200408536 、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的製造方法，特 別是指一種利用陶瓷材料/玻璃材料體積不同比之生胚疊 層來抑制收縮的低溫共燒陶瓷基板，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 10 ，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 一 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 I 溫共燒陶瓷技術及低溫（低於1000 °C )共燒陶瓷（Low200408536, 玖, description of the invention (1 > ~ [Technical Field to which the Invention belongs]-The present invention relates to a method for manufacturing a low temperature co-fired ceramic substrate, in particular to a green embryo laminate using a ceramic / glass material with different volume ratios Low-temperature co-fired ceramic substrate to suppress shrinkage, and its manufacturing method. 5 [Previous technology] In recent years, portable information electronics and mobile communication products have been developed to be thin, light, short, versatile, highly reliable, and low-cost. High component density and multi-functionality have become the development trend of electronic components and components, so the active and passive components used in the circuit must also develop in the direction of integration, waferization10, and modularization. To reach Miniaturization and lightweight high-density mounting requirements require substrates to be manufactured with fine wires and multilayers using newly developed materials. Multilayer co-fired ceramic substrates have high reliability, and can be used as circuit substrate materials. It can also be used as a high-density adhesive substrate for passive components. About 15 layers of co-fired ceramic substrate manufacturing technology, it depends on the sintering temperature. I divided into a high-temperature co-fired ceramic technology and low temperatures (below 1000 ° C) co-fired ceramics (Low
Temperature Co-fired Ceramics 9 LTCC)技術 °Temperature Co-fired Ceramics 9 LTCC) Technology °
、 其中，低溫共燒陶瓷技術因具有：可在低溫（l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、製作時無層數之限制、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 200408536 玫誠； ................. ...................................... :.:.::.:-.:^.沁.分'::斤:^;:::沒::::对::鱗 ................... ：·： ： 施的燒結程序中卻造成陶瓷體收縮，更有因不同的層間收 5 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 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煅燒，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，以此減少陶究體收縮；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K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,观，別號專利，係以至少兩個在共燒处 時具有和所包埋的電子構件實質相同之收縮特性的收^控 制層來達到抑制收縮的目的；再者，有透過在二種以不同 Μ =低溫燒結陶㈣料所構成之第—及第二基板生胚片間， 且置a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，使得自 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£基板者，例如USP 6,337，123號專利。 上述方法在抑龍縮方面都有不同程度的功效 200408536 '玖、發醒麵明（3) ' 资印淖谇约鴻ί;丨战妓沿:级Φΐκ奸;:淬沾 — ，然而，當同時考慮到燒結溫度、燒結緻密度、收縮特性 • 、以及電氣特性等因素，同時又期待能更簡化製程以降低 製造成本時，則開發符合產業需求之實質上無收縮低溫共 燒陶瓷基板，仍是非常重要的課題。 5【發明内容】_ 本發明為解決上述習知技術或有因被動元件需相對於 LTCC材料層呈對稱配置，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瓷材料所構成之第 一及第二基板生胚片，以及收縮抑制層生胚片，導致材料 10 及製程的複雜化等問題，而提供一種燒結後實質上無收縮 ^ ，且燒結緻密度符合需求，又能保有陶瓷材料之微波特性 / 的低溫共燒陶瓷基板，及其製造方法。 因此，為達成前述目的，本發明主要係利用陶瓷與玻 璃在不同體積比例下的反應機制，而於微波介電陶瓷材料 15 中添加不同體積比之玻璃材料，藉以獲得具有高介電係數 | 和低溫係數，以及高品質因子之多層低溫共燒陶瓷基板。 亦即，本發明透過在微波介電陶瓷材料中添加不同體 . 積比之玻璃材料的方式，製得具有不同收縮率和不同緻密 度之二種生胚，再以其中收縮率較小之生胚做為收縮抑制 20 層，和收縮率較大但敏密度較高之生胚疊層，如此即可有 效地將燒結溫度降低至90(TC左右或者更低。 此外，依據本發明之低溫共燒陶瓷基板的製造方法在 收縮抑制層生胚與緻密層生胚的疊層技術上，係採生胚對 稱方向排列疊層燒結的方式，亦即，以生胚在製程中所受 8 200408536 "----- 應力的方向為基準，做互呈0。、90。、18〇。、27〇。的對稱 方向排列疊層，經低溫共燒後，可獲得χ_γ軸向收縮率 小於2%之貫質上無收縮，^可得到預期尺寸及形狀之多 層陶瓷基板。 5 【發明之詳細說明】 據上所述，本發明主要係利用陶瓷與玻璃的體積比 例，和具有不同的收縮率與緻密度之生胚層的疊層結構， 藉以在900 C左右或更低的燒結溫度下，製得具有良好的 微波特性之低溫共燒陶瓷基板。 1〇 ㈣本發明人等之研究，發現陶£與玻璃的體積比例 約80 · 20呀，在燒結過程中所發生的收縮量最小，可達 〇·5%以下；而當陶瓷的體積比例降低至約5〇%，燒結後的 收細里增大’惟其密度亦增高，亦即形成緻密的結構。 因此，本發明即以陶究含量高而具有較低的收縮率之 b陶究玻璃材料層做為收縮抑制層，和玻璃含量高而具有較 緻密的結構之陶甍玻璃材料層做為緻密層，再以適當的疊 層方式形成生胚疊層，以獲得燒結收縮率小於2%之實質 上無收縮的陶瓷基板。 另外，為配合製造積層元件時，陶莞介電材料須與例 ★銀等之金屬^體層共燒，因此本發明係以具有高介電係 數、低溫度係數及高品質因子（Q factor)之微波介電陶 竟與玻璃材料共燒以有效降低燒結溫度至9〇代左 更低。 r 本發明所使用之陶究介電材料中尤以如办〇2〇因在 200408536 - ' 玖、發明祖.(:5) —介電上有低損耗及介電常數具有低溫度係數的特性，故特 •別適用。另，本發明所使用之玻璃材料並無特殊限制，一 般常見之玻璃材料，例如BBS (Ba〇_B2〇3_ Si〇2)或BABS (Ba〇-Al2〇3_B2〇3-Si〇2)，或 Ca〇-B2〇3-Si〇2、Sr0_B2(V 5 ⑽2、Mg〇_B2〇VSi〇2 玻璃等，而以 BBS (Ba0_B2〇3_ si〇2)和 BABS (Ba0_Al2〇3_B2〇3_Si〇2)為佳。而，Among them, the low-temperature co-fired ceramic technology has the following characteristics: it can be sintered at low temperature (below 1000 ° C), can be co-fired with Ag, Au, Cu and other 20 metals with low resistance and low dielectric loss. The advantages of limited number, easy control of dielectric thickness, ability to embed resistors, capacitors, and inductors in the component, etc., coupled with the low thermal expansion coefficient and water absorption of low-temperature co-fired ceramics, are very suitable for high-frequency communication tuples. On the production of pieces. However, even low-temperature co-fired ceramics are being compacted to make the ceramic body dense. 6 200408536 Meicheng; ............... .................:.:. ::.:-.: ^. 沁. 分 ':: jin: ^; ::: 没有 :::: Yes :: scale ......... ::: The ceramic body shrinks during the sintering process, and it is more different. The shrinkage between layers is different, and the low-temperature co-fired components are easily deformed when they are easily sintered. In addition, due to the difference in the coefficient of thermal expansion between the ceramic body and the metal conductor, it is easy to generate thermal stress during cooling, leading to cracking and deformation of the low-temperature co-fired element. In order to control or eliminate the problem of ceramic body shrinkage during sintering, the following solutions are known, such as pre-firing or calcining the green body first, thereby reducing the content of organic binder in the green body and reducing the sintering process. Holes in the embryo body due to solvent volatilization to reduce the shrinkage of the ceramic body; there have also been researches on the use of mechanical forces to limit the shrinkage direction of the ceramic body during press forming; . In addition, in the production of multilayer low-temperature co-fired ceramic substrates, it is known that LTCC tape layers are laminated above and below a passive device so that they are symmetrical with respect to the center of a high-K dielectric material, 15 Design to reduce the shrinkage of the substrate, such as USP No. 5,144,526 patents, or, such as USP 5, Kan, other patents, based on at least two contractions in the co-firing area with substantially the same shrinkage of the embedded electronic components Control layer to achieve the purpose of suppressing shrinkage; in addition, there are two kinds of sintered ceramic materials with different M = low-temperature sintering of the first and second substrates, and a The sintering of the inorganic ceramic substrate at the sintering temperature of the ceramic substrate was suppressed and the green sheet was co-sintered together, so that the glass exuding from the green sheet of the substrate penetrated into the contraction suppressing layer and was made without For multilayer ceramic substrates with interlayer peeling, for example, USP 6,337,123. The above methods have different degrees of effectiveness in suppressing dragon shrinkage. 200408536 '玖, awake face (3)' Zi Yin 淖 谇 Yue Hong ί; 丨 war prostitutes: level Φΐκtrait ;: quenching —, but when Taking into account factors such as sintering temperature, sintering density, shrinkage characteristics, and electrical characteristics, and also looking to simplify the process to reduce manufacturing costs, the development of a substantially non-shrinking low-temperature co-fired ceramic substrate that meets the needs of the industry, still Is a very important subject. 5 [Summary of the Invention] _ In order to solve the above-mentioned conventional technologies, the passive components of the present invention need to be symmetrically arranged with respect to the LTCC material layer, so as to reduce the lack of design flexibility of the substrate, or two kinds of low temperature must be prepared. The first and second substrate green slabs composed of sintered ceramic materials, and the shrinkage suppression layer green slabs cause problems such as the complication of the material 10 and the process, and provide a sintering that has substantially no shrinkage ^ and has a dense sintering density. A low-temperature co-fired ceramic substrate 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 mainly uses the reaction mechanism of ceramic and glass at different volume ratios, and adds glass materials with different volume ratios to the microwave dielectric ceramic material 15 to obtain a high dielectric constant | and Low temperature coefficient and high quality multi-layer low temperature co-fired ceramic substrate. That is, in the present invention, by adding different volume and volume ratios of glass materials to microwave dielectric ceramic materials, two kinds of raw embryos with different shrinkage rates and different densities are prepared, and the raw materials with smaller shrinkage rates are produced. The embryo is laminated with 20 layers of shrinkage inhibition, and a green embryo with a large shrinkage rate but a high sensitivity density, which can effectively reduce the sintering temperature to about 90 ° C or lower. In addition, the low-temperature co-fired ceramic according to the present invention The manufacturing method of the substrate is based on the lamination technology of shrinkage-inhibiting layered embryos and dense layered embryos, which is a method of arranging and sintering the raw embryos in a symmetrical direction, that is, the raw embryos are subjected to the process 8 200408536 "- ---- The direction of the stress is used as a reference, and the layers are arranged in symmetrical directions of 0 °, 90 °, 18 °, and 27 °. After co-firing at low temperature, the χ_γ axial shrinkage can be less than 2%. There is no shrinkage throughout, and a multilayer ceramic substrate of the desired size and shape can be obtained. 5 [Detailed description of the invention] According to the above, the present invention mainly uses the volume ratio of ceramic to glass, and has different shrinkage rates and densities. Degree of embryo The low-temperature co-fired ceramic substrate with good microwave characteristics is prepared at a sintering temperature of about 900 C or lower. According to research by the inventors, it was found that the volume ratio of ceramics to glass About 80 · 20, the shrinkage that occurs during the sintering process is the smallest, which can reach less than 0.5%; and when the volume ratio of the ceramic is reduced to about 50%, the shrinkage after sintering increases, but its density also increases. Increase, that is, form a dense structure. Therefore, in the present invention, a ceramic glass material layer with a high ceramic content and a low shrinkage rate is used as a shrinkage suppression layer, and a glass structure with a high glass content has a denser structure. The pottery glass material layer is used as a dense layer, and then a green embryo stack is formed by an appropriate stacking method to obtain a substantially non-shrinkable ceramic substrate with a sintering shrinkage of less than 2%. In addition, in order to cooperate with the manufacture of laminated components, Tao Wanjie The electric material must be co-fired with a metal layer such as silver. Therefore, the present invention uses a microwave dielectric ceramic with a high dielectric coefficient, a low temperature coefficient, and a high quality factor (Q factor) to co-fire with the glass material to be effective. Decrease the sintering temperature to be lower than the 90th generation. R The ceramic dielectric materials used in the present invention are particularly good. The reason is 200408536-玖, the ancestor of the invention. (: 5)-there is a low dielectric The loss and dielectric constant have the characteristics of a low temperature coefficient, so they are particularly suitable. In addition, the glass material used in the present invention is not particularly limited, and common glass materials such as BBS (Ba〇_B2〇3_ Si〇2 ) Or BABS (Ba〇-Al2〇3_B2〇3-Si〇2), or Ca〇-B2〇3-Si〇2, Sr0_B2 (V 5 ⑽2, Mg〇_B2〇VSi〇2 glass, etc., and BBS (Ba0_B2〇3_ SiO2) and BABS (Ba0_Al2 03_B2 03_SiO2) are preferred. and,
BasTipOM陶瓷材料與玻璃材料之體積比則以$ : $至$ : 2 ^ 為宜。 本發明之低溫共燒陶瓷基板的製造方法中，關於生胚 H)的疊層技術，主要係因生胚的製程，例如刮刀製程中，會 。在生胚薄帶上產生具有方向性的應力，故可以此應力方: -為基準，將乾燥後裁切成適當大小之生胚，互呈〇。、9〇。 180 27G的對無方向排列疊層，供後續熱壓及燒结之 用。 15 因此’本發明之陶兗基板製造方法包括生胚成型、疊 • 層及燒結步驟。生胚成型步驟係先製作陶瓷粉體，再將該 陶竟粉體與玻璃粉體混合成體積比分別介於8〇:2〇至= -·· 50之二種複合材料，並添加分散劑及黏結劑，製成做 •為收縮抑制層和緻密層生胚的漿料，接著成型為生胚片。 疊層步驟係分別取陶兗粉體含量較高而具有較小的收縮率 之稷數個生胚片做為中間層’以複數個陶竟含量較低而具 有較高之密度的複數個生胚諸為上、下層，並使其等Z 生胚成型步驟中所產生之應力方向為基準，互呈〇。、 、HOM對稱方向排列疊層’然後加以熱屬。經過 10 200408536 玖、發明說明(6) 熱壓之陶瓷生胚疊層接著以階段昇溫的方式完成低溫燒結 〇 在本發明之上述製造方法中，生胚成型步驟中係採用 非水系溶劑來溶解黏結劑及塑化劑，並使陶瓷粉體均勻分 5 散其中。常用之非水性溶劑可舉例如甲乙酮、酒精、甲苯 、二甲苯、己烷、三氯乙醇及乙醇等之混合液。 另外，生胚成型步驟中所使用之黏結劑係為提供原料 粉體暫時性的黏結，以利生胚片之成型及厚膜金屬化等後 續製程之進行。黏結劑之種類只要具有高玻璃轉移溫度、 10 高分子量及良好的脫脂燒除和易溶於揮發性有機溶劑等特 性，並無特殊限制；惟以熱塑性高分子化合物，能在最少 添加量下獲得最高生胚密度，燒結熱分解後之殘餘灰分少 ，且儲存穩定性高，又不與陶瓷粉體起反應者為宜，其中 較合適者可舉例如PVB (Polyvinyl Butyral)及壓克力系黏 15 結劑（acrylic binder)等。此等黏結劑可以在空氣或鈍氣環 境中，以300〜400°C的溫度燒除，其添加量以相對於生胚 漿料總重為1〜5%以上較佳，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致基板收縮率增 局。 20 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 溫度，使生胚片具有撓屈性。適當之塑化劑可舉例如適當 之塑化劑可舉例如 酸鹽、磷酸鹽、醇醚類、單甘油酯酸 丨飞7 、石黃物油（Petroleum)、多元酯、松香衍生物（Rosin 11 200408536 玖、發明說明（7)The volume ratio of BasTipOM ceramic material to glass material is preferably from $: $ to $: 2 ^. In the manufacturing method of the low-temperature co-fired ceramic substrate of the present invention, the lamination technology of the green embryos is mainly due to the process of the green embryos, such as during the doctor blade process. The directional stress is generated on the raw embryo thin strip, so this stress can be used as a reference:-After cutting, cut into dry embryos of an appropriate size, showing each other. , 90. 180 27G pairs are stacked in a non-directional arrangement for subsequent hot pressing and sintering. 15 Therefore, the method for manufacturing a ceramic substrate according to the present invention includes the steps of green embryo forming, lamination, and sintering. The green embryo forming step is to first make a ceramic powder, and then mix the ceramic powder and glass powder into two composite materials with a volume ratio of 80:20 to =-· 50, and add a dispersant. And binder, made into a paste that is used as a raw material for shrinkage inhibition layer and dense layer, and then formed into a green sheet. The lamination step is to take several green embryos with high powder content and small shrinkage as intermediate layers, and use a plurality of raw materials with low ceramic content and high density. The embryos are the upper and lower layers, and the direction of the stress generated during the forming step of the Z embryo is made as a reference, and they are 0. ,, And HOM are arranged in a symmetrical direction and stacked ', and then heat is added. After 10 200408536 发明, description of the invention (6) hot-pressed ceramic green embryo stacking and then low-temperature sintering in a step-temperature manner. In the above-mentioned manufacturing method of the present invention, the non-aqueous solvent is used in the green embryo forming step to dissolve the adhesion. And plasticizer, and make ceramic powder evenly divided into 5 pieces. Common non-aqueous solvents include, for example, a mixed solution of methyl ethyl ketone, alcohol, toluene, xylene, hexane, trichloroethanol, and ethanol. In addition, the binder used in the green embryo forming step is to provide temporary bonding of the raw material powder to facilitate the subsequent processes such as the forming of the green embryo sheet and the thick film metallization. The type of the binder is not particularly limited as long as it has the characteristics of high glass transition temperature, 10 high molecular weight, good degreasing and burning, and easy dissolving in volatile organic solvents; however, thermoplastic polymer compounds can be obtained at the minimum addition amount. Highest raw embryo density, less residual ash after sintering and thermal decomposition, high storage stability, and not reacting with ceramic powder. Among the more suitable ones are PVB (Polyvinyl Butyral) and acrylic adhesive. 15 Acrylic binder and so on. These adhesives can be burned in air or inert gas environment at a temperature of 300 ~ 400 ° C. The added amount is preferably 1 ~ 5% or more relative to the total weight of the raw embryo slurry, but it should not exceed 10%. In order to avoid increasing the sintering time and reducing the density of the powder when sintering, the shrinkage of the substrate is increased. 20 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 produce a green embryo slurry to reduce the glass transition temperature of the binder, so that the green embryo chip has flexibility. Suitable plasticizers include, for example, suitable plasticizers, such as acid salts, phosphates, alcohol ethers, monoglycerides, Fei7, petroleum, polyesters, and rosin derivatives. 11 200408536 发明 、 Explanation of invention (7)
Derivatives)、沙巴鹽類（Sabacate)、檸檬酸鹽等；其中 — PEG (Polyethylene glycol)和 DOP(Di-Octyl-Phthalate)因可 提供生胚強度，而DBP(Di-n-Butyl phathalate)則能改善生 胚延展性故尤其適用。 5 再者，本發明之低溫共燒陶瓷基板的製造方法在疊層 步驟中，生胚片疊層係先經熱壓再經均壓以使其更緻密， 藉以獲得更緻密之燒結體，並降低燒結後之收縮量。 > 又，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°C /min以下之昇溫 10 速度昇溫至一相對低溫，例如400°C〜500°C之預燒結階段 . ，停留1〜2小時，除去生胚片中之有機成分（亦稱脫脂） . ，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800°C〜900°C實施低溫 共燒。共燒過程可以在空氣中進行。 15 由於本發明之陶瓷基板中，緻密層與收縮抑制層所使 | 用的陶瓷材料與玻璃材料相同，僅各成分添加量的體積比 不同，因此，相對於習知技術，在生胚漿料的調製以及燒 . 結條件之控制上較為簡便，同時可以達到降低製造成本之 目的。 20【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 下配合參考圖式之一較佳實施例的詳細說明中，將可清楚 的呈現。 實施例 12 200408536 玖、發明說明（8) '；ΐ·:：'*Ηί：·ί^ί：ψ|ίΗί!；ί：ί；ί：；：ΐ；!：；：：;：：^；ί·：:：：ΐ^Ηί!：；：ί^^ ，，ν ' 純相BaiTit)〇9。粉末之製作 取試藥級粉末 BaC03 (R.D.H. 99.9%，-325 mesh)、 Ti02(CERAC 99.90%，-325 mesh)及 Sn02 (R.D.H. 99·9%，-325 mesh)，以 18·2 mol·% BaC03+79.8 mol. Ti02+2 mol·% 5 Sn02的劑量比混合，加入含去離子水及YTZ (Yttrium Toughened Zirconia)直徑1 mm磨球的衛星球磨罐中’球 磨混合30分鐘，經l〇〇°C烘乾及115〇°C下持溫6小時之 瑕燒，再過60 mesh篩網。 取經瑕燒並過60 mesh筛網的粉末，加入含直徑1 10 mm YTZ磨球的球磨罐，以去離子水為分散劑，球磨8小 時，再於100°C烘乾。取烘乾後過80 mesh篩網之粉末， 加入0.15 wt% PVA (0.04g/c.c)、0.5%蠟油，作乾式造粒混 合後烘乾再過80 mesh之篩網，獲得Ba2Ti9〇2〇粉末。 低溫燒結Ba,TiQ〇M陶瓷厚膜之製作 15 將曱苯、無水酒精、PVB、M1201以重量比66 ·· 28.3 :3.2 : 2·5均勻混合調配成分散劑（以下稱A液）。黏結 劑則由甲苯、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）。 2〇 將Ba2Ti9〇2〇陶瓷粉末和Ba0-B203-Si02玻璃粉末分 別以5 : 5、6 : 4、7 : 3和8 : 2不等的比例混合後，與分 散劑（A液）（重量比70 : 30 )球磨混合6小時，隨後加 入黏結劑（B液）（重量比83 : 17)，繼續球磨混合6小 時，並以真空抽氣將漿料除泡，並利用添加甲苯或抽氣處 13 200408536 理的方式將漿料黏度調整至75〇±3〇〇 CPS。 接著將所配製之漿料倒入儲料槽，以馬達帶動刮刀機 兩端之經脫模劑塗覆的承載軸，進行刮刀，再將刮刀後所 得之薄帶靜置風乾，製成陶瓷生胚。 5 其後，將該等生胚裁切成6X6 cm大小，以刮刀製程 時薄帶轉動方向為0度，每轉90度疊一層，形成如第二 圖所示之生胚疊層；先以單軸向熱壓持壓3分鐘，熱壓溫 .度60°C，壓力2000 psi ;繼之以5分鐘的水均壓成型，均 壓/皿度50C，成型壓力3500 psi，完成疊層作業。 1〇 接著，將上述生胚疊層置入去脂爐中進行燒結，升溫 速率2 C/min，至450 C持溫2小時，然後再以8艺/min ^ 的升溫速率繼續分別升溫至8〇〇°C、850°C及90(TC三種燒 、、口 /m度，進行持溫1〇分鐘的共燒處理，完成低溫共燒陶 瓷基板之製作。 15 微波介雷性質、收縮座及密彦 • 上述實施例所製成之，Ba2Ti9〇2。陶瓷粉末/Ba〇_B2〇广Derivatives), Sabacate, citrate, etc .; Among them-PEG (Polyethylene glycol) and DOP (Di-Octyl-Phthalate) can provide embryonic strength, while DBP (Di-n-Butyl phathalate) can It is especially suitable for improving the ductility of raw embryos. 5 Furthermore, in the manufacturing method of the low-temperature co-fired ceramic substrate of the present invention, in the laminating step, the green sheet lamination is first hot-pressed and then equalized to make it denser, thereby obtaining a denser sintered body, and Reduce the shrinkage after sintering. > Furthermore, in the method for manufacturing a low-temperature co-fired ceramic substrate of the present invention, the low-temperature co-fired process uses a staged sintering method, and first heats up to a relatively low temperature, such as 400 ° C, at a temperature increase rate of 10 ° C / min or less. Pre-sintering stage at ~ 500 ° C. Stay for 1 to 2 hours to remove the organic components (also known as degreasing) from the green slabs, so as to prevent the organic solvent from volatilizing during sintering to cause voids in the ceramic body and affect the density; Next, the temperature is raised to, for example, 800 ° C to 900 ° C, and low temperature co-firing is performed. The co-firing process can be performed in air. 15 In the ceramic substrate of the present invention, the dense layer and the shrinkage suppressing layer are used in the same ceramic material as the glass material, except that the volume ratio of each component is different. Therefore, compared with the conventional technology, The modulation and firing. The control of the junction conditions is relatively simple, and the purpose of reducing manufacturing costs can be achieved. [Embodiment] The foregoing and other technical contents, features, and advantages of the present invention will be clearly presented in the following detailed description of a preferred embodiment with reference to the drawings. Example 12 200408536 玖, description of the invention (8) '; ΐ · ::' * Ηί: · ί ^ ί: ψ | ίΗί !; ί: ί; :: ΐ;!:; ::::: ^ Ί · :::: ΐ ^ Ηί!:;: ^^^, ν 'pure phase BaiTit) 〇9. Preparation of powders: Test-grade powders BaC03 (RDH 99.9%, -325 mesh), Ti02 (CERAC 99.90%, -325 mesh), and Sn02 (RDH 99 · 9%, -325 mesh) were used at 18 · 2 mol ·%. BaC03 + 79.8 mol. Ti02 + 2 mol ·% 5 Sn02 was mixed at a dose ratio, and a satellite ball mill tank containing deionized water and YTZ (Yttrium Toughened Zirconia) diameter 1 mm was added to the ball mill and mixed for 30 minutes. Dry at ° C and burn at 115 ° C for 6 hours, then pass through a 60 mesh screen. Take the powder that has been burned and passed through a 60 mesh sieve, add it to a ball mill tank containing YTZ grinding balls with a diameter of 10 mm, use deionized water as a dispersant, and ball mill for 8 hours, and then dry at 100 ° C. Take the powder that has passed through the 80 mesh sieve after drying, add 0.15 wt% PVA (0.04g / cc), 0.5% wax oil, dry-granulate and mix, then dry and pass through the 80 mesh sieve to obtain Ba2Ti902. powder. Preparation of Ba, TiQOM ceramic thick film at low temperature sintering 15 Toluene, anhydrous alcohol, PVB, and M1201 are uniformly mixed to prepare a dispersant (hereinafter referred to as A liquid) at a weight ratio of 66 ·· 28.3: 3.2: 2 · 5. The adhesive is prepared by uniformly 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 (hereinafter referred to as B liquid ). 2．Ba2Ti9〇2〇 ceramic powder and Ba0-B203-Si02 glass powder are mixed at different ratios of 5: 5, 6: 4, 7: 3 and 8: 2 respectively, and then mixed with dispersant (Liquid A) (weight Ratio 70:30) ball milling and mixing for 6 hours, followed by adding a binder (Liquid B) (weight ratio 83:17), continuing ball milling and mixing for 6 hours, and defoaming the slurry with vacuum extraction, and adding toluene or extraction Process 13 200408536 to adjust the slurry viscosity to 75 ± 300 CPS. Then, the prepared slurry is poured into the storage tank, and the motor is used to drive the bearing shaft coated with the release agent at both ends of the scraper to perform a scraper. Then the thin strip obtained after the scraper is left to air dry to make ceramic raw materials. Embryo. 5 After that, cut the raw embryos into a size of 6X6 cm, and use the blade rotation direction of 0 degrees during the doctor blade process, and stack each layer at 90 degrees to form a raw embryo stack as shown in the second figure. Uniaxial hot pressing and holding for 3 minutes, hot pressing temperature: 60 ° C, pressure 2000 psi; followed by 5 minutes of water pressure forming, pressure equalization / disc degree 50C, forming pressure 3500 psi, complete the lamination operation . 10 Next, the above-mentioned green embryo stack is placed in a degreasing furnace for sintering, and the heating rate is 2 C / min, and the temperature is maintained at 450 C for 2 hours, and then the temperature is continuously increased to 8 at a heating rate of 8 art / min ^. 〇 ° C, 850 ° C, and 90 ° C (three kinds of firing, mouth / m degrees, and co-firing at a holding temperature of 10 minutes) to complete the production of low-temperature co-firing ceramic substrates. 15 Microwave dielectric properties, shrink seat Mihiko • Ba2Ti9〇2 made in the above examples. Ceramic powder / Ba〇_B2〇 广
Si〇2玻璃粉末之體積比分別為5 ·· 5、6 ·· 4、7 ·· 3和8 ·· 2 不寺比例的各種陶瓷生胚，以及陶兗粉末/玻璃粉末體積 - 比不同之生胚疊層燒結成之無收縮基板，在燒結後之厚膜 2〇 的收縮率、緻密度和微波介電特性（以HP8722ES網路分 析儀里測）寺具有如下之關係，亦即： 1，收縮率：如第三（幻圖所示，BBS破璃所佔體積比越高， X-Y方向之收縮率越大； 2.(緻）密度：如第三（13)圖所示，BBS玻璃所佔體積比越高 14 200408536 5 10 15 20The volume ratio of Si〇2 glass powder is 5 · 5, 6, 6 ·· 4, 7 ·· 3, and 8 ·· 2 Bulk ceramic embryos, and the volume of ceramic powder / glass powder-the ratio is different. The shrinkage-free, sintered, non-shrinkable substrate has a thickness of 20, and the shrinkage, density, and microwave dielectric properties of the thick film (measured in the HP8722ES network analyzer) have the following relationships, namely: 1 , Shrinkage rate: As shown in the third (magic picture, the higher the volume ratio of BBS broken glass, the greater the shrinkage rate in the XY direction; 2. (D) Density: As shown in the third (13) picture, BBS glass Higher volume ratio 14 200408536 5 10 15 20
厚膜之遂、度越大’結構越緻密，· 3.介電係數：如第三(C)圖所示，介電係數與密度呈正相關 ;燒結溫度升高時，介電係數雖上昇，但並無太大影響 ’在陶£材料/玻璃材料體積比=8 : 2，且_。。燒結下 有最大K值，約13.7 ; 70 4.Q值：如第三⑷圖所示，陶莞材料含量多者，q值較高 ，且燒結溫度昇高，Q值也明顯增大，， 璃材料體積比= 1650 ； 在陶瓷材料/玻 :2，且9〇〇。(：燒結下有最大Q值，約 無收縮基板之微波特性及收縮率：如第四圖所示，以 陶竟/玻璃體積比8 : 2之生胚層做為疊置於中間之收縮抑 制層，以陶竟/玻璃體積比5:5之生胚層做為疊置於上、 下之緻密層的4層生胚疊層’經低溫共燒後，χ_γ轴之收 縮率約〇·5%左右，而且具有優於市售陶曼基板之微波特 性：K=11’Q=1150’ 〇=]〇〇(註：市售 Dupont 951 基板· K=7.2，Q=300，r f=-50)。 。據上所述，依據本發明之低溫共燒陶瓷基板可在9〇〇 它左右或更低溫度下與銀等之金屬導體層共燒，同時具有 良好的微波特性，可以構成理想的微波介電陶瓷基板，且 口 /、衣k方法係利用相同的陶瓷/玻璃材料在添加比例上 之差異來製作收縮率、緻密不同的生胚，再將該二種生胚 積層共燒結而獲得χ_γ方向收縮率小於2%之實f上無收 鈿陶瓷基板，故相較於已知之低溫共燒陶瓷，有緻密層與 收縮抑制層在生胚漿料的調製上較簡便，燒結條件易於控 15 200408536 玖、發明說明（11) 紙:这ft,::鄕:沖沾務務^ •' ·. ’、·" ’ …..’:’:’你-:::::说、.’济沾妗;!;纖:辕雞鑛鐵發 制，且可以降低製造成本等優點。 惟以上所述者，僅為本發明之較佳實施例而已，當不 能以此限定本發明實施之範圍，即大凡依本發明申請:利 範圍及發明說明書内容所作之簡單的等效變化與修飾，皆 5 應仍屬本發明專利涵蓋之範圍内。 白 【圖式簡單說明】 第一圖為本發明之低溫共燒陶瓷基板的階段式燒結程 I 序例示圖； 第一圖為依據本發明實施例之低溫共燒陶瓷基板的疊 1〇 層模式示意圖； 第一（a)圖〜第二（d)圖為不同體積比之Ba2Ti9〇2〇/BBs •基板的燒結收縮率、密度、K值與Q值。 第（a)圖為依據本發明實施例之低溫共燒陶瓷基板 的㈣率與燒結溫度之關係示意圖； 15 第四⑼圖為依據本發明實施例之低溫共燒陶兗基板 籲 ^JK值Q值與燒結溫度之關係示意圖； -jj (a) (b)圖為依據本發明實施例所製得之低溫共 _ 燒陶瓷基板的顯微照片。 一 16 200408536 玖、發明說明（12) 繼戀i議繼藝·鐵鎮鐵繼__議__隳麗_薦^^ 【圖式之主要元件代表符號簡單說明】The thicker the thickness and the greater the degree, the denser the structure. · Dielectric coefficient: As shown in the third (C) diagram, the dielectric coefficient is positively related to the density. When the sintering temperature increases, the dielectric coefficient increases, But it didn't have much effect on the volume ratio of ceramic material / glass material = 8: 2, and _. . The maximum K value under sintering is about 13.7; 70 4.Q value: As shown in the third figure, the higher the q value is, the higher the sintering temperature and the Q value is, Glass material volume ratio = 1650; in ceramic material / glass: 2, and 900. (: The maximum Q value under sintering, about the microwave characteristics and shrinkage of the non-shrinking substrate: as shown in the fourth figure, the raw germ layer of ceramic / glass volume ratio of 8: 2 is used as the shrinkage suppression layer stacked in the middle The four-layer green embryo stack with a ceramic germ layer with a ceramic volume ratio of 5: 5 as the upper and lower dense layers was co-firing at low temperature, and the shrinkage of the χ_γ axis was about 0.5%. And has better microwave characteristics than the commercially available Taurman substrate: K = 11'Q = 1150 '〇 =] 〇〇 (Note: commercially available Dupont 951 substrate · K = 7.2, Q = 300, rf = -50). According to the above, the low-temperature co-fired ceramic substrate according to the present invention can be co-fired with a metallic conductor layer such as silver at a temperature of about 900 or lower, and has good microwave characteristics, which can constitute an ideal microwave dielectric. Electric ceramic substrate, and the method of mouth / coating is to use the difference in the addition ratio of the same ceramic / glass material to make different green embryos with different shrinkage rates and densities, and then co-sinter the two green embryo layers to obtain the χ_γ direction. There is no solid ceramic substrate with a shrinkage rate of less than 2%, so compared with known low-temperature co-fired ceramics, there are The dense layer and the shrinkage suppression layer are simple in the preparation of the raw embryo slurry, and the sintering conditions are easy to control. 15 200408536 玖, Description of the invention (11) Paper: This ft, :: 鄕: Washing service ^ • '..', · &Quot; '… ..': ':' You-::::: said, .'Ji Zhan 妗;!; Fiber: made of pheasant iron and iron, and can reduce manufacturing costs and other advantages. But the above This is only a preferred embodiment of the present invention. When the scope of implementation of the present invention cannot be limited in this way, that is, simple equivalent changes and modifications made in accordance with the scope of the invention and the contents of the invention specification are all 5 It still falls within the scope of the patent of the present invention. White [Simplified description of the drawings] The first diagram is an example of the step I sintering process I of the low-temperature co-fired ceramic substrate of the present invention; the first diagram is the low temperature according to the embodiment of the present invention Schematic diagram of 10 layers of co-fired ceramic substrates; Figures 1 (a) to 2 (d) are Ba2Ti920 / BBs with different volume ratios • Sintering shrinkage, density, K value and Q value of the substrate Figure (a) shows the relationship between the sintering temperature and the sintering temperature of a low-temperature co-fired ceramic substrate according to an embodiment of the present invention. Schematic diagram; 15 The fourth diagram is a schematic diagram of the relationship between the low-temperature co-fired ceramic substrate substrate JJ value Q value and sintering temperature according to the embodiment of the present invention; -jj (a) (b) diagram is made according to the embodiment of the present invention A photomicrograph of the low-temperature co-fired ceramic substrate. 16 200408536 玖 、 Explanation of the invention (12) Ji Lian i Yi Ji Yi · Tie Zhen Tie Ji __ Discuss__ 隳 丽 _Recommend ^^ [Schematic Simple description of component representative symbols]
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