594952 玖、發明說明（1) 【發明所屬之技術領域】 本發明係關於一種低溫共燒陶瓷基板，特別是一種以 陶瓷纖維/玻璃複合材料層做為收縮抑制層之低溫共燒陶 瓷基板，及其製造方法。 5【先前技術】 近年來可攜式資訊電子產品與行動通訊產品朝著輕薄 短小、多功能、高可靠度與低價化發展，因此，高元件密 度及多功能成為電子元件及組件的發展趨勢，從而線路中 所使用的主動元件及被動元件也必須朝向整體化、晶片化 1〇 ，及模組化的方向發展。為達小型化及輕量化的高密度構 裝要求，基板須利用新開發的材料以細微導線及積層化的 方式製造。 多層共燒陶瓷基板具有高信賴度，除可作為線路的基 板材料外，並可作為被動元件的高密度黏著基板。關於多 15 層共燒陶瓷基板之製造技術，依燒結溫度大致可區分為高 溫共燒陶瓷技術及低溫（低於1〇〇〇它）共燒陶兗（乙㈣594952 发明 Description of the invention (1) [Technical field to which the invention belongs] The present invention relates to a low-temperature co-fired ceramic substrate, particularly a low-temperature co-fired ceramic substrate using a ceramic fiber / glass composite material layer as a shrinkage suppression layer, and Its manufacturing method. 5 [Previous technology] In recent years, portable information electronics and mobile communications products have become thinner, lighter, more versatile, more reliable, and less expensive. Therefore, high component density and versatility have become the development trend of electronic components and components. Therefore, the active components and passive components used in the circuit must also develop in the direction of integration, waferization, and modularization. In order to achieve high-density packaging requirements for miniaturization and weight reduction, substrates must be manufactured using finely-conducted wires and laminates using newly developed materials. Multi-layer co-fired ceramic substrates have high reliability. In addition to being used as circuit substrate materials, they can also be used as high-density adhesive substrates for passive components. Regarding the manufacturing technology of 15-layer co-fired ceramic substrates, it can be roughly divided into high-temperature co-fired ceramic technology and low-temperature (less than 1,000) co-fired ceramic ㈣ (㈣) according to the sintering temperature.
Temperature Co_fired Ceramics，LTCC)技術。 其中，低溫共燒陶瓷技術因具有··可在低溫（1〇〇〇〇c 以下）燒結、能與低阻抗及低介電損失之Ag、Au ' Cu等 20 金屬共燒、製作時不受層數限制、介質厚度容易控制、能 將電阻電容及電感埋入元組件中等等的優點，再加上低溫 共燒陶瓷之熱膨脹係數與吸水率小，因此非常適合應用在 高頻通訊元組件之製作上。 然而’即使是低溫共燒陶瓷，在為使陶瓷體緻密而實 6 594952 玖、發明說明（2) 施燒結的程序中卻造成陶瓷體收縮，更有因不同的層間收 縮量不同，而易於燒結時導致低溫共燒元件有扭曲、破裂 、分層等變形的問題。另外，肇因於陶瓷體與金屬導體間 之熱膨脹係數的差異，也易於冷卻時產生熱應力，導致低 5 溫共燒元件的破裂和變形。 為控制或消除燒結時陶瓷體收縮之問題，已知有下列 解決方案被提出，例如先將生胚體預燒或是煆燒，藉此減 少生胚體中有機黏結劑之含量，降低燒結過程中生胚體内 因溶劑揮發所產生之孔洞，以此減少陶竟體收縮；也有研 10 究利用加壓成形時機械力限制陶瓷體的收縮方向；或是藉 由不同比例之陶瓷粉達到無收縮結果。 另外，在多層低溫共燒陶瓷基板的製作上，已知有透 過將LTCC薄帶層（LTCC tape layers)積層於被動元件的上 、下，使其等相對於中心的高κ值介電材料形成對稱， 15以減低基板之收縮的設計，例如USP 5，144,526號專利； 或者，如USP 5,7〇8,57〇號專利，係以至少兩個在共燒結 時具有和所包埋的電子構件實質相同之收縮特性的收Ζ 制層來達到抑制收縮的目的；再者，有透過在二種以不同 的低溫燒結陶瓷材料所構成之第一及第二基板生胚片間， 2〇 S置一含有未在該二陶竟基板的燒結溫度下被燒結之無機 材料的收縮抑制層生胚片，再將其等一起共燒結，使彳^自 基板生胚片滲出之玻璃滲透到收縮抑制層而製成不會有層 間剝離之多層陶瓷基板者，例如usp 6,337，123號專利。 雖然，上述方法在抑制收縮方面都有不同程度的功效 7 594952 玫、發明說明（3) ’然而，當同時考慮到燒結溫度、燒結緻密度、收縮特性 特性等因素’同時又期待能更簡化製程以降低 製這成本時，則開發符合產* 杲而衣之貫貝上無收縮低溫共 燒陶兗基板，仍是非常重要的課題。 【發明内容】 為解决上述習知技術或有因被動元件需相對於LTCC 材料層主對稱配晉，JT欠Λτ # 不U 置以致降低基板之設計彈性的缺點，·或 需製備二種以不同的低溫燒結陶究材料所構成之第一及第 ίο 二基板生胚片’以及一收縮抑制層生胚片，導致材料及製 程的複雜化等問題’因此，本發明之目的，即在提供一種 燒結後實質上無收縮，且燒結緻密度符合需求，又能保有 陶究材料之微波特性的低溫共燒陶£基板，及其製造方法 Ο 於是，為達成前述目的，本發明主要係藉陶竟纖維於 15長軸所具有之較優異的剛性來抑制生胚於燒結時所發生的 收知百，猎以製得實質上無收縮之低溫共燒陶竟基板。 •依據本發日狀實質上無收縮的低溫錢㈣基板係由 陶究纖維/玻璃複合材料構成之收縮抑制層，和陶竟粉體/ 2 玻璃複合材料構成之緻密層錯疊積層，再於9〇〇。(：左右或 更低的溫度下共燒結而成。更詳細地說，本發明之實質上 …、收縮的低溫共燒陶瓷基板中，錯疊在緻密層間的複數個 收縮抑制層，係以陶瓷纖維長向呈大致可以互相抑制收縮 的角度排列，藉以減少或抑制燒結時陶瓷基板之χ/γ軸 向的收縮率。 8 594952 玖、發明說明（4) 此外，依據本發明之低溫共燒陶瓷基板的製造方法， 因緻遂、層和收縮層僅在材料上，有前者使用之陶莞粉體， 在後者係以陶瓷纖維取代的差異，其餘如生胚的製作條件 ，最後的燒結條件等並無區別，故不僅製程簡化，製程條 5 件亦易於控制。 【發明之詳細說明】 據上所述，本冑明所提供之低溫共燒陶竟基板係由複 數個緻密層和複數個含有陶莞纖維之收縮抑制層錯疊再共 燒結而成，其中’錯疊方式並無特殊限制，惟以上、下層 Η) I緻密層者為宜，其中又以中間各層係由緻密層與收縮： 制層間隔疊層者為較佳。關於收縮抑制層之配列方式則可 依其層數而做彈性選擇，例如，在包括多層收縮抑制層的 陶瓷基板中，可使收縮抑制層依次以〇。、％。、WO。、 270°排列。 15 , 哪Y所便用之陶瓷纖維/玻璃複合材 料，其中陶兗纖維之含有比例以超過5〇%為宜，但 ,70%，：為纖維含量越高，雖然燒結後收縮率越小，但° 是燒結緻密性也越差。❿，陶輯維之種類只要是高溫不 會軟化，且不會與陶瓷及玻璃產疋门/亚 v ^ ^ ^ 王汉應，與陶瓷及玻璃間 又有良好濕潤性的陶瓷纖維，並盔 输維^ …、特殊限制，一般的陶瓷 、義、准’例如氧化鋁、氧化鍅纖維等，且 V— ，、有兩 Q 值（〇=2π X母週期最大能量儲存/每週期的平均 你、 -r 里/为耗）之微波 "電材枓均可適用於本發明。破 R Π cλ ^ Γ 知用 BBS (BaO- 2〇3- Si〇2R BABS ⑺办A1 2 3 B2.Sl〇2)，或 CaO- 9 20 594952 玖、發明說明（5) B2〇3-Si02、SrO-B203-Si〇2、MgO-B2〇3_Si02 玻璃等，而 以 BBS (Ba0-B203- Si02)和 BABS (BaO-Al203-B203-Si〇2) 為佳。 另外，本發明中之緻密層所使用的陶瓷粉體/玻璃複 5 合材料中，陶瓷粉體的含有比例以體積計介於20〜80%。 而’陶瓷粉體的種類可依基板熱膨脹係數的需求而定，其 中，高熱膨脹係數之基板原料可舉例如氧化鋁、石英、锆 酸鈣（CaZr〇3)、鎂撖欖石（Mg2Si〇4)等；低熱膨脹係數之基 板原料可舉例如矽石、紅柱石（A16Si2〇13)、堇青石 10 (Mg2Al4Si5〇18)、氧化錯（Zr〇2)等。 另外’與陶瓷材料形成複合材料之玻璃粉體可使用常 見的原料，例如石朋石夕酸約玻璃（B〇rosiiicate Giass)或約鎮 銘石夕酉夂玻璃（Calicia-Magnesia-Alumina Silicate Glass)。透 過玻璃粉的添加可以調整陶瓷材料的熱膨脹係數，使其與 15搭載的導體材料之熱膨脹係數接近，藉以避免熱應力之產 生’同時降低製程燒結溫度。 接著將就本發明之實質無收縮低溫共燒陶瓷基板的製 造方法做說明。 本發明之陶瓷基板製造方法包括生胚成型、疊層及燒 2〇 、、Ό等步驟。生胚成型步驟係分別取體積比20/80〜80/20之 陶瓷粉體/玻璃粉體，和體積比5〇/5〇〜7〇/3〇之陶瓷纖維/ 玻璃伞刀體，並分別添加分散劑及黏結劑，混合製成緻密層 和收縮抑制層生胚的襞料，接著成型為生胚片。疊層步驟 係依分別取複數個緻密層生胚和複數收縮抑制層生胚片， 10 594952 玖、發明說明（6) 以收縮抑制層的陶瓷纖維方向係呈可分別抑制緻密層之不 同向的收縮之排列方式交錯疊置，然後加以熱壓。經過熱 壓之多層陶究接著以階段昇溫的方式完成低温燒結。、 在本發明之上述製造方法中，生胚成型步驟中係使用 有機溶劑做為分散劑以促進原料粉體之分散，並於揮發時 在生胚片中形成微細孔洞，提供生胚片在後續之疊層步驟 吁文壓縮變形的能力。有機溶劑之種類可舉例如甲醇、乙 醇（95% )、正丁醇、戊醇、甲苯乙醇 等之醇類；丙酮、甲基乙基酮、戊酮、 ίο (95% )、雙丙酮醇 甲基異丁酮、環己 酮等之酮類；醋酸甲醋、乙酸乙酯（85% )、乙酸丁酉旨、 醋酸：戊酯等之酯類；醋酸等之羧酸類；四氯化碳、二氯 丙烧等之為_素取代的烴類和甲苯、二氧陸圜及甲基溶纖 劑、乙基溶纖劑等有機溶劑。 15 本么明之製造方法中，在陶兗纖維/玻璃原料中添加分散劑以分散纖維時’需注意維持纖維長度，使其經過混 ό仍Sb維持長轴優勢。 20 另外’生胚成型步驟中所使用之黏結劑係為提供原料 =暫時性的黏結’以利生胚片之成型及厚膜金屬化等後 :=進行。黏結劑之種類只要具有高玻璃轉移溫度、 间刀子里及良好的脫脂燒除和易溶於揮發性有機溶劑等特 性’ f無特殊限制；惟以熱塑性高分子化合物，能在最少 添加里下獲得最高生胚密度，燒結熱分解後之殘餘灰分少 4儲存穩定性高，又不與陶體起反應者為宜，其中 車乂口適者可舉例如pvB (p咖㈣仙㈣）、聚丙鋼、低 11 594952 砍、發明說明（7) 烷基丙烯酸酯共聚物和甲基丙烯酸酯等。此等黏結劑可以 在空氣或鈍氣環境中，以400〜500°C的溫度燒除，其添加 量以相對於生胚漿料總重為上較佳，惟不宜超過 10%，以免增加燒結時間，同時降低粉體燒結時之密度導 5 致基板收縮率增高。 此外，本發明之低溫共燒陶瓷基板的製造方法在製作 生胚漿料時可進一步添加塑化劑以降低黏結劑之玻璃轉移 度，使生胚片具有撓屈性。適當之塑化劑可舉例如酸 鹽、磷酸鹽、醇醚類、單甘油酯酸、磺物油（Petr〇1_)、 ίο 多元酯、松香衍生物（Rosin Derivatives)、沙巴鹽類 (Sabacate)、檸檬酸鹽等；其中 pEG (p〇lyethylene 和DOP(Di-〇ctyl-Phthalate)因可提供生胚強度而 DBP(Di_n-Butyl phathalate)則能改善生胚延展性故特別適 用。 15 另，本發明之低溫共燒陶瓷基板的製造方法在疊層步 驟中係採「收縮抑制層」之纖維排列方向為〇。、9〇。、 180°、270°的方式排列，使得經過燒結而獲得之陶瓷基板 在X、Y方向之收縮率小於2.5%，較佳為小於2%，更佳 者則小於1%。而，其中又以陶瓷基板的上、下層為緻密 20 層之璺層方式較佳，而且緻密層與收抑制層相間疊層者更 佳。 上述璺層步驟中，生胚片疊層係先經熱壓再經均壓以 使其更緻岔，藉以獲得更緻密之燒結體，並降低燒結後之 收縮量。 12 594952 玖、發明說明（8) 再者，本發明之低溫共燒陶瓷基板的製造方法中，低 溫共燒製程係採用階段式燒結法，先以2^^^以下之昇 溫速度昇溫至一相對低溫，例如4〇(rC〜5〇(rc之溶劑燒除 階段，停留1〜2小時，除去生胚片中之有機成分（亦稱脫 5 脂），藉以防止有機溶劑在燒結時大量揮發造成陶瓷體的 孔洞，影響緻密度；接著再昇溫至例如8〇〇。〇〜9〇〇(^實施 低溫共燒。共燒過程可以在空氣中進行。 【實施方式】 本發明之前述以及其他技術内容、特點與優點，在以 10 下配合爹考圖式之一較佳實施例的詳細說明中，將可清楚 的呈現。 下列實施例所使用之陶瓷粉體及玻璃粉體，係將純度 99%，平均粒徑3〜5μηι之氧化鋁粉末，和BBS ( Ba-B203-Si〇2 —重量比 51% : 45% : 4% )玻璃，或 BABS ( Ba- 15 A12〇3-B2〇3_Si02—重量比 51% ·· 5% : 40% : 4%)以球磨 機研磨而獲得粒徑約1 μηι的粉體供用。陶瓷纖維係採用 SAFFIL Alumina fibre (α-phase)。分散液係由甲苯、無水 酒精、PVB、M1201 ( Fuji Chemical 製）以重量比 66 : 28_3 : 3.2 : 2.5均勻混合調配成（以下稱a液）。黏結劑 20 則由甲苯、無水酒精、PVB、DOP (Di_Octyl Phthatate)、 EG (Ethylene Glycol)以重量比 44·1 : 18·9 : 21 : 13·6 : 2.4 均勻混合調配成（以下稱Β液）。 所製得之低溫共燒陶瓷基板以SPDR (Split-post Dielectric Resonator)厚膜量測法（參見 J· Krupka et al， 13 594952 玖、發明說明（Π) 表1 實 施 緻密層(陶瓷粉體/ 玻璃粉體)體積比 收縮抑制層(陶瓷纖維 /玻璃粉體)體積比 燒結條件 收縮率 (%) 例 AI2O3 BBS BABS Fiber BBS BABS 溫度 時間 X軸 Y軸 (°C) (min) 1 4 6 麵 6 4 - 10 0 <2 800 20 <2 <2 30 0 <2.5 10 0 <2 850 20 0 0 30 0 0 900 10 0 0 20 0 0 30 0 <2.5 2 5 5 - 6 4 - 800 10 2.5 2.5 20 2.5 2.5 30 2.5 2.5 850 10 <2.5 <2.5 20 <2 <2 30 <2.5 <2.5 900 10 0 <2.5 20 2.5 2.5 3 5 - 5 6 - 4 800 30 <2 <2 850 30 <2 <2 900 30 <2 <2 3 4 - 6 6 - 4 800 30 0 <2 850 30 <1 <1 900 30 <1 <1Temperature Co_fired Ceramics (LTCC) technology. Among them, the low-temperature co-fired ceramic technology is sintered at low temperatures (below 10000c), and can be co-fired with 20 metals such as Ag, Au 'Cu and other materials with low resistance and low dielectric loss. The advantages of limited number of layers, easy control of dielectric thickness, ability to embed resistors, capacitors, and inductors in the element, etc., coupled with the low coefficient of thermal expansion and water absorption of low-temperature co-fired ceramics, make it ideal for high-frequency communication element components. Making. However, even for low-temperature co-fired ceramics, in order to make the ceramic body compact 6 594952 玖, the description of the invention (2) the process of sintering causes the ceramic body to shrink, and it is easy to sinter because of the different shrinkage between layers. This causes distortion problems such as distortion, cracking, and delamination of low-temperature co-fired components. In addition, due to the difference in thermal expansion coefficient between the ceramic body and the metal conductor, it is also easy to generate thermal stress during cooling, leading to cracking and deformation of the low temperature co-fired component. In order to control or eliminate the problem of ceramic body shrinkage during sintering, the following solutions are known, for example, pre-firing the green body or calcining it first, thereby reducing the content of organic binder in the green body and reducing the sintering process Mesozoic embryos have holes in the body due to solvent volatilization to reduce the shrinkage of the ceramic body. There are also researches that use mechanical force to limit the shrinkage direction of the ceramic body during pressure forming; or use different proportions of ceramic powder to achieve no shrinkage. result. In addition, in the production of multilayer low-temperature co-fired ceramic substrates, it is known to form a high-k dielectric material by laminating LTCC tape layers on top and bottom of a passive device with respect to the center. Symmetric, 15 to reduce the shrinkage of the substrate, such as USP 5,144,526; or, such as USP 5,708,57, based on at least two electrons with and embedded in co-sintering The shrinking layer with substantially the same shrinkage characteristics of the members can achieve the purpose of suppressing shrinkage. Furthermore, there are two kinds of green sheets, which are formed between two kinds of first and second substrate green sintered ceramics made of different low-temperature sintered ceramic materials. A shrinkage-suppressing green sheet containing an inorganic material that has not been sintered at the sintering temperature of the ceramic substrate is placed, and then co-sintered together, so that the glass exuded from the green-slab of the substrate penetrates into the shrinkage-suppression For example, there is a USP patent No. 6,337,123 for a multilayer ceramic substrate without peeling between layers. Although the above methods have different degrees of effectiveness in inhibiting shrinkage, 7 594952, invention description (3) 'However, when considering factors such as sintering temperature, sintering density, shrinkage characteristics and so on', it is also expected to simplify the process. In order to reduce the manufacturing cost, it is still a very important issue to develop non-shrinkable low-temperature co-fired ceramic substrates that meet the production requirements. [Summary of the Invention] In order to solve the above-mentioned conventional technologies or the reason that passive components need to be symmetrically matched with respect to the LTCC material layer, JT is less than Δτ # and is not set to reduce the design flexibility of the substrate, or two different types need to be prepared. The first and second substrates made of low-temperature sintered ceramic materials and the second substrate green sheet "and a shrinkage-inhibiting layer green sheet, leading to problems such as complication of materials and processes" Therefore, the object of the present invention is to provide a Low-temperature co-fired ceramic substrate with substantially no shrinkage after sintering, and with sintered dense density that meets the requirements, and can retain the microwave characteristics of ceramic materials, and its manufacturing method. Therefore, in order to achieve the foregoing object, the present invention is mainly based on ceramics. The fiber has a relatively good rigidity on the 15 major axis to suppress the occurrence of sintering during the sintering process. The low-temperature co-fired ceramic substrate with substantially no shrinkage is obtained. • According to the current situation, the low-temperature Qianqian substrate is a shrinkage suppression layer composed of ceramic fiber / glass composite material, and a dense layer composed of ceramic powder / 2 glass composite material. 900. (: Co-sintered at a temperature of about left or lower. In more detail, in the present invention, substantially ..., the shrinking low-temperature co-fired ceramic substrate, a plurality of shrinkage suppressing layers staggered between dense layers are made of ceramics The fiber lengths are arranged at an angle that substantially suppresses shrinkage to each other, thereby reducing or suppressing the χ / γ axial shrinkage of the ceramic substrate during sintering. 8 594952 发明, Description of the Invention (4) In addition, the low-temperature co-fired ceramic according to the present invention The manufacturing method of the substrate is due to the fact that the layer, the shrink layer, and the shrink layer are only on the material. The former uses the ceramic powder, and the latter is replaced by ceramic fibers. The rest are the production conditions of the green embryo and the final sintering conditions. There is no difference, so not only the manufacturing process is simplified, but the 5 process conditions are also easy to control. [Detailed description of the invention] According to the above, the low-temperature co-fired ceramic substrate provided by the present invention is composed of a plurality of dense layers and a plurality of containing The shrinkage inhibition layer of Tao Wan fiber is made by staggering and co-sintering. There is no special limitation on the “staggering method, but the upper and lower layers Η) I dense layers are suitable, and the middle layers are used Dense layer and shrinkage: It is better to make a layer and interval stack. The arrangement of the shrinkage suppression layers can be elastically selected according to the number of layers. For example, in a ceramic substrate including a plurality of shrinkage suppression layers, the shrinkage suppression layers can be sequentially set to zero. ,%. , WO. , 270 °. 15. The ceramic fiber / glass composite material that is used by any Y, in which the content of ceramic fiber is more than 50%, but 70%: the higher the fiber content, although the smaller the shrinkage after sintering, But ° is the worse the sintered compactness. Alas, as long as the type of pottery is high temperature, it will not soften, and it will not produce ceramics / glasses. 汉 ^ ^ ^ Wang Hanying, ceramic fibers with good wettability between ceramics and glass, and helmets. ^…, Special restrictions, general ceramics, meaning, quasi 'such as alumina, hafnium oxide fibers, etc., and V —, have two Q values (0 = 2π X maximum energy storage in the mother cycle / average you per cycle,-- All microwaves " electrical materials " in the r-r / s) are applicable to the present invention. Break R Π cλ ^ Γ Known BBS (BaO- 2〇3- Si〇2R BABS Office A1 2 3 B2.Sl02), or CaO- 9 20 594952 玖, Invention Description (5) B2〇3-Si02 , SrO-B203-SiO2, MgO-B203-Si02 glass, etc., and BBS (Ba0-B203-SiO2) and BABS (BaO-Al203-B203-SiO2) are preferred. In addition, in the ceramic powder / glass composite material used in the dense layer in the present invention, the content ratio of the ceramic powder is 20 to 80% by volume. The type of ceramic powder can be determined according to the thermal expansion coefficient of the substrate. Among them, the raw materials of the substrate with high thermal expansion coefficient can be alumina, quartz, calcium zirconate (CaZr〇3), magnesite (Mg2Si〇4). ), Etc .; the raw materials of the substrate with a low thermal expansion coefficient include, for example, silica, andalusite (A16Si2O13), cordierite 10 (Mg2Al4Si5O18), and oxide (ZrO2). In addition, the glass powder that forms a composite material with ceramic materials can use common raw materials, such as Borosiiicate Giass or Calicia-Magnesia-Alumina Silicate Glass. . The thermal expansion coefficient of the ceramic material can be adjusted through the addition of glass frit so that it is close to the thermal expansion coefficient of the conductor material carried in the 15 to avoid the generation of thermal stress' while reducing the sintering temperature of the process. Next, a method for manufacturing a substantially non-shrinkable low-temperature co-fired ceramic substrate according to the present invention will be described. The method for manufacturing a ceramic substrate of the present invention includes steps such as green embryo forming, lamination, and firing. The green embryo forming step is to take a ceramic powder / glass powder with a volume ratio of 20/80 ~ 80/20, and a ceramic fiber / glass umbrella blade with a volume ratio of 50/50 to 70/30, respectively. Add dispersant and binder, mix to make the dense layer and shrinkage-inhibited layer embryo, and then shape into a green embryo piece. The lamination step is based on taking a plurality of dense layers of raw embryos and a plurality of shrinkage-inhibiting layered green slabs. 10 594952 玖, description of the invention (6) The ceramic fiber orientation of the shrinkage-inhibiting layer is different in the direction of the dense layer. The shrinking arrangement is staggered and then hot-pressed. Hot-pressed multilayer ceramics are then used to perform low-temperature sintering in a step-wise manner. In the above manufacturing method of the present invention, an organic solvent is used as a dispersant in the green embryo forming step to promote the dispersion of the raw material powder, and when the volatilization is formed, fine holes are formed in the green embryo chip to provide the green embryo chip in the subsequent stage. The lamination step calls for the ability of the text to compress and deform. Examples of the organic solvent include alcohols such as methanol, ethanol (95%), n-butanol, pentanol, and toluene ethanol; acetone, methyl ethyl ketone, pentanone, ίο (95%), diacetone methyl alcohol Ketones such as methyl isobutyl ketone, cyclohexanone; methyl acetate, ethyl acetate (85%), butyl acetate, acetic acid: amyl esters; carboxylic acids such as acetic acid; carbon tetrachloride, two Chloropropenes are organic solvents such as toluene-substituted hydrocarbons, toluene, dioxolane, methyl cellosolve, and ethyl cellosolve. 15 In the manufacturing method of Benmin, when dispersing agent is added to the ceramic fiber / glass raw material to disperse the fiber, it is necessary to pay attention to maintaining the fiber length so that it still maintains the long-axis advantage after mixing. 20 In addition, the bonding agent used in the “green embryo forming step is to provide raw materials = temporary bonding” to facilitate the forming of the green embryo sheet and thick-film metallization, etc .: = performed. As long as the type of the binder has characteristics such as high glass transition temperature, good knives, good degreasing and burning, and easy dissolving in volatile organic solvents, there is no special limitation; however, thermoplastic polymer compounds can be obtained with a minimum of additives. Highest raw embryo density, less residual ash after sintering and thermal decomposition. 4 High storage stability, and those that do not react with pottery are suitable. Among them, those with suitable car mouths can be, for example, pvB (pCa㈣xian㈣), polypropylene steel, Low 11 594952 chop, description of invention (7) Alkyl acrylate copolymer and methacrylate etc. These adhesives can be burned in the air or inert gas environment at a temperature of 400 ~ 500 ° C. The added amount is better than the total weight of the raw embryo slurry, but it should not exceed 10%, so as not to increase sintering. At the same time, reducing the density of the powder during sintering results in an increase in substrate shrinkage. In addition, in the method for manufacturing a low-temperature co-fired ceramic substrate of the present invention, a plasticizer may be further added to reduce the glass transition degree of the binder during the production of the green embryo slurry, so that the green embryo chip has flexibility. Suitable plasticizers include, for example, acid salts, phosphates, alcohol ethers, monoglycerides, sulphate oils (Petr〇1_), polyhydric esters, rosin derivatives (Rosin Derivatives), and Sabacate salts. , Citrate, etc. Among them, pEG (p〇lyethylene and DOP (Di-octyl-Phthalate)) can provide raw embryo strength, while DBP (Di_n-Butyl phathalate) can improve the ductility of raw embryos. 15 In addition, In the manufacturing method of the low-temperature co-fired ceramic substrate of the present invention, in the lamination step, the fiber arrangement direction of the "shrinkage suppressing layer" is aligned at 0 °, 90 °, 180 °, and 270 °, so that it can be obtained by sintering. The shrinkage rate of the ceramic substrate in the X and Y directions is less than 2.5%, preferably less than 2%, and more preferably less than 1%. Among them, it is preferable that the upper and lower layers of the ceramic substrate are dense 20 layers. In addition, the dense layer and the suppression layer are better laminated. In the above-mentioned step of lamination, the green sheet stack is first hot-pressed and then equalized to make it more bifurcated, so as to obtain a denser sintered body, And reduce the shrinkage after sintering. 12 594952 发明, Description of the invention 8) Furthermore, in the method for manufacturing a low-temperature co-fired ceramic substrate of the present invention, the low-temperature co-fired process adopts a staged sintering method, and first raises the temperature to a relatively low temperature at a temperature increase rate of 2 ^^^ or less, such as 4 ° (rC ~ 50 (the solvent burning stage of rc, stay for 1 to 2 hours, remove the organic components (also known as degreasing) from the green slabs, so as to prevent the organic solvent from volatilizing during sintering, which will cause pores in the ceramic body and affect compactness. The temperature is then increased to, for example, 80. 00 to 900. (^ Low-temperature co-firing is performed. The co-firing process can be performed in the air. [Embodiment] The foregoing and other technical contents, features, and advantages of the present invention are in It will be clearly shown in the detailed description of one of the preferred embodiments with 10 times of the dauco pattern. The ceramic powder and glass powder used in the following examples will have a purity of 99% and an average particle size of 3 ~ 5μηι alumina powder, and BBS (Ba-B203-Si〇2—51% by weight: 45%: 4%) glass, or BABS (Ba-15 A12〇3-B2〇3_Si02—51% by weight ··· 5%: 40%: 4%) Grinded with a ball mill to obtain a powder with a particle size of about 1 μm The ceramic fiber is made of SAFFIL Alumina fibre (α-phase). The dispersion is made of toluene, anhydrous alcohol, PVB, M1201 (manufactured by Fuji Chemical) at a weight ratio of 66: 28_3: 3.2: 2.5, and mixed (hereinafter referred to as a) Liquid). Binder 20 is prepared by mixing toluene, anhydrous alcohol, PVB, DOP (Di_Octyl Phthatate), and EG (Ethylene Glycol) at a weight ratio of 44 · 1: 18 · 9: 21: 13 · 6: 2.4. Called B liquid). The prepared low-temperature co-fired ceramic substrate was measured by the SPDR (Split-post Dielectric Resonator) thick film measurement method (see J. Krupka et al, 13 594952 玖, description of the invention (Π) Table 1 Implementation of a dense layer (ceramic powder / Glass powder) Volume ratio shrinkage suppression layer (ceramic fiber / glass powder) Volume ratio Sintering condition Shrinkage (%) Example AI2O3 BBS BABS Fiber BBS BABS Temperature time X axis Y axis (° C) (min) 1 4 6 sides 6 4-10 0 < 2 800 20 < 2 < 2 30 0 < 2.5 10 0 < 2 850 20 0 0 30 0 0 900 10 0 0 20 0 0 30 0 < 2.5 2 5 5-6 4-800 10 2.5 2.5 20 2.5 2.5 30 2.5 2.5 850 10 < 2.5 < 2.5 20 < 2 < 2 30 < 2.5 < 2.5 900 10 0 < 2.5 20 2.5 2.5 3 5-5 6-4 800 30 < 2 < 2 850 30 < 2 < 2 900 30 < 2 < 2 3 4-6 6-4 800 30 0 < 2 850 30 < 1 < 1 900 30 < 1 < 1
由表1之結果可知，本發明之陶瓷基板可以在900°C 16As can be seen from the results in Table 1, the ceramic substrate of the present invention can be used at 900 ° C 16