瓷之電極層向外擴散之現象 可降低。可使用銀作爲本發明之陶瓷多層組件之各電極 層用之材料。本發明之陶瓷材料若未添加Ag20來進行 559841 五、發明說明(3) 摻雜,則各電極層中所存在之銀可大量地擴散至陶瓷 中,這樣會使各電極層不穩定。 電極金屬之已減小之擴散現象允許電容器可被製成, 此時在介電質層之厚度介於5和60 // m之間時,電極層 厚度最大是1 . 5 μ m時即足夠在燒結之後保持一種均勻 而連續之電極層。 這些薄電極層之優點是:除了較少之材料損耗(其特別 是在使用貴金屬(例如,銀或鈀)時很重要)之外,由於電 極層及介電質層之收縮特性之差異很小而使積層 (Delamination)變小。此外,厚度較小之電極層所具有 之優點是:在電容器之電容相同時體積之使用率較高。 又,當陶瓷材料含有1至1〇重量百分比之Bi4Ti3012 時是有利的。鈦酸鉍具有燒結輔助劑之功能。藉由添加 一種燒結輔助劑至陶瓷材料’則可達成之優點是:陶瓷 材料在燒結時之燒結溫度可下降至1 000至I200°c之 間,這樣可使電極層中之銀成份較局。 因此,多層組件是特別有利的’其中電極層包含一種 由銀及鈀(重量比是Ag/Pd = 80/20)所形成之混合物。電 極層中較高之銀成份可藉由下述方式達成:陶瓷材料中 以Ag20來摻雜以及藉由燒結輔助劑使燒結溫度下降。 若燒結溫度未下降,則鈀成份須較高’此乃因鈀在較銀 還高之溫度時才會溶化。但較高之鈀成份會使此種組件 製造時之成本較高。559841 V. Description of the invention (1) The present invention relates to a ceramic material containing barium titanate. The invention also relates to a ceramic multilayer component containing a ceramic material and a method for manufacturing the same. Ceramic materials are known which are suitable for manufacturing multilayer capacitors and have a dielectric constant ε of about 50 or more. The disadvantage of these ceramic materials is that it is difficult to make multilayer capacitors with very small capacitances due to the large dielectric constant. "Mic rowave Dielectric Properties of Doped BaTi409" written by Mhaisalkar, SG; Ready, DW; Akbar, SA ·; et al .; J. Am Ceram. Soc. 74 [8] (1 99 1) 1 894- Some ceramic materials are known from 1 898, which have a low dielectric constant ε = 35 and still contain Mn02 or BaCo3 in addition to BaTi4O9. The disadvantage of these ceramic materials is that they must be sintered at a very high sintering temperature greater than 120 ° C and therefore cannot use internal electrodes with a high silver content, because the melting point of pure silver is 10 8 ° C. In When these conventional ceramic materials are used to manufacture multilayer capacitors, the material cost of each internal electrode will be higher. The internal electrode is usually a mixture of silver and lead. The Ag / Pt ratio is 50. / 5 0. However, rhenium is expensive, so the cost is high. The object of the present invention is to provide a ceramic material which has a lower dielectric constant. The purpose of the present invention is to use the ceramic material of the first scope of the patent application. Achieved. In another advantageous form of the present invention, a ceramic multilayer component having the ceramic material of the present invention and a method for manufacturing the same are described in each appended item of the scope of patent application. 559841 V. Description of the Invention (2) The ceramic component in the present invention contains titanic acid Barium (BaTi4〇9) and an additional 0.1 to 0.5% by weight of Mη203 ° By adding Mη203, the ceramic material based on barium titanate has a lower dielectric constant (which is between 3 5 Between 3 and 8). Therefore, when manufacturing multilayer capacitors, it is easy to set a smaller capacitance 就 with regard to the thickness (effective dielectric) of this capacitor and its area (determining the area of the effective capacitor plate) The layers used do not have to adhere to a very precise dimensional accuracy. In an advantageous embodiment of the invention, the ceramic material additionally contains an Nd203 component, which does not exceed 0.2% by weight. By adding Nd203, it is possible The advantage achieved is that the ceramic material of the present invention has a so-called "COG characteristic". The present invention also provides a ceramic multilayer component whose layer stack is composed of electrode layers and dielectric layers which are alternately arranged and a dielectric layer The ceramic material of the present invention is included. Such a ceramic multilayer component may be, for example, a multilayer capacitor in which each dielectric layer forms a dielectric. Each electrode layer is a capacitor plate. By appropriately disposing each external electrode (which is a Layer-to-layer contact), it is possible to connect multiple single capacitors in parallel. This is advantageous if the ceramic material contains an Ag20 component of 0.2 to 1.5 weight percent. By appropriately doping the ceramic material with silver, the phenomenon that silver diffuses outward from the electrode layer of the multilayer ceramic of the present invention can be reduced. Silver can be used as a material for each electrode layer of the ceramic multilayer component of the present invention. If the ceramic material of the invention is not added with Ag20 for 559841 V. Explanation of the invention (3) Doping, the silver present in each electrode layer can be diffused into the ceramic in large quantities, which will make each electrode layer unstable. Reduced diffusion allows capacitors to be made. At this time, when the thickness of the dielectric layer is between 5 and 60 // m, the electrode layer thickness of 1.5 μm is sufficient after sintering. Maintain a uniform and continuous electrode layer. The advantage of these thin electrode layers is that in addition to less material loss (which is important especially when using precious metals (eg, silver or palladium)), due to the electrode layer and the dielectric The difference in the shrinkage characteristics of the stratum is small so that the delamination becomes smaller. In addition, the smaller thickness of the electrode layer has the advantage that the volume usage is higher when the capacitance of the capacitor is the same. In addition, it is advantageous when the ceramic material contains 1 to 10 weight percent of Bi4Ti3012. Bismuth titanate has the function of sintering aid. The advantage achieved by adding a sintering aid to the ceramic material is that the sintering temperature of the ceramic material during sintering can be reduced to between 1,000 and I200 ° c, which can make the silver content in the electrode layer more local. Therefore, a multilayer component is particularly advantageous' in which the electrode layer contains a mixture of silver and palladium (the weight ratio is Ag / Pd = 80/20). The higher silver content in the electrode layer can be achieved by doping Ag20 in the ceramic material and lowering the sintering temperature by a sintering aid. If the sintering temperature does not decrease, the palladium content must be higher 'because palladium will melt only at a higher temperature than silver. However, higher palladium content can make such components more expensive to manufacture.

559841 五、 發明說明 ( 4) 陶 瓷 材 料 之 製 造方法例如包含以下各步驟: a) 製 成 一 由 多 種適當之原始材料所形成之混合物。 b) 在 1 00 0和 1 1 5 0 °C之間之溫度對該混合物進行轉換 約 1 至 5 小 時之久。 c) 使 已 轉 換 之 混合物被磨細。 下 述 之 其 它 步 驟亦是可能的: d) 由 已 轉 換 之 混合物製成一種沈積物。 e) 添 加 Ba4Ti3 〇12及Ag02至沈積物。 此 外 本 發 明 亦提供陶瓷多層組件之製造方法,其中 對 由 重 疊 配 置 之 陶瓷原箔(其BaTi4〇9具有1至l〇Wt% 之 B i 4 T i 3 0 ! 2成份)及電極層所構成之堆疊進行燒結且此 種 燒 結 在 溫 度 1 0 0 0至1 1 5 0 °c時進行。 本 發 明 之 方 法 可藉由燒結輔助劑之添加來達成。這樣 所 具 有 之 優 點 是 :燒結溫度可保持較低,因此可使用之 電 極 層 除 了 鈀 以 外亦可含有相當多之銀成份。特別是可 使 用 Ag/Pd 比 (rc itio)是在7 0/3 0和80/20之間之電極 層 〇 本 發 明 以 下 將 依據實施例及圖式來詳述。圖式簡單說 明 ; 第 1 圖 本 發 明 陶瓷多層組件之橫切面。 第 2 圖 本 發 明 之組件之電容之溫度特性之圖解。 第 1 圖 是 -- 種 電容器,其是可表面安裝之組件(SMD) 且 具 有 互 相 重 疊 之電極層1,各電極層1含有電極金屬 -6- 559841 五、發明說明(5) 且藉由陶瓷材料所形成之介電質層2而互相隔開。在電 容器之正面上配置各金屬層3,其中每一電極層1恰巧 與各金屬層3之一在電性上相連。金‘屬層3例如可以是 由銀,鎳及錫所構成之層堆疊,其可特別容易焊接,其 中錫層是最外層,其以電鍍方式沈積在鎳層上。 本發明之陶瓷材料特別適合用來製成多層式電容器, 其幾何大小是0 · 6 nim長,0.8刪1寬及1 .2 ± 0 .1 mm高且電容 是 0.5 〜1 OOPF ° 介電質層可由陶瓷材料(其含有鈦酸鋇及0.2重量百 分比之Μη304)所製成。 由鈦酸鋇開始,以5個內電極及介於其間之陶瓷層來 製成一種多層式電容器,其中陶瓷層由本發明之陶瓷成 份所構成,其包含0.2Wt%之Μη203及O.lWt%之 Nd203。另須對此多層式電容器測定各種不同之電性額 定資料。卜表顯不電容C之電性額定資料,例如,損耗 角度tan5,介電常數ε及-55°C及125°C時電容値相對於 25 t (TKC)時電容値之相對改變率。 表:電容器或本發明之陶瓷之電性額定資料 C TPF1 T an δ [xlO·3] ε TKC(-55 °C ) TKC(125 °C ) 151.68 0.85 38.6 0.1 6 % -0 · 0 6 % 此表顯示:本發明之陶瓷材料所具有之介電常數是 38.6 第2圖是上表中該電容器之電容對溫度之相對改變 559841 五、發明說明(6) 符號說明 1 ...電極層 2...介電質層 3 ...金屬層559841 V. Description of the invention (4) The manufacturing method of ceramic materials includes, for example, the following steps: a) A mixture of a plurality of appropriate raw materials is prepared. b) The mixture is converted at a temperature between 1 00 and 1 150 ° C for approximately 1 to 5 hours. c) grinding the converted mixture. Other steps described below are also possible: d) A deposit is made from the converted mixture. e) Add Ba4Ti3 〇12 and Ag02 to the sediment. In addition, the present invention also provides a method for manufacturing a ceramic multilayer component, in which a pair of ceramic raw foils (BaTi4 09 having a B i 4 T i 3 0! 2 component of 1 to 10 Wt%) and an electrode layer are arranged in an overlapping arrangement. The stack is sintered and this sintering is performed at a temperature of 100 to 115 ° C. The method of the present invention can be achieved by adding a sintering aid. This has the advantage that the sintering temperature can be kept low, so the electrode layer that can be used can contain a considerable amount of silver in addition to palladium. In particular, an electrode layer whose Ag / Pd ratio (rc itio) is between 70/30 and 80/20 can be used. The present invention will be described in detail below with reference to examples and drawings. The diagram is briefly explained; FIG. 1 is a cross-section of a ceramic multilayer component of the present invention. Figure 2 is an illustration of the temperature characteristics of the capacitors of the present invention. Figure 1 is a kind of capacitor, which is a surface-mountable component (SMD) and has an electrode layer 1 overlapping each other, each electrode layer 1 contains an electrode metal-6- 559841 5. Description of the invention (5) and the use of ceramics The dielectric layers 2 formed of materials are separated from each other. Each metal layer 3 is arranged on the front surface of the capacitor, and each of the electrode layers 1 happens to be electrically connected to one of the metal layers 3. The gold 'metal layer 3 may be, for example, a layer stack of silver, nickel, and tin, which can be particularly easily soldered, in which the tin layer is the outermost layer and is deposited on the nickel layer by electroplating. The ceramic material of the present invention is particularly suitable for making multilayer capacitors. Its geometric size is 0 · 6 nim long, 0.8 mm wide and 1.2 ± 0.1 mm high, and the capacitance is 0.5 ~ 1 OOPF ° dielectric. The layer may be made of a ceramic material (which contains barium titanate and 0.2 weight percent Mn 304). Starting from barium titanate, a multilayer capacitor is made with 5 internal electrodes and a ceramic layer in between, wherein the ceramic layer is composed of the ceramic component of the present invention, which contains 0.2 Wt% of Mn203 and 0.1 Wt% Nd203. It is also necessary to determine various electrical rating data for this multilayer capacitor. The table shows the electrical rating data of capacitor C, for example, the loss angle tan5, the dielectric constant ε and the relative change rate of capacitance 时 at -55 ° C and 125 ° C relative to capacitance 25 at 25 t (TKC). Table: Electrical ratings of capacitors or ceramics of the invention C TPF1 T an δ [xlO · 3] ε TKC (-55 ° C) TKC (125 ° C) 151.68 0.85 38.6 0.1 6% -0 · 0 6% The table shows that the dielectric constant of the ceramic material of the present invention is 38.6. The second figure is the relative change of the capacitor's capacitance to temperature in the table above. 559841 5. Description of the invention (6) Symbol description 1 ... electrode layer 2. ..Dielectric layer 3 ... metal layer

Claims (1)

559841559841 θ 餺 # 六、申請專利範圍 第9 1 1 1 1 667號「陶瓷材料,陶瓷多層組件及其製造方法 」專利案 (9 2年7月修正) 六申請專利範圍: 1· 一種以BaTi 409爲主之陶瓷材料,其另外包含0.1至 〇·5重量百分比之Μη203及可達〇·2重量百分比之 Nd2〇3 〇 2.如申請專利範圍第1項之陶瓷材料,其中陶瓷材料另 含有可達2重量百分比之Ag2〇。 3·如申請專利範圍第1或 2項之陶瓷材料,其中陶瓷 材料另含有1至10重量百分比之Bi4Ti3012作爲燒結 輔助劑。 4. 一種陶瓷多層組件,其層堆疊是由交替重疊配置之電 極層(1)及介電質層(2)所構成,其特徵爲:介電質層 (2 )含有一種如申請專利範圍第1至3項中任一項之 陶瓷材料。 5·如申請專利範圍第4項之組件,其中電極層(1 )含有 一由銀及鈀所構成之混合物,其重量比(rati0)Ag/Pd 是介於70/30及80/20之間。 6.如申請專利範圍第4或5項之組件’其中各電極層在 層堆疊之外側上是與金屬層(3 )相接觸’相鄰之各電 極層(1)是與不同之金屬層(3)相接觸,層堆疊之外部 尺寸未超過1.5 _高,1.6 _寬及2 nun長’在各金屬 559841 六、申請專利範圍 層(3)之間所測得之電容未超過100PF。 7. —種陶瓷多層組件之製造方法,其特徵爲:由重疊配 置之陶瓷原箔(其含有BaTi4〇9及1至1〇重量百分比 之B i 4T i 30i 2以作爲燒結輔助劑且配置在其各電極層 (1 )之間)所構成之堆疊須進行燒結且此種燒結是在 1 000至1150°C之間進行。θ 馎 # VI. Patent Application No. 9 1 1 1 1 667 "Ceramic Materials, Ceramic Multilayer Components and Manufacturing Method" Patent Case (Amended in July 1992) 6 Patent Application Scope: 1 · One with BaTi 409 as The main ceramic material further comprises 0.1 to 0.5 wt% of Mn203 and up to 0.2 wt% of Nd203. For example, the ceramic material of the first scope of the patent application, wherein the ceramic material additionally contains up to 2% by weight of Ag20. 3. The ceramic material as claimed in item 1 or 2 of the patent application scope, wherein the ceramic material additionally contains 1 to 10 weight percent of Bi4Ti3012 as a sintering aid. 4. A ceramic multilayer component, whose layer stack is composed of electrode layers (1) and dielectric layers (2) arranged alternately and overlapped, and is characterized in that the dielectric layer (2) contains A ceramic material according to any one of items 1 to 3. 5. The component as claimed in item 4 of the patent application, wherein the electrode layer (1) contains a mixture of silver and palladium, and its weight ratio (rati0) Ag / Pd is between 70/30 and 80/20 . 6. The component according to item 4 or 5 of the scope of patent application, wherein each electrode layer is in contact with the metal layer (3) on the outer side of the layer stack. The adjacent electrode layers (1) are different metal layers ( 3) In contact, the outer dimensions of the layer stacks do not exceed 1.5 _ height, 1.6 _ width, and 2 nun length 'in each metal 559841 VI. The capacitance measured between the patent application layers (3) does not exceed 100PF. 7. A method for manufacturing a ceramic multilayer component, characterized in that: a ceramic raw foil (which contains BaTi4 09 and 1 to 10% by weight of B i 4T i 30i 2 is used as a sintering assistant and is arranged in an overlapping arrangement; The stack consisting of its electrode layers (1) must be sintered and this sintering is performed between 1 000 and 1150 ° C.
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