TWI660932B - Ceramic sintered body and passive component including the same - Google Patents

Ceramic sintered body and passive component including the same Download PDF

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TWI660932B
TWI660932B TW106137344A TW106137344A TWI660932B TW I660932 B TWI660932 B TW I660932B TW 106137344 A TW106137344 A TW 106137344A TW 106137344 A TW106137344 A TW 106137344A TW I660932 B TWI660932 B TW I660932B
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ceramic
ceramic phase
sintered body
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TW201917110A (en
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藤本正之
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國巨股份有限公司
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Abstract

本發明提供一種陶瓷燒結體,其具有較佳的介電常數。於本發明的某些實施例中,該陶瓷燒結體包含一半導體陶瓷相分散於一介電陶瓷相中,其中該半導體陶瓷相及該介電常數相共同形成一逾滲複合體,且該半導體陶瓷相的體積分率接近且低於一逾滲閾值。The present invention provides a ceramic sintered body having a preferable dielectric constant. In some embodiments of the present invention, the ceramic sintered body comprises a semiconductor ceramic phase dispersed in a dielectric ceramic phase, wherein the semiconductor ceramic phase and the dielectric constant together form a percolation composite, and the semiconductor The volume fraction of the ceramic phase is close to and below a percolation threshold.

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<title lang="zh">陶瓷燒結體及包含其之被動元件</title><title lang="en">CERAMIC SINTERED BODY AND PASSIVE COMPONENT INCLUDING THE SAME</title><technical-field><p>本發明關於一種陶瓷燒結體(ceramic sintered body)及包含其之被動元件(passive component),特別是一種具有較佳介電常數(dielectric constant)的陶瓷燒結體,及包含該陶瓷燒結體的被動元件。</p></technical-field><background-art><p>諸如電容器(capacitor)之被動元件通常由介電材料(dielectric material)製成。一般而言,電容器的電容(capacitance)與製成電容器之介電材料的介電常數有關。亦即,介電材料之介電常數較高使得電容器之電容較高。由於理想的電容器應具有較小的尺寸及較高的電容,故需要提供介電常數較高的材料。</p></background-art><disclosure><p>本發明提供一種具有較佳的介電常數的陶瓷燒結體。</p><p>於本發明的某些實施例中,該陶瓷燒結體包含一半導體陶瓷相(semiconductor ceramic phase)分散於一介電陶瓷相(dielectric ceramic phase)中,其中該半導體陶瓷相及該介電陶瓷相共同形成一逾滲複合體(percolative composite),且該半導體陶瓷相的體積分率(volume fraction)接近且低於一逾滲閾值(percolation threshold)。</p><p>本發明更提供一種被動元件,包含前述之陶瓷燒結體。</p></disclosure><mode-for-invention><p>理論上,鐵電材料(ferroelectric materials)被預期僅在接近鐵電-順電相變(ferroelectric-paraelectric phase transition)的非常窄的溫度範圍內可具有極高介電常數。然而,習知獲得具有可接受之介電常數的電容器的方法是藉由多層結構來實現。特定言之,其係將多個鐵電陶瓷材料薄層置放於多個導電層之間,以形成多層陶瓷電容器(multilayered ceramic capacitor,MLCC)。在習知MLCC中,鐵電陶瓷層之厚度為影響其電容的關鍵因素。藉由使用較小顆粒尺寸(grain size)之鐵電陶瓷材料減小鐵電陶瓷層之厚度,可增大MLCC之電容。然而,由於所謂的「尺寸效應(Size-Effect)」,顆粒尺寸較小的鐵電陶瓷材料卻呈現較小介電常數。藉由更薄的電介質層得到MLCC之較高電容之習知準則理論上將陷入僵局。</p><p>獲得具有可接受之介電常數的電容器的另一種方法是藉由逾滲複合體實現,其可根據逾滲理論進行解釋。一般而言,「逾滲理論(percolation theory)」係描述隨機圖(random graph)中連接叢集(connected cluster)之行為。在電容器相關之技術領域中,逾滲理論可用於描述導電粒(conductive grains)形成電流路徑以穿過由絕緣粒(insulating grains)所填充之空間的情況。在導電粒與絕緣粒混合時,導電粒足以形成電流路徑以穿過由絕緣粒所填充之空間的最低體積分率定義為「逾滲閾值」。換言之,在導電粒之體積分率達至逾滲閾值時,一部分導電粒彼此連接,形成電流路徑以穿過由絕緣粒所填充之空間。導電粒之體積分率增加致使複合體所顯現的介電常數增加。在導電粒之體積分率恰好處於逾滲閾值之前(此情況意謂逾滲閾值前之最高導電粒體積分率)時,複合物呈現巨大的介電常數。逾滲閾值冪次律(percolative threshold power law)描述如下。 <tables><table border="1" bordercolor="#000000" width="85%"><tbody><tr><td><img wi="197" he="98" file="02_image001.tif" img-format="tif"/></img></td><td><i>ε</i><sub>0</sub>為基質介電常數(matrix dielectric constant) <i>f</i>為填充因子(filling factor) <i>f</i><sub>c</sub>為逾滲閾值 <b><i>q</i></b>為臨界指數(critical exponent) </td></tr></tbody></table></tables></p><p>前述逾滲複合體分別將金屬材料及介電陶瓷材料用作導電粒及絕緣粒。細小的金屬粒具有大的表面能(surface energy)。在與介電陶瓷粒混合時,金屬粒往往會聚結(agglomerate)在一起,因此無法均勻分散於混合物中。當混合過程以大規模進行時,金屬粒之聚集情形甚至可能更為嚴重。此外,因為金屬粒(諸如鎳)之熔點通常低於陶瓷粒之熔點,所以在燒結過程中金屬粒會早於絕緣粒熔化,導致燒結過程中巨大的粒生長(異常晶粒生長,abnormal grain growth)。可使用由具有高熔點之貴金屬(諸如鉑)製成之金屬粒以避免燒結過程期間之異常晶粒生長,同時成本可能相應地增加。鑒於以上,此類逾滲複合體無法滿足工業要求。</p><p>為至少解決以上問題,本發明提供一種陶瓷燒結體,其包含半導體陶瓷相分散於介電陶瓷相中,其中半導體陶瓷相及介電陶瓷相共同形成逾滲複合體,且半導體陶瓷相之體積分率接近且低於逾滲閾值。藉由使用半導體陶瓷材料代替前述金屬材料作為導電相,可避免導電相之聚集及異常晶粒生長。因此,可成功製造出具有良好介電常數的此類逾滲複合體。</p><p>如本文中所使用,術語「大致」、「實質上」、「實質的」及「約」用以描述及考慮小變化。當與事件或情形結合使用時,術語可指事件或情形明確發生之情況以及事件或情形極近似於發生之情況。舉例而言,當結合數值使用時,該等術語可指小於或等於彼數值之±10%的變化範圍,諸如小於或等於±5%、小於或等於±4%、小於或等於±3%、小於或等於±2%、小於或等於±1%、小於或等於±0.5%、小於或等於±0.1%、或小於或等於±0.05%。</p><p>另外,有時在本文中按範圍格式呈現量、比率及其他數值。應理解,此類範圍格式係為便利及簡潔起見而使用,且應靈活地理解為不僅包括明確指定為範圍限制之數值,且亦包括涵蓋於彼範圍內之所有個別數值或子範圍,如同明確指定每一數值及子範圍一般。</p><p>於本發明中,術語「陶瓷燒結體」係指一燒結體,其係由陶瓷材料製成。該陶瓷燒結體可由兩種或更多種陶瓷材料燒結而成。舉例而言,該陶瓷燒結體可由複數陶瓷粒(grains)燒結而成,且這些陶瓷粒共同結合而形成一單體結構(monolithic structure)。</p><p>在本發明中,術語「相」係指空間區域,在整個該空間區域中的材料之所有物理性質基本上為均勻的。物理性質之實例包括但不限於密度、折射率、磁化強度、導電性、介電常數及化學組成。相較佳為物理上及化學上均勻的材料區域,且在物理上區隔(physically distinct)。舉例而言,在本發明之一些實施例中,陶瓷燒結體包括分散於介電陶瓷相中之半導體陶瓷相。半導體陶瓷相實質上由具有一電導率(conductivity)的材料製成,該材料在半導體陶瓷相內基本上是均勻的。類似地,介電陶瓷相實質上由另一種具有一電導率的材料製成,該材料在介電陶瓷相內基本上是均勻的。此外,半導體陶瓷相之電導率不同於介電陶瓷相之電導率。</p><p>在本發明之一些實施例中,在與半導體陶瓷相比較時,介電陶瓷相更類似於連續相(continuous phase)。另一方面,半導體陶瓷相更類似於分散於介電陶瓷相中之分散相(dispersed phase)。出於說明之目的,圖1展示根據本發明之一些實施例之陶瓷燒結體的微觀結構。陶瓷相11分散於介電陶瓷相12中,形成逾滲複合體。值得注意的是,根據本發明之一些實施例之陶瓷燒結體可包括超過一種半導體陶瓷相及/或超過一種介電陶瓷相。</p><p>於本發明的某些實施例中,該介電陶瓷相係指由具有介電性質之陶瓷材料所構成的相。舉例而言,該介電陶瓷相距有高於約10 <sup>8</sup>Ω-cm之電阻率。 </p><p>於本發明的某些實施例中,該半導體陶瓷相係指由具有半導體性質之陶瓷材料所組成的相。舉例而言,該半導體陶瓷相可為n型半導體,且其電導率高於約0.5 S/m,或高於約1.0 S/m。</p><p>在本發明之一些實施例中,逾滲電容(percolation capacitance)係指半導體陶瓷相之最高體積分率,其恰好在足以形成電流路徑穿過介電陶瓷相之前。逾滲閾值係指半導體陶瓷相恰好足以形成電流路徑穿過介電陶瓷相的體積分率。逾滲閾值的確切數值可視半導體陶瓷相及介電陶瓷相之材料、材料的顆粒尺寸及陶瓷燒結體之燒結溫度而定。逾滲閾值可藉由量測或模擬而獲得,其可為本領域中具通常知識者所理解。</p><p>在本發明中,該逾滲複合體之半導體陶瓷相的體積分率非常接近逾滲閾值。逾滲複合體中之半導體陶瓷相的體積分率可低於逾滲閾值數個百分點。</p><p>陶瓷燒結體(包含介電陶瓷相及半導體陶瓷相)之介電常數在逾滲閾值處發散(diverge)。因此,由於介電陶瓷相及半導體陶瓷相共同形成逾滲結構(percolative structure),且半導體陶瓷相之體積分率非常接近逾滲閾值,故陶瓷燒結體可具有提升的介電常數。亦即,在半導體陶瓷相的體積分率在接近逾滲閾值之區域中增加時,陶瓷燒結體的介電常數以指數比例增加。</p><p>在一些實施例中,逾滲複合體中之半導體陶瓷相的體積分率可低於逾滲閾值約0.05%至約20%。舉例而言,若在特定條件下之逾滲閾值為30%,則在相同條件下之亞逾滲複合體(sub-percolative composite)中之半導體陶瓷相之體積分率可為約30-0.05%至約30-20%。在一些實施例中,逾滲複合體中之半導體陶瓷相的體積分率可為低於逾滲閾值約0.05%至約10%、約0.05%至約5%、或約0.05%至約3%。在本發明之一些實施例中,半導體陶瓷相之體積分率接近且低於逾滲閾值。在一些實施例中,半導體陶瓷相之體積分率可為逾滲閾值之精確值的約0.999倍至約0.33倍。舉例而言,若在特定條件下之逾滲閾值為30%,則在相同條件下之亞逾滲複合體中之半導體陶瓷相之體積分率可為約(30 × 0.999)%至約(30 × 0.33)%。在一些實施例中,半導體陶瓷相之體積分率可為逾滲閾值之精確值的約0.999倍至約0.65倍、約0.999倍至約0.75倍、約0.999倍至約0.85倍、或約0.999倍至約0.9倍。</p><p>於某些實施例中,舉例而言,在預定情況下的逾滲閾值可被計算。用以計算預定情況下的逾滲閾值的模型至少可見於C.D. Lorenz and R.M. Ziff, <i>J. Chem.</i><i>Phys</i>. <b>114</b>3659 (2001), S. Kirkpatrick, <i>Rev. Mod. Phys</i>. <b>45</b>574 (1973), D. Stauffer, <i>Phys Rep</i>. <b>54</b>1 (1979), and T.G. Castner, et al., <i>Phys. Rev. Lett.</i><b>3</b><b>4</b>1627 (1975)等文獻中。 </p><p>亞逾滲複合體中之半導體陶瓷相的體積分率的確切數值在很大程度上可視半導體陶瓷相及介電陶瓷相之粒子尺寸及其幾何分佈而定。舉例而言,若介電陶瓷相之顆粒尺寸比半導體陶瓷相之顆粒尺寸小得多,且若其非常均勻地分佈,則半導體陶瓷相之體積分率可能較大。另一方面,若介電陶瓷相之顆粒尺寸比半導體陶瓷相之顆粒尺寸大得多,且若其在幾何上分佈良好,則半導體陶瓷相之體積分率可能較小。然而,在一些實施例中,若半導體陶瓷相之顆粒尺寸為約3.0微米,且介電陶瓷相之顆粒尺寸為約0.2微米,則半導體陶瓷相之體積分率較佳為約5%至約60%;更佳為約15%至約40%;再更佳為約20%至約35%。若半導體陶瓷相之顆粒尺寸為約1.0微米,且介電陶瓷相之顆粒尺寸為約0.2微米,則半導體陶瓷相之體積分率較佳為約5%至約60%,更佳為約15%至約40%,再更佳為約25%至約35%。且若半導體陶瓷相之顆粒尺寸為約0.2微米,且介電陶瓷相之顆粒尺寸為約0.1微米,則半導體陶瓷相之體積分率為5%至55%,更佳為15%至35%,再更佳為約20%至30%。然而,在一些實施例中,半導體陶瓷相之形狀可顯著影響逾滲閾值之確切數值。</p><p>舉例而言,根據本發明之一些實施例之介電陶瓷相的材料包括CaZrTi <sub>2</sub>O <sub>7</sub>(鈣鈦鋯石,zirconolite)、CaZrO <sub>3</sub>、SrZrO <sub>3</sub>、BaZrO <sub>3</sub>、TiO <sub>2</sub>(金紅石,rutile)、ZrO <sub>2</sub>,或其固體溶液(solid solution,例如,其固體溶液可包括Ti <sub>1</sub><sub>-</sub><sub>x</sub>Zr <sub>x</sub>O <sub>2</sub>,其中x為0與1之間的合理數;或Ca <sub>1</sub><sub>-</sub><sub>x</sub>Sr <sub>x</sub>ZrO <sub>3</sub>,其中x為0與1之間的合理數)。在介電陶瓷相包括鈣鈦鋯石之情況下,可幫助介電陶瓷相明確地與半導體陶瓷相區隔。 </p><p>舉例而言,根據本發明之一些實施例之半導體陶瓷相的材料包括鈣鈦礦(perovskite)材料。如一般熟習此項技術者可容易地理解,「鈣鈦礦材料」係指一類化合物,其具有相同類型之晶體結構 <sup>XII</sup>A <sup>2</sup><sup>+</sup><sup>VI</sup>B <sup>4</sup><sup>+</sup>X <sup>2</sup><sup>−</sup><sub>3</sub>。「A」及「B」為兩個尺寸差別極大之陽離子,且「X」為鍵結至兩者之陰離子。「A」原子比「B」原子大。理想的立方對稱結構具有6配位的「B」陽離子,其由陰離子之八面體包圍之;及12配位立方八面體之「A」陽離子。在本發明之一些實施例中,鈣鈦礦材料包括鈦酸鍶(SrTiO <sub>3</sub>)、鈦酸鋇(BaTiO <sub>3</sub>)、鈦酸鈣(CaTiO <sub>3</sub>)、鈦酸鎳(NiTiO <sub>3</sub>)、鈦酸錳(MnTiO <sub>3</sub>)、鈦酸鈷(CoTiO <sub>3</sub>)、鈦酸銅(CuTiO <sub>3</sub>)、鈦酸鎂(MgTiO <sub>3</sub>)或其錯合物。較佳地,鈣鈦礦材料可呈還原態,諸如由例如還原氣氛還原。在本發明之一些實施例中,半導體陶瓷相之材料包括還原之TiO <sub>2</sub>(金紅石),亦即,TiO <sub>2</sub><sub>-</sub><sub>x</sub>;缺氧狀態(oxygen deficient state)半導體。還原之TiO <sub>2</sub>(金紅石)可由例如還原氣氛還原。 </p><p>儘管在鈣鈦礦材料、CaZrTi <sub>2</sub>O <sub>7</sub>、TiO <sub>2</sub>(金紅石)及ZrO <sub>2</sub>當中存在晶格不匹配(lattice mismatch),但因為在燒結過程期間Ti會在鈣鈦礦材料(其中 <sup>XII</sup>A <sup>2</sup><sup>+</sup><sup>VI</sup>B <sup>4</sup><sup>+</sup>X <sup>2</sup><sup>−</sup><sub>3</sub>之「B」為Ti)與CaZrTi <sub>2</sub>O <sub>7</sub>、TiO <sub>2</sub>(金紅石)之間相互擴散(mutual diffusion),且Zr會在CaZrTi <sub>2</sub>O <sub>7</sub>、CaZrO <sub>3</sub>、SrZrO <sub>3</sub>、BaZrO <sub>3</sub>與ZrO <sub>2</sub>之間相互擴散,所以可解決此類晶格不匹配之問題。因此,在上列材料用作半導體陶瓷相及介電陶瓷相時,其可燒結在一起而無開裂(crack)、斷裂(rupture)、脆性破壞(brittle failure)及破裂(fracture),從而提供陶瓷燒結體良好的結構強度。 </p><p>此外,在本發明之一些實施例中,介電陶瓷相進一步摻雜(doped)另一種添加劑(additive)。舉例而言,添加劑為受體型(acceptor-type)添加劑,諸如V、Nb、Cr。此外,添加劑可為錳化合物、鎂化合物、矽酸鹽化合物、鎢化合物或氧化鋁化合物以提高介電性質。在本發明之一些實施例中,介電陶瓷相可進一步摻雜摻雜劑(dopant),諸如MnO <sub>2</sub>、MgO或WO <sub>3</sub>。此類摻雜劑可增強介電陶瓷相之介電性質,例如,提高介電陶瓷相之電阻率及可靠性。 </p><p>類似地,在本發明之一些實施例中,半導體陶瓷相進一步摻雜添加劑。舉例而言,添加劑為施體型(donor-type)添加劑,諸如Y、Nb或La,因此在半導體陶瓷相中形成Y <sub>2</sub>O <sub>3</sub>、Nb <sub>2</sub>O <sub>5</sub>、La <sub>2</sub>O <sub>3</sub>。此類添加劑可增強半導體陶瓷相之半導性質,例如,提高半導體陶瓷相之電導率。摻雜有施體添加劑且經還原之鈣鈦礦化合物可形成高施體密度n型半導材料(high donor density n-type semiconducting material)。 </p><p>本發明進一步提供一種被動元件,其包含前述陶瓷燒結體。在本發明中,被動元件為除其所連接之可用交流電(alternating current,AC)電路以外不需要能量來操作之電子元件。被動元件不具功率增益(power gain)且非為能量源(energy source)。舉例而言,被動元件包括兩端元件(two-terminal components),諸如電阻器(resistors)、電容器、電感器(inductors)及變壓器(transformers)。</p><p>本發明可關於一種製造上述陶瓷燒結體的方法。該方法包含混合半導體陶瓷粒及介電陶瓷粒以形成一混合物,以及於中性氣氛(neutral atmosphere)下燒結該混合物。</p><p>在本發明之一些實施例中,半導體陶瓷粒由與上文所描述之半導體陶瓷相相同的材料製成。然而,值得注意的是,金紅石及銳鈦礦(anatase)結構兩者中均可提供TiO <sub>2</sub>顆粒。半導體陶瓷粒之尺寸可為約0.1微米至約5微米,較佳為約0.2微米至約2微米。類似地,介電陶瓷粒由與上文所描述之介電相相同的材料製成。介電陶瓷粒之尺寸可為約0.1微米至約5微米,較佳為約0.2微米至約2微米。半導體陶瓷粒與介電陶瓷粒之混合可藉由例如珠磨機(bead miller)來達成。混合後,在諸如N <sub>2</sub>、He、Ar等之中性氣氛下燒結混合物。燒結溫度可為例如約1100℃至約1500℃。 </p><p>在本發明之一些實施例中,該方法進一步包括混合半導體粒、介電粒及黏合劑(binder)於溶劑中,及在燒結前移除黏合劑及溶劑。舉例而言,黏合劑包括聚乙烯醇(polyvinyl alcohol,PVA)、聚丙烯酸酯(polyacrylate)及乙基纖維素(ethyl cellulose)。溶劑包括乙醇、甲苯(toluene)、甲基乙基酮(methyl ethyl ketone,MEK)、二甘醇單丁醚(diethylene glycol monobutyl ether,BC)及丁基卡必醇乙酸酯(butyl carbitol acetate,BCA)以及其組合。亦可添加其他燒結助劑,諸如SiO <sub>2</sub>、GeO <sub>2</sub>、B <sub>2</sub>O <sub>3</sub>等,以增大燒結密度且降低燒結溫度。溶劑係指用於混合半導體陶瓷粒及介電陶瓷粒之液體。較佳地,溶劑不與半導體陶瓷粒、介電陶瓷粒及/或黏合劑反應。舉例而言,溶劑包括醇、醚等。 </p><p>下列範例僅用於說明本發明,惟本發明之範圍並不以此為限。</p><p>實例1:包含TiO <sub>2</sub>-ZrO <sub>2</sub>固體溶液作為介電陶瓷相及SrTiO <sub>3</sub>-CaTiO <sub>3</sub>固體溶液作為半導體陶瓷相之陶瓷燒結體 </p><p>圖2展示實例1之示意性製造流程。將0.075莫耳碳酸鍶(SrCO <sub>3</sub>)、0.075莫耳碳酸鈣(CaCO <sub>3</sub>)及0.15莫耳TiO <sub>2</sub>(金紅石)以珠磨機(氧化鋯珠粒,直徑為0.1 mm)在乙醇中混合。混合後在氮氣流中乾燥混合粉末。將所得混合物進行乾磨(dry-ground)並在1,000℃下於N <sub>2</sub>+H <sub>2</sub>(95%+5%)氣流中煅燒5小時,以獲得黑色半導體(Sr <sub>0.5</sub>Ca <sub>0.5</sub>)TiO <sub>3</sub>粉末。將0.5莫耳氧化鋯(ZrO <sub>2</sub>)及0.5莫耳氧化鈦(TiO <sub>2</sub>)(金紅石)添加至經乾磨之粉末中且再次由珠磨機混合。 </p><p>將100重量份由此形成之粉末混合於乙醇中並進行研磨,且隨後與15重量份PVA黏合劑、0.1重量份SiO <sub>2</sub>及0.05重量份Al <sub>2</sub>O <sub>3</sub>混合以形成研磨漿(slurry)。使用塗佈機將研磨漿塗佈於聚對苯二甲酸乙二酯(polyethylene terephthalate)載帶上以形成生胚片(green sheet)。衝壓生胚片以形成複數個胚料(pellet)。在高於0.015 atm之氧氣分壓及550℃之溫度下將胚料加熱60分鐘以移除有機黏合劑。隨後於含有N <sub>2</sub>之氣氛下在1250℃之溫度下將胚料燒結30分鐘以形成陶瓷燒結體。以上條件之理論逾滲閾值為約28.95%,且陶瓷燒結體中之半導體陶瓷相(SrTiO <sub>3</sub>-CaTiO <sub>3</sub>)之體積分率為約27%。為驗證燒結陶瓷體中之半導體陶瓷粒及介電陶瓷粒之均勻混合狀態,在量測介電性質之前分別將樣品在800℃、900及1000℃下於空氣中再氧化(re-oxidized)30分鐘。在再氧化期間,半導體陶瓷粒可藉由晶界(grain boundary)處之氧氣擴散,自晶界區開始氧化。同時,在介電陶瓷粒中,同樣會於晶界處發生氧氣擴散。適當的再氧化條件可增強燒結陶瓷體之性質。然而,在較高再氧化溫度下,氧氣擴散不僅會於晶界處發生,亦會於顆粒之整體(bulk of grain)發生。強烈的氧氣擴散導致半導體陶瓷粒降解(degradation),因此降低其電導率。所得燒結體自兩側拋光100微米深,以沈積用於介電量測的Au電極。 </p><p>圖3A展示實例1中之陶瓷燒結體之高角度環形暗場(HAADF)圖像。圖像之對比度差異顯示至少一第一陶瓷相(較亮的粒子)及第二陶瓷相(較暗的粒子)。此外,STEM-EDX化學分析(圖3B至圖3E)證明第一陶瓷相(Sr-Ca-Ti)及第二陶瓷相(Ti-Zr)之存在。</p><p>圖4A展示自第一陶瓷相(在STEM-EDX化學分析中呈現Sr、Ca及Ti的較亮的粒子)獲得之選區電子繞射圖譜(SAED)。結果顯示第一陶瓷相(較亮的粒子)為(213) (Sr <sub>0</sub><sub>.</sub><sub>5</sub>Ca <sub>0</sub><sub>.</sub><sub>5</sub>)TiO <sub>3</sub>。圖4B展示自第二陶瓷相(在STEM-EDX化學分析中呈現Ti及Zr的較暗的粒子)獲得之選區電子繞射圖譜(SAED)。結果顯示第二陶瓷相(較暗的粒子)為(001) TiO <sub>2</sub>(金紅石),且推論為金紅石結構TiO <sub>2</sub>-ZrO <sub>2</sub>固體溶液。 </p><p>圖5展示實例1中之陶瓷燒結體之XRD(X射線繞射)。數個波峰亦顯示陶瓷燒結體中存在第一陶瓷相(亦即,(Sr <sub>0</sub><sub>.</sub><sub>5</sub>Ca <sub>0</sub><sub>.</sub><sub>5</sub>)TiO <sub>3</sub>相)及第二陶瓷相(亦即,金紅石結構TiO <sub>2</sub>-ZrO <sub>2</sub>固體溶液相)。 </p><p>圖6A、圖6B及圖6C展示在幾種不同再氧化條件下實例1中之陶瓷燒結體之相對介電常數、介電損耗(dielectric loss)及電阻率(resistivity)。介電常數及介電損耗減小及電阻率提高表明(Sr <sub>0</sub><sub>.</sub><sub>5</sub>Ca <sub>0</sub><sub>.</sub><sub>5</sub>)TiO <sub>3</sub>半導體相之再氧化程度上升。所得燒結陶瓷體(在圖6A至6D中標記為「燒結」)之介電常數顯著高於(Sr <sub>0</sub><sub>.</sub><sub>5</sub>Ca <sub>0</sub><sub>.</sub><sub>5</sub>)TiO <sub>3</sub>及TiO <sub>2</sub>-ZrO <sub>2</sub>之介電常數,且介電常數對應於再氧化溫度之升高而減小。對應半導體陶瓷相((Sr <sub>0</sub><sub>.</sub><sub>5</sub>Ca <sub>0</sub><sub>.</sub><sub>5</sub>)TiO <sub>3</sub>)之氧化程度減小的介電常數顯示燒結陶瓷體為亞逾滲複合體。亦即,所呈現的巨大的相對介電常數係源自於其亞逾滲結構。 </p><p>因此,以上分析結果展示實例1中之陶瓷燒結體包括半導體陶瓷相(亦即,(Sr <sub>0</sub><sub>.</sub><sub>5</sub>Ca <sub>0</sub><sub>.</sub><sub>5</sub>)TiO <sub>3</sub>相)分散於介電陶瓷相(亦即,金紅石結構TiO <sub>2</sub>-ZrO <sub>2</sub>固體溶液相)中,其中半導體陶瓷相及介電陶瓷相共同形成亞逾滲複合體。 </p><p>實例2:包含TiO <sub>2</sub>-ZrO <sub>2</sub>固體溶液作為介電陶瓷相及SrTiO <sub>3</sub>-CaTiO <sub>3</sub>固體溶液作為半導體陶瓷相之陶瓷燒結體 </p><p>圖7展示實例2之示意性製造流程。將0.11莫耳碳酸鍶(SrCO <sub>3</sub>)、0.046莫耳碳酸鈣(CaCO <sub>3</sub>)及0.154莫耳TiO <sub>2</sub>(金紅石)以珠磨機(氧化鋯珠粒,直徑為0.1 mm)在乙醇中混合。混合後在氮氣流中乾燥混合粉末。將所得混合物進行乾磨並在1,100℃下於N <sub>2</sub>+H <sub>2</sub>(95%+5%)氣流中煅燒5小時,以獲得黑色半導體(Sr <sub>0.7</sub>Ca <sub>0.3</sub>)TiO <sub>3</sub>粉末。將0.7莫耳氧化鋯(ZrO <sub>2</sub>)及0.3莫耳氧化鈦(TiO <sub>2</sub>)(金紅石)添加至經乾磨之粉末中且再次由珠磨機混合。 </p><p>將100重量份由此形成之粉末於包含20% MEK及80% BCA (v/v)之溶液中進行研磨,且隨後與15重量份乙基纖維素、0.3重量份CaSiO <sub>3</sub>、0.1重量份GeO <sub>2</sub>及0.05重量份Al <sub>2</sub>O <sub>3</sub>混合以形成研磨漿。使用塗佈機將研磨漿塗佈於聚對苯二甲酸乙二酯(PET)載帶上以形成生胚片。衝壓生胚片以形成複數個胚料。在高於0.015 atm之氧氣分壓及450℃之溫度下將胚料加熱60分鐘以移除黏合劑。隨後於含有N <sub>2</sub>之氣氛下在1300℃之溫度下將胚料燒結30分鐘以形成陶瓷燒結體。以上條件之理論逾滲閾值為約28.95%,且陶瓷燒結體中之半導體陶瓷相(SrTiO <sub>3</sub>-CaTiO <sub>3</sub>)之體積分率為約27.3%。為驗證燒結陶瓷體中之半導體陶瓷粒及介電陶瓷粒之均勻混合狀態,在量測介電性質之前分別將樣品在800℃、900及1000℃下於空氣中再氧化30分鐘。所得燒結體自兩側拋光100微米深,以沈積用於介電量測的Au電極。 </p><p>圖8A展示實例2中之陶瓷燒結體之高角度環形暗場(HAADF)圖像。圖像之對比度差異顯示數個陶瓷相。此外,STEM-EDX化學分析(圖8B至圖8E)證明第一陶瓷相(Sr-Ca-Ti)、第二陶瓷相(Ti-Zr)及第三陶瓷相(Ca-Zr-Ti)之存在。</p><p>圖9A展示自第一陶瓷相(在STEM-EDX化學分析中呈現Sr、Ca及Ti的粒子)獲得之選區電子繞射圖譜(SAED)。結果顯示第一陶瓷相為(212) (Sr <sub>0</sub><sub>.7</sub>Ca <sub>0</sub><sub>.3</sub>)TiO <sub>3</sub>。圖9B展示自第二陶瓷相(在STEM-EDX化學分析中呈現Ti及Zr的粒子)獲得之選區電子繞射圖譜(SAED)。結果顯示第二陶瓷相為(311) TiO <sub>2</sub>(金紅石),且推論為金紅石結構TiO <sub>2</sub>-ZrO <sub>2</sub>固體溶液。圖9C展示自第三陶瓷相(在STEM-EDX化學分析中呈現Ca、Zr及Ti的粒子)獲得之選區電子繞射圖譜(SAED)。比對圖9D所示之(150) CaZrTiO <sub>7</sub>(鈣鈦鋯石)的模擬圖譜結果,咸信第三陶瓷相為(150) CaZrTiO <sub>7</sub>(鈣鈦鋯石)。 </p><p>圖10展示實例2中之陶瓷燒結體之XRD(X射線繞射)。數個波峰亦顯示陶瓷燒結體中存在第一陶瓷相(亦即,(Sr <sub>0</sub><sub>.</sub><sub>5</sub>Ca <sub>0</sub><sub>.</sub><sub>5</sub>)TiO <sub>3</sub>相)、第二陶瓷相(亦即,金紅石結構TiO <sub>2</sub>-ZrO <sub>2</sub>固體溶液相)及第三陶瓷相(亦即,CaZrTiO <sub>7</sub>相)。 </p><p>圖11A、圖11B及圖11C展示在幾種不同再氧化條件下實例2中之陶瓷燒結體之相對介電常數、介電損耗及電阻率。介電常數及介電損耗減小及電阻率提高表明(Sr <sub>0</sub><sub>.</sub><sub>5</sub>Ca <sub>0</sub><sub>.</sub><sub>5</sub>)TiO <sub>3</sub>半導體相之再氧化程度上升。所得燒結陶瓷體(在圖11A至11C中標記為「燒結」)之介電常數顯著高於(Sr <sub>0</sub><sub>.</sub><sub>5</sub>Ca <sub>0</sub><sub>.</sub><sub>5</sub>)TiO <sub>3</sub>、CaZrTiO <sub>7</sub>及TiO <sub>2</sub>-ZrO <sub>2</sub>之介電常數,且介電常數對應於再氧化溫度之升高而減小。對應半導體陶瓷相((Sr <sub>0</sub><sub>.</sub><sub>5</sub>Ca <sub>0</sub><sub>.</sub><sub>5</sub>)TiO <sub>3</sub>)之氧化程度減小的介電常數顯示燒結陶瓷體為亞逾滲複合體。亦即,所呈現的巨大的相對介電常數係源自於其亞逾滲結構。 </p><p>因此,以上分析結果展示實例2中之陶瓷燒結體包括半導體陶瓷相(亦即,(Sr <sub>0</sub><sub>.</sub><sub>5</sub>Ca <sub>0</sub><sub>.</sub><sub>5</sub>)TiO <sub>3</sub>相)分散於介電陶瓷相(亦即,金紅石結構TiO <sub>2</sub>-ZrO <sub>2</sub>固體溶液相及CaZrTiO <sub>7</sub>相)中,其中半導體陶瓷相及介電陶瓷相共同形成亞逾滲複合體。 </p><p>實例3:包含TiO <sub>2</sub>-ZrO <sub>2</sub>固體溶液作為介電陶瓷相及SrTiO <sub>3</sub>固體溶液作為半導體陶瓷相之陶瓷燒結體 </p><p>圖12展示實例3之示意性製造流程。將0.25莫耳碳酸鍶(SrCO <sub>3</sub>)及0.25莫耳TiO <sub>2</sub>(銳鈦礦)以珠磨機(氧化鋯珠粒,直徑為0.1 mm)在乙醇中混合。混合後在氮氣流中乾燥混合粉末。將所得混合物進行乾磨並在1,000℃下於N <sub>2</sub>+H <sub>2</sub>(95%+5%)氣流中煅燒5小時,以獲得黑色半導體SrTiO <sub>3</sub>粉末。將0.5莫耳氧化鋯(ZrO <sub>2</sub>)及0.5莫耳氧化鈦(TiO <sub>2</sub>)(銳鈦礦)添加至經乾磨之粉末中且再次由珠磨機混合。 </p><p>將100重量份由此形成之粉末於包含35%甲苯及65% MEK (v/v)之溶液中進行研磨,且隨後與15重量份聚丙烯酸酯、0.3重量份SrSiO <sub>3</sub>、0.1重量份GeO <sub>2</sub>及0.1重量份MnO <sub>2</sub>混合以形成研磨漿。使用塗佈機將研磨漿塗佈於PET載帶上以形成生胚片。衝壓生胚片以形成複數個胚料。在高於0.015 atm之氧氣分壓及450℃之溫度下將胚料加熱60分鐘以移除有機黏合劑。隨後於含有N <sub>2</sub>之氣氛下在1300℃之溫度下將胚料燒結30分鐘以形成陶瓷燒結體。以上條件之理論逾滲閾值為約28.95%,且陶瓷燒結體中之半導體陶瓷相(SrTiO <sub>3</sub>)之體積分率為約27.8%。為驗證燒結陶瓷體中之半導體陶瓷粒及介電陶瓷粒之均勻混合狀態,在量測介電性質之前分別將樣品在800℃、900及1000℃下於空氣中再氧化30分鐘。所得燒結體自兩側拋光100微米深,以沈積用於介電量測的Au電極。 </p><p>圖13A展示實例3中之陶瓷燒結體之高角度環形暗場(HAADF)圖像。圖像之對比度差異顯示數個陶瓷相。此外,STEM-EDX化學分析(圖13B至圖13D)證明第一陶瓷相(Sr-Ti)及第二陶瓷相(Ti-Zr)之存在。</p><p>圖14A展示自第一陶瓷相(在STEM-EDX化學分析中呈現Sr及Ti的粒子)獲得之選區電子繞射圖譜(SAED)。結果顯示第一陶瓷相為(112) SrTiO <sub>3</sub>。圖14B展示自第二陶瓷相(在STEM-EDX化學分析中呈現Ti及Zr的粒子)獲得之選區電子繞射圖譜(SAED)。結果顯示第二陶瓷相為(101) TiO <sub>2</sub>(金紅石),且推論為金紅石結構TiO <sub>2</sub>-ZrO <sub>2</sub>固體溶液。 </p><p>圖15展示實例3中之陶瓷燒結體之XRD(X射線繞射)。數個波峰亦顯示陶瓷燒結體中存在第一陶瓷相(亦即,SrTiO <sub>3</sub>相)及第二陶瓷相(亦即,金紅石結構TiO <sub>2</sub>-ZrO <sub>2</sub>固體溶液相)。 </p><p>圖16A、圖16B及圖16C展示在幾種不同再氧化條件下實例3中之陶瓷燒結體之相對介電常數、介電損耗及電阻率。介電常數及介電損耗減小及電阻率提高表明SrTiO <sub>3</sub>半導體相之再氧化程度上升。所得燒結陶瓷體(在圖16A至16C中標記為「燒結」)之介電常數顯著高於SrTiO <sub>3</sub>及TiO <sub>2</sub>-ZrO <sub>2</sub>之介電常數,且介電常數對應於再氧化溫度之升高而減小。對應半導體陶瓷相((Sr <sub>0</sub><sub>.</sub><sub>5</sub>Ca <sub>0</sub><sub>.</sub><sub>5</sub>)TiO <sub>3</sub>)之氧化程度減小的介電常數顯示燒結陶瓷體為亞逾滲複合體。亦即,所呈現的巨大的相對介電常數係源自於其亞逾滲結構。 </p><p>實例4:包含CaZrTi <sub>2</sub>O <sub>7</sub>固體溶液作為介電陶瓷相及SrTiO <sub>3</sub>固體溶液作為半導體陶瓷相之陶瓷燒結體 </p><p>圖17展示實例4之示意性製造流程。將0.56莫耳碳酸鍶(SrCO <sub>3</sub>)、0.56莫耳TiO <sub>2</sub>(銳鈦礦)及0.015莫耳Y <sub>2</sub>O <sub>3</sub>以珠磨機(氧化鋯珠粒,直徑為0.1 mm)在乙醇中混合。混合後在氮氣流中乾燥混合粉末。將所得混合物進行乾磨並在1,000℃下於N <sub>2</sub>+H <sub>2</sub>(95%+5%)氣流中煅燒5小時,以獲得黑色半導體SrTiO <sub>3</sub>粉末。將1莫耳鈣鈦鋯石(CaZrTi <sub>2</sub>O <sub>7</sub>)添加至經乾磨之粉末中且再次由珠磨機混合。 </p><p>將100重量份由此形成之粉末於包含甲苯及MEK之溶液中進行研磨,且隨後與15重量份乙基纖維素黏合劑、0.3重量份SrSiO <sub>3</sub>、0.1重量份GeO <sub>2</sub>及0.1重量份MnO <sub>2</sub>混合以形成研磨漿。使用塗佈機將研磨漿塗佈於PET載帶上以形成生胚片。衝壓生胚片以形成複數個胚料。在高於0.015 atm之氧氣分壓及550℃之溫度下將胚料加熱60分鐘以移除有機黏合劑。隨後於含有N <sub>2</sub>之氣氛下在1300℃之溫度下將胚料燒結30分鐘以形成陶瓷燒結體。以上條件之理論逾滲閾值為約28.95%,且陶瓷燒結體中之半導體陶瓷相(SrTiO <sub>3</sub>)之體積分率為約28%。為驗證燒結陶瓷體中之半導體陶瓷粒及介電陶瓷粒之均勻混合狀態,在量測介電性質之前分別將樣品在800℃、900及1000℃下於空氣中再氧化30分鐘。所得燒結體自兩側拋光100微米深,以沈積用於介電量測的Au電極。 </p><p>圖18A展示實例4中之陶瓷燒結體之高角度環形暗場(HAADF)圖像。圖像之對比度差異顯示數個陶瓷相。此外,STEM-EDX化學分析(圖18B至圖18ED)證明第一陶瓷相(Sr-Ti)及第二陶瓷相(Ca-Zr-Ti)之存在。</p><p>圖19A展示自第一陶瓷相(在STEM-EDX化學分析中呈現Sr及Ti的粒子)獲得之選區電子繞射圖譜(SAED)。結果顯示第一陶瓷相為(102) SrTiO <sub>3</sub>。圖19B展示自第二陶瓷相(在STEM-EDX化學分析中呈現Ca、Ti及Zr的粒子)獲得之選區電子繞射圖譜(SAED)。結果顯示第二陶瓷相為(011) CaZrTi <sub>2</sub>O <sub>7</sub>(鈣鈦鋯石)。比對圖19C所示之(011) CaZrTiO <sub>7</sub>(鈣鈦鋯石)的模擬圖譜結果,咸信第二陶瓷相為(011) CaZrTiO <sub>7</sub>(鈣鈦鋯石)。 </p><p>圖20展示實例4中之陶瓷燒結體之XRD(X射線繞射)。數個波峰亦顯示陶瓷燒結體中存在第一陶瓷相(亦即,SrTiO <sub>3</sub>相)及第二陶瓷相(亦即,CaZrTi <sub>2</sub>O <sub>7</sub>(鈣鈦鋯石))。 </p><p>圖21A、圖21B及圖21C展示在幾種不同再氧化條件下實例4中之陶瓷燒結體之相對介電常數、介電損耗及電阻率。介電常數及介電損耗減小及電阻率提高表明SrTiO <sub>3</sub>半導體相之再氧化程度上升。所得燒結陶瓷體(在圖11A至11C中標記為「燒結」)之介電常數顯著高於SrTiO <sub>3</sub>及CaZrTi <sub>2</sub>O <sub>7</sub>之介電常數,且介電常數對應於再氧化溫度之升高而減小。對應半導體陶瓷相(SrTiO <sub>3</sub>)之氧化程度減小的介電常數顯示燒結陶瓷體為亞逾滲複合體。亦即,所呈現的巨大的相對介電常數係源自於其亞逾滲結構。 </p><p>儘管已參看本發明之特定實施例描述並說明本發明,但此等描述及說明並不作為限制。熟習此項技術者應理解,在不脫離如由所附申請專利範圍所界定之本發明之真實精神及範疇的情況下,可作出各種改變且可替代等效物。說明可不必按比例繪製。歸因於製造程序及容限,本發明中之藝術再現與實際設備之間可存在區別。可存在並未明確說明的本發明之其他實施例。應將本說明書及圖式視為說明性而非限制性的。可作出修改,以使特定情形、材料、物質組成、方法或製程適應於本發明之目標、精神及範疇。所有此類修改均意欲處於此處所附之申請專利範圍的範疇內。儘管已參看按特定次序執行之特定操作描述本文中所揭示的方法,但應理解,在不脫離本發明之教示的情況下,可組合、再細分,或重新定序此等操作以形成等效方法。因此,除非本文中明確指示,否則操作的次序及分組並非本發明之限制。</p></mode-for-invention><description-of-drawings><description-of-element><p>11 陶瓷相 12 介電陶瓷相</p></description-of-element><p>圖1示意性說明根據本發明之一些實施例之陶瓷燒結體的微觀結構(microstructure)。</p><p>圖2展示實例1之示意性製造流程。</p><p>圖3A展示實例1中之陶瓷燒結體的高角度環形暗場(high-angle annular dark-field,HAADF)圖像。</p><p>圖3B展示對實例1之陶瓷燒結體中之Sr的STEM-EDX化學分析。</p><p>圖3C展示對實例1之陶瓷燒結體中之Ca的STEM-EDX化學分析。</p><p>圖3D展示對實例1之陶瓷燒結體中之Ti的STEM-EDX化學分析。</p><p>圖3E展示對實例1之陶瓷燒結體中之Zr的STEM-EDX化學分析。</p><p>圖4A展示自實例1之陶瓷燒結體中之第一陶瓷相(在STEM-EDX化學分析中呈現Sr、Ca及Ti的較亮的粒子)獲得的選區電子繞射(selected area electron diffraction,SAED)圖譜。</p><p>圖4B展示自實例1之陶瓷燒結體中之第二陶瓷相(在STEM-EDX化學分析中呈現Ti及Zr的較暗的粒子)獲得的選區電子繞射(SAED)圖譜。</p><p>圖5展示實例1中之陶瓷燒結體之X光繞射(x-ray diffraction,XRD)圖譜。</p><p>圖6A展示實例1中之陶瓷燒結體在幾種不同再氧化條件(re-oxidation conditions)下的相對介電常數(relative dielectric constant)。</p><p>圖6B展示實例1中之陶瓷燒結體在幾種不同再氧化條件下的介電損耗(dielectric loss)。</p><p>圖6C展示實例1中之陶瓷燒結體在幾種不同再氧化條件下的電阻率(resistivity)。</p><p>圖7展示實例2之示意性製造流程。</p><p>圖8A展示實例2中之陶瓷燒結體的高角度環形暗場(HAADF)圖像。</p><p>圖8B展示對實例2之陶瓷燒結體中之Sr的STEM-EDX化學分析。</p><p>圖8C展示對實例2之陶瓷燒結體中之Ca的STEM-EDX化學分析。</p><p>圖8D展示對實例2之陶瓷燒結體中之Ti的STEM-EDX化學分析。</p><p>圖8E展示對實例2之陶瓷燒結體中之Zr的STEM-EDX化學分析。</p><p>圖9A展示自實例2之陶瓷燒結體中之第一陶瓷相(在STEM-EDX化學分析中呈現Sr、Ca及Ti的粒子)獲得的選區電子繞射(SAED)圖譜。</p><p>圖9B展示自實例2之陶瓷燒結體中之第二陶瓷相(在STEM-EDX化學分析中呈現Ti及Zr的粒子)獲得的選區電子繞射(SAED)圖譜。</p><p>圖9C展示自實例2之陶瓷燒結體中之第三陶瓷相(在STEM-EDX化學分析中呈現Ca、Zr及Ti的粒子)獲得的選區電子繞射(SAED)圖譜。</p><p>圖9D展示(150) CaZrTiO <sub>7</sub>(鈣鈦鋯石,zirconolite)的選區電子繞射(SAED)的模擬圖譜(simulation pattern)。 </p><p>圖10展示實例2中之陶瓷燒結體之X光繞射(XRD)圖譜。</p><p>圖11A展示實例2中之陶瓷燒結體在幾種不同再氧化條件下的相對介電常數。</p><p>圖11B展示實例2中之陶瓷燒結體在幾種不同再氧化條件下的介電損耗。</p><p>圖11C展示實例2中之陶瓷燒結體在幾種不同再氧化條件下的電阻率。</p><p>圖12展示實例3之示意性製造流程。</p><p>圖13A展示實例3中之陶瓷燒結體的高角度環形暗場(HAADF)圖像。</p><p>圖13B展示對實例3之陶瓷燒結體中之Zr的STEM-EDX化學分析。</p><p>圖13C展示對實例3之陶瓷燒結體中之Ti的STEM-EDX化學分析。</p><p>圖13D展示對實例3之陶瓷燒結體中之Sr的STEM-EDX化學分析。</p><p>圖14A展示自實例3之陶瓷燒結體中之第一陶瓷相(在STEM-EDX化學分析中呈現Sr、Ca及Ti的粒子)獲得的選區繞射(selected area diffraction,SAD)圖譜。</p><p>圖14B展示自實例3之陶瓷燒結體中之第二陶瓷相(在STEM-EDX化學分析中呈現Zr及Ti的粒子)獲得的選區繞射(SAD)圖譜。</p><p>圖15展示實例3中之陶瓷燒結體之X光繞射(XRD)圖譜。</p><p>圖16A展示實例3中之陶瓷燒結體在幾種不同再氧化條件下的相對介電常數。</p><p>圖16B展示實例3中之陶瓷燒結體在幾種不同再氧化條件下的介電損耗。</p><p>圖16C展示實例3中之陶瓷燒結體在幾種不同再氧化條件下的電阻率。</p><p>圖17展示實例4之示意性製造流程。</p><p>圖18A展示實例4中之陶瓷燒結體的高角度環形暗場(HAADF)圖像。</p><p>圖18B展示對實例4之陶瓷燒結體中之Ca的STEM-EDX化學分析。</p><p>圖18C展示對實例4之陶瓷燒結體中之Ti的STEM-EDX化學分析。</p><p>圖18D展示對實例4之陶瓷燒結體中之Zr的STEM-EDX化學分析。</p><p>圖18E展示對實例4之陶瓷燒結體中之Sr的STEM-EDX化學分析。</p><p>圖19A展示自實例4之陶瓷燒結體中之第一陶瓷相(在STEM-EDX化學分析中呈現Sr及Ti的粒子)獲得的選區繞射(selected area diffraction,SAD)圖譜。</p><p>圖19B展示自實例4之陶瓷燒結體中之第二陶瓷相(在STEM-EDX化學分析中呈現Ca、Zr及Ti的粒子)獲得的選區繞射(SAD)圖譜。</p><p>圖19C展示(011) CaZrTiO <sub>7</sub>的選區電子繞射(SAED)的模擬圖譜。 </p><p>圖20展示實例4中之陶瓷燒結體之X光繞射(XRD)圖譜。</p><p>圖21A展示實例4中之陶瓷燒結體在幾種不同再氧化條件下的相對介電常數。</p><p>圖21B展示實例4中之陶瓷燒結體在幾種不同再氧化條件下的介電損耗。</p><p>圖21C展示實例4中之陶瓷燒結體在幾種不同再氧化條件下的電阻率。</p></description-of-drawings><bio-deposit /><sequence-list-text /><title lang="zh">ceramic sintered body and passive components containing the same </title> <title lang="en">CERAMIC SINTERED BODY AND PASSIVE COMPONENT INCLUDING THE SAME </title> <technical-field> <p>The present invention relates to a ceramic sintered body and a passive component comprising the same, in particular to a ceramic sintered body having a preferred dielectric constant, and comprising the ceramic sintered body Passive component. </p> </technical-field> <background-art> <p> Passive components such as capacitors are typically made of a dielectric material. In general, the capacitance of a capacitor is related to the dielectric constant of the dielectric material from which the capacitor is made. That is, the dielectric constant of the dielectric material is higher so that the capacitance of the capacitor is higher. Since an ideal capacitor should have a small size and a high capacitance, it is necessary to provide a material having a high dielectric constant. </p> </background-art> <disclosure> <p> The present invention provides a ceramic sintered body having a preferable dielectric constant. </p> <p> In some embodiments of the present invention, the ceramic sintered body comprises a semiconductor ceramic phase dispersed in a dielectric ceramic phase, wherein the semiconductor ceramic phase and the dielectric The ceramic phases together form a percolative composite, and the volume fraction of the semiconductive ceramic phase is close to and below a percolation threshold. </p> <p> The present invention further provides a passive component comprising the aforementioned ceramic sintered body. </p> </disclosure> <mode-for-invention> <p>In theory, ferroelectric materials are expected to have extremely high dielectric constants only in a very narrow temperature range close to a ferroelectric-paraelectric phase transition. However, it is conventional to obtain a capacitor having an acceptable dielectric constant by a multilayer structure. Specifically, a plurality of ferroelectric ceramic material layers are placed between a plurality of conductive layers to form a multilayered ceramic capacitor (MLCC). In the conventional MLCC, the thickness of the ferroelectric ceramic layer is a key factor affecting its capacitance. The capacitance of the MLCC can be increased by reducing the thickness of the ferroelectric ceramic layer using a ferroelectric ceramic material having a smaller grain size. However, due to the so-called "Size-Effect", ferroelectric ceramic materials having a small particle size exhibit a small dielectric constant. The conventional criteria for obtaining a higher capacitance of the MLCC by a thinner dielectric layer will theoretically be deadlocked. </p> <p>Another method of obtaining a capacitor having an acceptable dielectric constant is achieved by a percolation complex, which can be explained in terms of percolation theory. In general, "percolation theory" describes the behavior of a connected cluster in a random graph. In the field of capacitor related art, percolation theory can be used to describe the case where conductive grains form a current path to pass through a space filled by insulating grains. When the conductive particles are mixed with the insulating particles, the conductive particles are sufficient to form a current path to define a "permeation threshold" through the lowest volume fraction of the space filled by the insulating particles. In other words, when the volume fraction of the conductive particles reaches the percolation threshold, a portion of the conductive particles are connected to each other to form a current path to pass through the space filled by the insulating particles. An increase in the volume fraction of the conductive particles causes an increase in the dielectric constant exhibited by the composite. The composite exhibits a large dielectric constant when the volume fraction of the conductive particles is just before the percolation threshold (this is the highest conductive particle volume fraction before the percolation threshold). The percolative threshold power law is described below.   <tables> <table border="1" bordercolor="#000000" width="85%"> <tbody> <tr> <td> <img wi="197" he="98" file="02_image001.tif" img-format="tif"/> </img> </td> <td> <i>ε </i> <sub>0 </sub> is the matrix dielectric constant (matrix dielectric constant) <i>f </i> is a filling factor <i>f </i> <sub>c </sub> is the percolation threshold <b> <i>q </i> </b> is a critical exponent </td> </tr> </tbody> </table> </tables> </p> <p> The above-mentioned percolation composite uses a metal material and a dielectric ceramic material as conductive particles and insulating particles, respectively. The fine metal particles have a large surface energy. When mixed with dielectric ceramic particles, the metal particles tend to agglomerate together and thus cannot be uniformly dispersed in the mixture. When the mixing process is carried out on a large scale, the aggregation of metal particles may even be more serious. In addition, since the melting point of the metal particles (such as nickel) is usually lower than the melting point of the ceramic particles, the metal particles melt earlier than the insulating particles during the sintering process, resulting in a large grain growth during the sintering process (abnormal grain growth). ). Metal particles made of a noble metal having a high melting point such as platinum can be used to avoid abnormal grain growth during the sintering process, while the cost may be correspondingly increased. In view of the above, such percolation composites cannot meet industrial requirements. </p> <p> In order to at least solve the above problems, the present invention provides a ceramic sintered body comprising a semiconductor ceramic phase dispersed in a dielectric ceramic phase, wherein the semiconductor ceramic phase and the dielectric ceramic phase together form a percolation composite, and the semiconductor ceramic phase The volume fraction is close to and below the percolation threshold. By using a semiconductor ceramic material instead of the aforementioned metal material as the conductive phase, aggregation of the conductive phase and abnormal grain growth can be avoided. Therefore, such percolation composites having a good dielectric constant can be successfully produced. </p> <p> As used herein, the terms "substantially", "substantially", "substantial" and "about" are used to describe and account for minor changes. When used in connection with an event or circumstance, the term can refer to the circumstances in which the event or circumstance occurs explicitly and the event or circumstance is very similar. For example, when used in connection with a value, the terms may mean a range of variation less than or equal to ±10% of the value, such as less than or equal to ±5%, less than or equal to ±4%, less than or equal to ±3%, Less than or equal to ±2%, less than or equal to ±1%, less than or equal to ±0.5%, less than or equal to ±0.1%, or less than or equal to ±0.05%. </p> <p>In addition, sometimes quantities, ratios, and other values are presented in a range format in this article. It is to be understood that the scope of the present invention is to be construed as being limited to the scope of the Each value and sub-range are explicitly specified. </p> <p> In the present invention, the term "ceramic sintered body" means a sintered body which is made of a ceramic material. The ceramic sintered body may be sintered from two or more ceramic materials. For example, the ceramic sintered body may be sintered from a plurality of ceramic grains, and these ceramic particles are combined to form a monolithic structure. </p> <p> In the present invention, the term "phase" means a spatial region in which all physical properties of a material throughout the spatial region are substantially uniform. Examples of physical properties include, but are not limited to, density, refractive index, magnetization, electrical conductivity, dielectric constant, and chemical composition. The phase is preferably a physically and chemically uniform region of material and is physically distinct. For example, in some embodiments of the invention, the ceramic sintered body includes a semiconducting ceramic phase dispersed in a dielectric ceramic phase. The semiconducting ceramic phase is substantially made of a material having a conductivity that is substantially uniform within the semiconducting ceramic phase. Similarly, the dielectric ceramic phase is substantially made of another material having a conductivity that is substantially uniform within the dielectric ceramic phase. In addition, the electrical conductivity of the semiconducting ceramic phase is different from the electrical conductivity of the dielectric ceramic phase. </p> <p> In some embodiments of the invention, the dielectric ceramic phase is more similar to a continuous phase when compared to a semiconducting ceramic. On the other hand, the semiconducting ceramic phase is more similar to the dispersed phase dispersed in the dielectric ceramic phase. For purposes of illustration, Figure 1 shows the microstructure of a ceramic sintered body in accordance with some embodiments of the present invention. The ceramic phase 11 is dispersed in the dielectric ceramic phase 12 to form a percolation composite. It is noted that the ceramic sintered body according to some embodiments of the present invention may include more than one semiconducting ceramic phase and/or more than one dielectric ceramic phase. </p> <p> In certain embodiments of the invention, the dielectric ceramic phase refers to a phase composed of a ceramic material having dielectric properties. For example, the dielectric ceramics have a spacing greater than about 10   <sup>8 </sup>The resistivity of Ω-cm.   </p> <p> In certain embodiments of the invention, the semiconducting ceramic phase refers to a phase composed of a ceramic material having semiconducting properties. For example, the semiconducting ceramic phase can be an n-type semiconductor and have an electrical conductivity greater than about 0.5 S/m, or greater than about 1.0 S/m. </p> <p> In some embodiments of the invention, percolation capacitance refers to the highest volume fraction of the semiconducting ceramic phase that is just prior to forming a current path through the dielectric ceramic phase. The percolation threshold is the fraction of the semiconductor ceramic phase that is just sufficient to form a current path through the dielectric ceramic phase. The exact value of the percolation threshold can be determined by the material of the semiconducting ceramic phase and the dielectric ceramic phase, the particle size of the material, and the sintering temperature of the ceramic sintered body. The percolation threshold can be obtained by measurement or simulation, which can be understood by those of ordinary skill in the art. </p> <p> In the present invention, the volume fraction of the semiconductive ceramic phase of the percolation composite is very close to the percolation threshold. The volume fraction of the semiconductive ceramic phase in the percolation composite may be several percentage points below the percolation threshold. </p> <p> The dielectric constant of the ceramic sintered body (including the dielectric ceramic phase and the semiconductive ceramic phase) diverge at the percolation threshold. Therefore, since the dielectric ceramic phase and the semiconductive ceramic phase together form a percolative structure, and the volume fraction of the semiconductive ceramic phase is very close to the percolation threshold, the ceramic sintered body can have an elevated dielectric constant. That is, as the volume fraction of the semiconductive ceramic phase increases in a region close to the percolation threshold, the dielectric constant of the ceramic sintered body increases exponentially. </p> <p> In some embodiments, the volume fraction of the semiconductive ceramic phase in the percolation composite can be from about 0.05% to about 20% below the percolation threshold. For example, if the percolation threshold under specific conditions is 30%, the volume fraction of the semiconductive ceramic in the sub-percolative composite under the same conditions may be about 30-0.05%. Up to about 30-20%. In some embodiments, the volume fraction of the semiconductive ceramic phase in the percolation composite can be from about 0.05% to about 10%, from about 0.05% to about 5%, or from about 0.05% to about 3% below the percolation threshold. . In some embodiments of the invention, the volume fraction of the semiconducting ceramic phase is near and below the percolation threshold. In some embodiments, the volume fraction of the semiconducting ceramic phase can be from about 0.999 to about 0.33 times the exact value of the percolation threshold. For example, if the percolation threshold under specific conditions is 30%, the volume fraction of the semiconductive ceramic phase in the sub-permeability composite under the same conditions may be about (30 × 0.999)% to about (30) × 0.33)%. In some embodiments, the volume fraction of the semiconducting ceramic phase can be from about 0.999 to about 0.65, about 0.999 to about 0.75, about 0.999 to about 0.85, or about 0.999 times the exact value of the percolation threshold. Up to about 0.9 times. </p> <p> In some embodiments, for example, a percolation threshold under predetermined conditions may be calculated. The model used to calculate the percolation threshold under predetermined conditions can be found at least in C.D. Lorenz and R.M. Ziff,   <i>J. Chem. </i> <i>Phys </i>.   <b>114 </b>3659 (2001), S. Kirkpatrick,   <i>Rev. Mod. Phys </i>.   <b>45 </b>574 (1973), D. Stauffer,   <i>Phys Rep </i>.   <b>54 </b>1 (1979), and T.G. Castner, et al.,   <i>Phys. Rev. Lett. </i> <b>3 </b> <b>4 </b>1627 (1975) and other documents.   </p> <p>The exact value of the volume fraction of the semiconducting ceramic phase in the sub-permeate composite depends to a large extent on the particle size of the semiconducting ceramic phase and the dielectric ceramic phase and its geometrical distribution. For example, if the particle size of the dielectric ceramic phase is much smaller than the particle size of the semiconductive ceramic phase, and if it is distributed very uniformly, the volume fraction of the semiconducting ceramic phase may be large. On the other hand, if the particle size of the dielectric ceramic phase is much larger than the particle size of the semiconductive ceramic phase, and if it is geometrically well distributed, the volume fraction of the semiconductive ceramic phase may be small. However, in some embodiments, if the semiconductor ceramic phase has a particle size of about 3.0 microns and the dielectric ceramic phase has a particle size of about 0.2 microns, the volume fraction of the semiconductive ceramic phase is preferably from about 5% to about 60. More preferably, it is from about 15% to about 40%; still more preferably from about 20% to about 35%. If the semiconductor ceramic phase has a particle size of about 1.0 μm and the dielectric ceramic phase has a particle size of about 0.2 μm, the volume fraction of the semiconductive ceramic phase is preferably from about 5% to about 60%, more preferably about 15%. Up to about 40%, more preferably from about 25% to about 35%. And if the semiconductor ceramic phase has a particle size of about 0.2 μm and the dielectric ceramic phase has a particle size of about 0.1 μm, the semiconductor ceramic phase has a volume fraction of 5% to 55%, more preferably 15% to 35%. More preferably, it is about 20% to 30%. However, in some embodiments, the shape of the semiconducting ceramic phase can significantly affect the exact value of the percolation threshold. </p> <p> For example, a material of a dielectric ceramic phase according to some embodiments of the present invention includes CaZrTi   <sub>2 </sub>O   <sub>7 </sub>(zirconolite, zirconolite), CaZrO   <sub>3 </sub>, SrZrO   <sub>3 </sub>, BaZrO   <sub>3 </sub>, TiO   <sub>2 </sub>(rutile,rutile), ZrO   <sub>2 </sub>, or a solid solution thereof (for example, a solid solution thereof may include Ti   <sub>1 </sub> <sub>- </sub> <sub>x </sub>Zr   <sub>x </sub>O   <sub>2 </sub>, where x is a reasonable number between 0 and 1; or Ca   <sub>1 </sub> <sub>- </sub> <sub>x </sub>Sr   <sub>x </sub>ZrO   <sub>3 </sub>, where x is a reasonable number between 0 and 1.) In the case where the dielectric ceramic phase comprises calcium-titanium zircon, the dielectric ceramic phase can be clearly distinguished from the semiconducting ceramic phase.   </p> <p> For example, the material of the semiconductive ceramic phase according to some embodiments of the present invention includes a perovskite material. As is generally understood by those skilled in the art, "perovskite material" refers to a class of compounds having the same type of crystal structure.   <sup>XII </sup>A   <sup>2 </sup> <sup>+ </sup> <sup>VI </sup>B   <sup>4 </sup> <sup>+ </sup>X   <sup>2 </sup> <sup>− </sup> <sub>3 </sub>. "A" and "B" are two cations with extremely different sizes, and "X" is an anion bonded to both. The "A" atom is larger than the "B" atom. The ideal cubic symmetry has a 6-coordinate "B" cation surrounded by an anionic octahedron; and a 12-coordinated cubic octahedral "A" cation. In some embodiments of the invention, the perovskite material comprises barium titanate (SrTiO)   <sub>3 </sub>), barium titanate (BaTiO   <sub>3 </sub>), calcium titanate (CaTiO   <sub>3 </sub>), nickel titanate (NiTiO   <sub>3 </sub>), manganese titanate (MnTiO   <sub>3 </sub>), cobalt titanate (CoTiO   <sub>3 </sub>), copper titanate (CuTiO   <sub>3 </sub>), magnesium titanate (MgTiO   <sub>3 </sub>) or a complex thereof. Preferably, the perovskite material can be in a reduced state, such as reduced by, for example, a reducing atmosphere. In some embodiments of the invention, the material of the semiconducting ceramic phase comprises reduced TiO   <sub>2 </sub>(rutile), that is, TiO   <sub>2 </sub> <sub>- </sub> <sub>x </sub>; oxygen deficient state semiconductor. Reduced TiO   <sub>2 </sub> (rutile) can be reduced by, for example, a reducing atmosphere.   </p> <p>Although in perovskite materials, CaZrTi   <sub>2 </sub>O   <sub>7 </sub>, TiO   <sub>2 </sub>(rutile) and ZrO   <sub>2 There is a lattice mismatch in </sub>, but because Ti will be in the perovskite material during the sintering process   <sup>XII </sup>A   <sup>2 </sup> <sup>+ </sup> <sup>VI </sup>B   <sup>4 </sup> <sup>+ </sup>X   <sup>2 </sup> <sup>− </sup> <sub>3 </sub>"B" is Ti) and CaZrTi   <sub>2 </sub>O   <sub>7 </sub>, TiO   <sub>2 </sub>(rutile) mutual diffusion, and Zr will be in CaZrTi   <sub>2 </sub>O   <sub>7 </sub>, CaZrO   <sub>3 </sub>, SrZrO   <sub>3 </sub>, BaZrO   <sub>3 </sub> with ZrO   <sub>2 </sub> spreads between each other, so the problem of such lattice mismatch can be solved. Therefore, when the above materials are used as the semiconductive ceramic phase and the dielectric ceramic phase, they can be sintered together without cracking, rupture, brittle failure, and fracture, thereby providing ceramics. Good structural strength of the sintered body.   </p> <p> Further, in some embodiments of the invention, the dielectric ceramic phase is further doped with another additive. For example, the additive is an acceptor-type additive such as V, Nb, Cr. Further, the additive may be a manganese compound, a magnesium compound, a phthalate compound, a tungsten compound or an alumina compound to improve dielectric properties. In some embodiments of the invention, the dielectric ceramic phase may be further doped with a dopant, such as MnO.   <sub>2 </sub>, MgO or WO   <sub>3 </sub>. Such dopants can enhance the dielectric properties of the dielectric ceramic phase, for example, increasing the resistivity and reliability of the dielectric ceramic phase.   </p> <p> Similarly, in some embodiments of the invention, the semiconducting ceramic phase is further doped with an additive. For example, the additive is a donor-type additive such as Y, Nb or La, thus forming Y in the semiconductor ceramic phase   <sub>2 </sub>O   <sub>3 </sub>, Nb   <sub>2 </sub>O   <sub>5 </sub>, La   <sub>2 </sub>O   <sub>3 </sub>. Such additives can enhance the semiconducting properties of the semiconducting ceramic phase, for example, to increase the electrical conductivity of the semiconducting ceramic phase. The reduced donor perovskite compound is doped with a donor additive to form a high donor density n-type semiconducting material.   </p> <p> The present invention further provides a passive element comprising the aforementioned ceramic sintered body. In the present invention, a passive component is an electronic component that does not require energy to operate in addition to the available alternating current (AC) circuitry to which it is connected. Passive components do not have power gain and are not energy sources. For example, passive components include two-terminal components such as resistors, capacitors, inductors, and transformers. </p> <p> The present invention relates to a method of producing the above ceramic sintered body. The method comprises mixing semiconductor ceramic particles and dielectric ceramic particles to form a mixture, and sintering the mixture under a neutral atmosphere. </p> <p> In some embodiments of the invention, the semiconductive ceramic particles are made of the same material as the semiconducting ceramic described above. However, it is worth noting that both rutile and anatase structures provide TiO.   <sub>2 </sub> particles. The semiconductor ceramic particles may range in size from about 0.1 microns to about 5 microns, preferably from about 0.2 microns to about 2 microns. Similarly, the dielectric ceramic particles are made of the same material as the dielectric phase described above. The dielectric ceramic particles may range in size from about 0.1 microns to about 5 microns, preferably from about 0.2 microns to about 2 microns. The mixing of the semiconductive ceramic particles with the dielectric ceramic particles can be achieved by, for example, a bead miller. After mixing, in such as N   <sub>2 The mixture is sintered under a neutral atmosphere such as </sub>, He, Ar, or the like. The sintering temperature can be, for example, from about 1100 ° C to about 1500 ° C.   </p> <p> In some embodiments of the invention, the method further comprises mixing the semiconductor particles, dielectric particles, and binder in a solvent, and removing the binder and solvent prior to sintering. For example, the binder includes polyvinyl alcohol (PVA), polyacrylate, and ethyl cellulose. The solvent includes ethanol, toluene, methyl ethyl ketone (MEK), diethylene glycol monobutyl ether (BC), and butyl carbitol acetate (butyl carbitol acetate, BCA) and combinations thereof. Other sintering aids such as SiO can also be added.   <sub>2 </sub>, GeO   <sub>2 </sub>, B   <sub>2 </sub>O   <sub>3 </sub>, etc., to increase the sintered density and lower the sintering temperature. Solvent refers to a liquid used to mix semiconductor ceramic particles and dielectric ceramic particles. Preferably, the solvent does not react with the semiconducting ceramic particles, the dielectric ceramic particles and/or the binder. For example, the solvent includes an alcohol, an ether, and the like.   </p> <p> The following examples are merely illustrative of the invention, but the scope of the invention is not limited thereto. </p> <p>Example 1: Containing TiO   <sub>2 </sub>-ZrO   <sub>2 </sub>solid solution as dielectric ceramic phase and SrTiO   <sub>3 </sub>-CaTiO   <sub>3 </sub>solid solution as ceramic sintered body of semiconductor ceramic phase   </p> <p> Figure 2 shows a schematic manufacturing flow of Example 1. 0.075 mol of strontium carbonate (SrCO)   <sub>3 </sub>), 0.075 mol calcium carbonate (CaCO   <sub>3 </sub>) and 0.15 mole TiO   <sub>2 </sub> (rutile) was mixed in a bead mill (zirconia beads, 0.1 mm in diameter) in ethanol. After mixing, the mixed powder was dried in a stream of nitrogen. The resulting mixture was dry-ground and centrifuged at 1,000 ° C.   <sub>2 </sub>+H   <sub>2 </sub>(95%+5%) calcination in a gas stream for 5 hours to obtain a black semiconductor (Sr   <sub>0.5 </sub>Ca   <sub>0.5 </sub>)TiO   <sub>3 </sub> powder. 0.5 m zirconia (ZrO)   <sub>2 </sub>) and 0.5 mole titanium oxide (TiO   <sub>2 </sub>) (rutile) is added to the dry milled powder and mixed again by a bead mill.   </p> <p> 100 parts by weight of the powder thus formed is mixed in ethanol and ground, and then with 15 parts by weight of PVA binder, 0.1 part by weight of SiO   <sub>2 </sub> and 0.05 parts by weight of Al   <sub>2 </sub>O   <sub>3 </sub> mixing to form a slurry. The slurry was coated on a polyethylene terephthalate carrier tape using a coater to form a green sheet. The green sheets are stamped to form a plurality of pellets. The billet was heated at a partial pressure of oxygen above 0.015 atm and a temperature of 550 ° C for 60 minutes to remove the organic binder. Subsequent to containing N   <sub>2 The billet was sintered at a temperature of 1250 ° C for 30 minutes under an atmosphere of </sub> to form a ceramic sintered body. The theoretical percolation threshold of the above conditions is about 28.95%, and the semiconducting ceramic phase (SrTiO) in the ceramic sintered body   <sub>3 </sub>-CaTiO   <sub>3 The volume fraction of </sub>) is about 27%. In order to verify the uniform mixing state of the semiconducting ceramic particles and the dielectric ceramic particles in the sintered ceramic body, the samples were re-oxidized in air at 800 ° C, 900 and 1000 ° C, respectively, before measuring the dielectric properties. minute. During reoxidation, the semiconducting ceramic particles can be oxidized from the grain boundary region by diffusion of oxygen at the grain boundary. At the same time, in the dielectric ceramic grains, oxygen diffusion also occurs at the grain boundaries. Appropriate reoxidation conditions enhance the properties of the sintered ceramic body. However, at higher reoxidation temperatures, oxygen diffusion occurs not only at the grain boundaries, but also at the bulk of the grain. The strong oxygen diffusion leads to the degradation of the semiconducting ceramic particles, thus reducing their electrical conductivity. The resulting sintered body was polished to a depth of 100 μm from both sides to deposit an Au electrode for dielectric measurement.   </p> <p> Figure 3A shows a high angle annular dark field (HAADF) image of the ceramic sintered body of Example 1. The difference in contrast of the image shows at least a first ceramic phase (lighter particles) and a second ceramic phase (darker particles). In addition, STEM-EDX chemical analysis (Fig. 3B to Fig. 3E) demonstrates the presence of the first ceramic phase (Sr-Ca-Ti) and the second ceramic phase (Ti-Zr). </p> <p> Figure 4A shows a selected area electron diffraction pattern (SAED) obtained from a first ceramic phase (lighter particles exhibiting Sr, Ca, and Ti in STEM-EDX chemical analysis). The result shows that the first ceramic phase (lighter particles) is (213) (Sr   <sub>0 </sub> <sub>. </sub> <sub>5 </sub>Ca   <sub>0 </sub> <sub>. </sub> <sub>5 </sub>)TiO   <sub>3 </sub>. 4B shows a selected area electron diffraction pattern (SAED) obtained from a second ceramic phase (dark particles exhibiting Ti and Zr in STEM-EDX chemical analysis). The results show that the second ceramic phase (darker particles) is (001) TiO   <sub>2 </sub>(rutile), and inferred to be rutile TiO   <sub>2 </sub>-ZrO   <sub>2 </sub> solid solution.   </p> <p> FIG. 5 shows XRD (X-ray diffraction) of the ceramic sintered body in Example 1. Several peaks also show the presence of the first ceramic phase in the ceramic sintered body (ie, (Sr)   <sub>0 </sub> <sub>. </sub> <sub>5 </sub>Ca   <sub>0 </sub> <sub>. </sub> <sub>5 </sub>)TiO   <sub>3 </sub> phase) and second ceramic phase (ie, rutile structure TiO   <sub>2 </sub>-ZrO   <sub>2 </sub>solid solution phase).   </p> <P> Figures 6A, 6B and 6C show the relative dielectric constant, dielectric loss and resistivity of the ceramic sintered body of Example 1 under several different reoxidation conditions. Dielectric constant and dielectric loss reduction and resistivity increase indicate (Sr   <sub>0 </sub> <sub>. </sub> <sub>5 </sub>Ca   <sub>0 </sub> <sub>. </sub> <sub>5 </sub>)TiO   <sub>3 </sub> The degree of reoxidation of the semiconductor phase increases. The dielectric constant of the obtained sintered ceramic body (labeled as "sintering" in Figs. 6A to 6D) is remarkably higher than (Sr   <sub>0 </sub> <sub>. </sub> <sub>5 </sub>Ca   <sub>0 </sub> <sub>. </sub> <sub>5 </sub>)TiO   <sub>3 </sub> and TiO   <sub>2 </sub>-ZrO   <sub>2 The dielectric constant of </sub>, and the dielectric constant decreases corresponding to an increase in the reoxidation temperature. Corresponding to semiconductor ceramic phase ((Sr   <sub>0 </sub> <sub>. </sub> <sub>5 </sub>Ca   <sub>0 </sub> <sub>. </sub> <sub>5 </sub>)TiO   <sub>3 The reduced dielectric constant of </sub>) indicates that the sintered ceramic body is a sub-permeate composite. That is, the large relative dielectric constant exhibited is derived from its sub-permeability structure.   </p> <p> Therefore, the above analysis results show that the ceramic sintered body in Example 1 includes a semiconductor ceramic phase (that is, (Sr)   <sub>0 </sub> <sub>. </sub> <sub>5 </sub>Ca   <sub>0 </sub> <sub>. </sub> <sub>5 </sub>)TiO   <sub>3 </sub>phase) dispersed in a dielectric ceramic phase (ie, rutile TiO   <sub>2 </sub>-ZrO   <sub>2 </sub> solid solution phase), wherein the semiconductive ceramic phase and the dielectric ceramic phase together form a sub-permeation composite.   </p> <p>Example 2: Containing TiO   <sub>2 </sub>-ZrO   <sub>2 </sub>solid solution as dielectric ceramic phase and SrTiO   <sub>3 </sub>-CaTiO   <sub>3 </sub>solid solution as ceramic sintered body of semiconductor ceramic phase   </p> <p> Figure 7 shows a schematic manufacturing flow of Example 2. 0.11 mole of strontium carbonate (SrCO)   <sub>3 </sub>), 0.046 mole calcium carbonate (CaCO   <sub>3 </sub>) and 0.154 mole TiO   <sub>2 </sub> (rutile) was mixed in a bead mill (zirconia beads, 0.1 mm in diameter) in ethanol. After mixing, the mixed powder was dried in a stream of nitrogen. The resulting mixture was dry milled and dried at 1,100 ° C.   <sub>2 </sub>+H   <sub>2 </sub>(95%+5%) calcination in a gas stream for 5 hours to obtain a black semiconductor (Sr   <sub>0.7 </sub>Ca   <sub>0.3 </sub>)TiO   <sub>3 </sub> powder. 0.7 m zirconia (ZrO)   <sub>2 </sub>) and 0.3 mole titanium oxide (TiO   <sub>2 </sub>) (rutile) is added to the dry milled powder and mixed again by a bead mill.   </p> <p> 100 parts by weight of the powder thus formed is ground in a solution containing 20% MEK and 80% BCA (v/v), and then with 15 parts by weight of ethyl cellulose, 0.3 parts by weight of CaSiO   <sub>3 </sub>, 0.1 parts by weight of GeO   <sub>2 </sub> and 0.05 parts by weight of Al   <sub>2 </sub>O   <sub>3 </sub> mixing to form a slurry. The slurry was coated on a polyethylene terephthalate (PET) carrier tape using a coater to form a green sheet. The green sheets are stamped to form a plurality of blanks. The billet was heated at a partial pressure of oxygen above 0.015 atm and a temperature of 450 ° C for 60 minutes to remove the binder. Subsequent to containing N   <sub>2 The billet was sintered at a temperature of 1300 ° C for 30 minutes under an atmosphere of </sub> to form a ceramic sintered body. The theoretical percolation threshold of the above conditions is about 28.95%, and the semiconducting ceramic phase (SrTiO) in the ceramic sintered body   <sub>3 </sub>-CaTiO   <sub>3 The volume fraction of </sub>) is about 27.3%. In order to verify the uniform mixing state of the semiconducting ceramic particles and the dielectric ceramic particles in the sintered ceramic body, the samples were respectively reoxidized in air at 800 ° C, 900 ° C, and 1000 ° C for 30 minutes before measuring the dielectric properties. The resulting sintered body was polished to a depth of 100 μm from both sides to deposit an Au electrode for dielectric measurement.   </p> <P> Fig. 8A shows a high angle annular dark field (HAADF) image of the ceramic sintered body in Example 2. The difference in contrast of the image shows several ceramic phases. In addition, STEM-EDX chemical analysis (Fig. 8B to Fig. 8E) demonstrates the existence of the first ceramic phase (Sr-Ca-Ti), the second ceramic phase (Ti-Zr) and the third ceramic phase (Ca-Zr-Ti). . </p> <p> Figure 9A shows a selected area electron diffraction pattern (SAED) obtained from a first ceramic phase (particles exhibiting Sr, Ca, and Ti in STEM-EDX chemical analysis). The result shows that the first ceramic phase is (212) (Sr   <sub>0 </sub> <sub>.7 </sub>Ca   <sub>0 </sub> <sub>.3 </sub>)TiO   <sub>3 </sub>. Figure 9B shows a selected area electron diffraction pattern (SAED) obtained from a second ceramic phase (particles exhibiting Ti and Zr in STEM-EDX chemical analysis). The result shows that the second ceramic phase is (311) TiO   <sub>2 </sub>(rutile), and inferred to be rutile TiO   <sub>2 </sub>-ZrO   <sub>2 </sub> solid solution. Figure 9C shows a selected area electron diffraction pattern (SAED) obtained from a third ceramic phase (particles exhibiting Ca, Zr, and Ti in STEM-EDX chemical analysis). Aligning (150) CaZrTiO shown in Figure 9D   <sub>7 </sub>(Calcium-titanium zircon) simulation results, the third ceramic phase of Xianxin is (150) CaZrTiO   <sub>7 </sub>(Calcium titanium zircon).   </p> <p> Figure 10 shows XRD (X-ray diffraction) of the ceramic sintered body in Example 2. Several peaks also show the presence of the first ceramic phase in the ceramic sintered body (ie, (Sr)   <sub>0 </sub> <sub>. </sub> <sub>5 </sub>Ca   <sub>0 </sub> <sub>. </sub> <sub>5 </sub>)TiO   <sub>3 </sub>phase), second ceramic phase (ie, rutile structure TiO   <sub>2 </sub>-ZrO   <sub>2 </sub>solid solution phase) and a third ceramic phase (ie, CaZrTiO   <sub>7 </sub>phase).   </p> <p> Figures 11A, 11B and 11C show the relative dielectric constant, dielectric loss and electrical resistivity of the ceramic sintered body of Example 2 under several different reoxidation conditions. Dielectric constant and dielectric loss reduction and resistivity increase indicate (Sr   <sub>0 </sub> <sub>. </sub> <sub>5 </sub>Ca   <sub>0 </sub> <sub>. </sub> <sub>5 </sub>)TiO   <sub>3 </sub> The degree of reoxidation of the semiconductor phase increases. The dielectric constant of the obtained sintered ceramic body (labeled "sinter" in Figs. 11A to 11C) is remarkably higher than (Sr   <sub>0 </sub> <sub>. </sub> <sub>5 </sub>Ca   <sub>0 </sub> <sub>. </sub> <sub>5 </sub>)TiO   <sub>3 </sub>, CaZrTiO   <sub>7 </sub> and TiO   <sub>2 </sub>-ZrO   <sub>2 The dielectric constant of </sub>, and the dielectric constant decreases corresponding to an increase in the reoxidation temperature. Corresponding to semiconductor ceramic phase ((Sr   <sub>0 </sub> <sub>. </sub> <sub>5 </sub>Ca   <sub>0 </sub> <sub>. </sub> <sub>5 </sub>)TiO   <sub>3 The reduced dielectric constant of </sub>) indicates that the sintered ceramic body is a sub-permeate composite. That is, the large relative dielectric constant exhibited is derived from its sub-permeability structure.   </p> <p> Therefore, the above analysis results show that the ceramic sintered body in Example 2 includes a semiconductor ceramic phase (that is, (Sr)   <sub>0 </sub> <sub>. </sub> <sub>5 </sub>Ca   <sub>0 </sub> <sub>. </sub> <sub>5 </sub>)TiO   <sub>3 </sub>phase) dispersed in a dielectric ceramic phase (ie, rutile TiO   <sub>2 </sub>-ZrO   <sub>2 </sub>solid solution phase and CaZrTiO   <sub>7 In the </sub> phase, wherein the semiconductive ceramic phase and the dielectric ceramic phase together form a sub-permeation composite.   </p> <p>Example 3: Containing TiO   <sub>2 </sub>-ZrO   <sub>2 </sub>solid solution as dielectric ceramic phase and SrTiO   <sub>3 </sub>solid solution as ceramic sintered body of semiconductor ceramic phase   </p> <p> Figure 12 shows a schematic manufacturing flow of Example 3. 0.25 mol of barium carbonate (SrCO)   <sub>3 </sub>) and 0.25 mole TiO   <sub>2 </sub> (anatase) was mixed in a bead mill (zirconia beads, 0.1 mm in diameter) in ethanol. After mixing, the mixed powder was dried in a stream of nitrogen. The resulting mixture was dry milled and centrifuged at 1,000 ° C.   <sub>2 </sub>+H   <sub>2 </sub>(95%+5%) calcination in a gas stream for 5 hours to obtain a black semiconductor SrTiO   <sub>3 </sub> powder. 0.5 m zirconia (ZrO)   <sub>2 </sub>) and 0.5 mole titanium oxide (TiO   <sub>2 </sub>) (anatase) is added to the dry milled powder and mixed again by a bead mill.   </p> <p> 100 parts by weight of the powder thus formed is ground in a solution containing 35% of toluene and 65% MEK (v/v), and then with 15 parts by weight of polyacrylate, 0.3 parts by weight of SrSiO   <sub>3 </sub>, 0.1 parts by weight of GeO   <sub>2 </sub> and 0.1 parts by weight of MnO   <sub>2 </sub> mixing to form a slurry. The slurry was coated on a PET carrier tape using a coater to form a green sheet. The green sheets are stamped to form a plurality of blanks. The billet was heated at a partial pressure of oxygen above 0.015 atm and a temperature of 450 ° C for 60 minutes to remove the organic binder. Subsequent to containing N   <sub>2 The billet was sintered at a temperature of 1300 ° C for 30 minutes under an atmosphere of </sub> to form a ceramic sintered body. The theoretical percolation threshold of the above conditions is about 28.95%, and the semiconducting ceramic phase (SrTiO) in the ceramic sintered body   <sub>3 The volume fraction of </sub>) is about 27.8%. In order to verify the uniform mixing state of the semiconducting ceramic particles and the dielectric ceramic particles in the sintered ceramic body, the samples were respectively reoxidized in air at 800 ° C, 900 ° C, and 1000 ° C for 30 minutes before measuring the dielectric properties. The resulting sintered body was polished to a depth of 100 μm from both sides to deposit an Au electrode for dielectric measurement.   </p> <p> Figure 13A shows a high angle annular dark field (HAADF) image of the ceramic sintered body of Example 3. The difference in contrast of the image shows several ceramic phases. In addition, STEM-EDX chemical analysis (Fig. 13B to Fig. 13D) demonstrates the presence of the first ceramic phase (Sr-Ti) and the second ceramic phase (Ti-Zr). </p> <p> Figure 14A shows a selected area electron diffraction pattern (SAED) obtained from a first ceramic phase (particles exhibiting Sr and Ti in STEM-EDX chemical analysis). The results show that the first ceramic phase is (112) SrTiO   <sub>3 </sub>. Figure 14B shows a selected area electron diffraction pattern (SAED) obtained from a second ceramic phase (particles exhibiting Ti and Zr in STEM-EDX chemical analysis). The result shows that the second ceramic phase is (101) TiO   <sub>2 </sub>(rutile), and inferred to be rutile TiO   <sub>2 </sub>-ZrO   <sub>2 </sub> solid solution.   </p> <p> Figure 15 shows XRD (X-ray diffraction) of the ceramic sintered body in Example 3. Several peaks also indicate the presence of a first ceramic phase in the ceramic sintered body (ie, SrTiO   <sub>3 </sub> phase) and second ceramic phase (ie, rutile structure TiO   <sub>2 </sub>-ZrO   <sub>2 </sub>solid solution phase).   </p> <p> Figures 16A, 16B and 16C show the relative dielectric constant, dielectric loss and electrical resistivity of the ceramic sintered body of Example 3 under several different reoxidation conditions. Dielectric constant and dielectric loss decrease and resistivity increase indicate SrTiO   <sub>3 </sub> The degree of reoxidation of the semiconductor phase increases. The resulting sintered ceramic body (labeled "sintered" in Figs. 16A to 16C) has a significantly higher dielectric constant than SrTiO.   <sub>3 </sub> and TiO   <sub>2 </sub>-ZrO   <sub>2 The dielectric constant of </sub>, and the dielectric constant decreases corresponding to an increase in the reoxidation temperature. Corresponding to semiconductor ceramic phase ((Sr   <sub>0 </sub> <sub>. </sub> <sub>5 </sub>Ca   <sub>0 </sub> <sub>. </sub> <sub>5 </sub>)TiO   <sub>3 The reduced dielectric constant of </sub>) indicates that the sintered ceramic body is a sub-permeate composite. That is, the large relative dielectric constant exhibited is derived from its sub-permeability structure.   </p> <p>Example 4: Contains CaZrTi   <sub>2 </sub>O   <sub>7 </sub>solid solution as dielectric ceramic phase and SrTiO   <sub>3 </sub>solid solution as ceramic sintered body of semiconductor ceramic phase   </p> <p> Figure 17 shows a schematic manufacturing flow of Example 4. 0.56 moles of strontium carbonate (SrCO)   <sub>3 </sub>), 0.56 mole TiO   <sub>2 </sub>(anatase) and 0.015 mole Y   <sub>2 </sub>O   <sub>3 </sub> was mixed in a bead mill (zirconia beads, 0.1 mm in diameter) in ethanol. After mixing, the mixed powder was dried in a stream of nitrogen. The resulting mixture was dry milled and centrifuged at 1,000 ° C.   <sub>2 </sub>+H   <sub>2 </sub>(95%+5%) calcination in a gas stream for 5 hours to obtain a black semiconductor SrTiO   <sub>3 </sub> powder. 1 mole of calcium titanium zircon (CaZrTi   <sub>2 </sub>O   <sub>7 </sub>) is added to the dry milled powder and mixed again by a bead mill.   </p> <p> 100 parts by weight of the powder thus formed is ground in a solution containing toluene and MEK, and then with 15 parts by weight of ethyl cellulose binder, 0.3 parts by weight of SrSiO   <sub>3 </sub>, 0.1 parts by weight of GeO   <sub>2 </sub> and 0.1 parts by weight of MnO   <sub>2 </sub> mixing to form a slurry. The slurry was coated on a PET carrier tape using a coater to form a green sheet. The green sheets are stamped to form a plurality of blanks. The billet was heated at a partial pressure of oxygen above 0.015 atm and a temperature of 550 ° C for 60 minutes to remove the organic binder. Subsequent to containing N   <sub>2 The billet was sintered at a temperature of 1300 ° C for 30 minutes under an atmosphere of </sub> to form a ceramic sintered body. The theoretical percolation threshold of the above conditions is about 28.95%, and the semiconducting ceramic phase (SrTiO) in the ceramic sintered body   <sub>3 The volume fraction of </sub>) is about 28%. In order to verify the uniform mixing state of the semiconducting ceramic particles and the dielectric ceramic particles in the sintered ceramic body, the samples were respectively reoxidized in air at 800 ° C, 900 ° C, and 1000 ° C for 30 minutes before measuring the dielectric properties. The resulting sintered body was polished to a depth of 100 μm from both sides to deposit an Au electrode for dielectric measurement.   </p> <P> Fig. 18A shows a high angle annular dark field (HAADF) image of the ceramic sintered body in Example 4. The difference in contrast of the image shows several ceramic phases. In addition, STEM-EDX chemical analysis (Fig. 18B to Fig. 18ED) demonstrates the presence of the first ceramic phase (Sr-Ti) and the second ceramic phase (Ca-Zr-Ti). </p> <p> Figure 19A shows a selected area electron diffraction pattern (SAED) obtained from a first ceramic phase (particles exhibiting Sr and Ti in STEM-EDX chemical analysis). The results show that the first ceramic phase is (102) SrTiO   <sub>3 </sub>. Figure 19B shows a selected area electron diffraction pattern (SAED) obtained from a second ceramic phase (particles exhibiting Ca, Ti, and Zr in STEM-EDX chemical analysis). The result shows that the second ceramic phase is (011) CaZrTi   <sub>2 </sub>O   <sub>7 </sub>(Calcium titanium zircon). Aligning (011) CaZrTiO shown in Fig. 19C   <sub>7 </sub>(Calcium-titanium zircon) simulation results, the second ceramic phase of Xianxin is (011) CaZrTiO   <sub>7 </sub>(Calcium titanium zircon).   </p> <p> Figure 20 shows XRD (X-ray diffraction) of the ceramic sintered body in Example 4. Several peaks also indicate the presence of a first ceramic phase in the ceramic sintered body (ie, SrTiO   <sub>3 </sub> phase) and second ceramic phase (ie, CaZrTi   <sub>2 </sub>O   <sub>7 </sub>(Calcium Titanium Zircon)).   </p> <P> Figure 21A, Figure 21B and Figure 21C show the relative dielectric constant, dielectric loss and electrical resistivity of the ceramic sintered body of Example 4 under several different reoxidation conditions. Dielectric constant and dielectric loss decrease and resistivity increase indicate SrTiO   <sub>3 </sub> The degree of reoxidation of the semiconductor phase increases. The dielectric constant of the obtained sintered ceramic body (labeled as "sintering" in Figs. 11A to 11C) is remarkably higher than that of SrTiO   <sub>3 </sub> and CaZrTi   <sub>2 </sub>O   <sub>7 The dielectric constant of </sub>, and the dielectric constant decreases corresponding to an increase in the reoxidation temperature. Corresponding to semiconducting ceramic phase (SrTiO   <sub>3 The reduced dielectric constant of </sub>) indicates that the sintered ceramic body is a sub-permeate composite. That is, the large relative dielectric constant exhibited is derived from its sub-permeability structure.   </p> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; It will be understood by those skilled in the art that various changes and alternatives may be made without departing from the true spirit and scope of the invention as defined by the appended claims. The description may not necessarily be drawn to scale. Due to manufacturing procedures and tolerances, there may be differences between the artistic representations of the present invention and actual devices. There may be other embodiments of the invention that are not explicitly described. The description and drawings are to be regarded as illustrative and not limiting. Modifications may be made to adapt a particular situation, material, material composition, method or process to the objectives, spirit and scope of the invention. All such modifications are intended to be within the scope of the appended claims. Although the methods disclosed herein have been described with reference to specific operations performed in a particular order, it is understood that the operations can be combined, sub-segmented, or re-sequenced to form equivalents without departing from the teachings of the present invention. method. Therefore, the order of operations and groupings are not limiting of the invention unless explicitly indicated herein. </p> </mode-for-invention> <description-of-drawings> <description-of-element> <p>11 Ceramic phase 12 Dielectric ceramic phase </p> </description-of-element> <p> Figure 1 schematically illustrates the microstructure of a ceramic sintered body in accordance with some embodiments of the present invention. </p> <p> Figure 2 shows a schematic manufacturing flow of Example 1. </p> <p> FIG. 3A shows a high-angle annular dark-field (HAADF) image of the ceramic sintered body in Example 1. </p> <p> Figure 3B shows STEM-EDX chemical analysis of Sr in the ceramic sintered body of Example 1. </p> <p> Figure 3C shows STEM-EDX chemical analysis of Ca in the ceramic sintered body of Example 1. </p> <p> Figure 3D shows STEM-EDX chemical analysis of Ti in the ceramic sintered body of Example 1. </p> <p> Figure 3E shows STEM-EDX chemical analysis of Zr in the ceramic sintered body of Example 1. </p> <p> Figure 4A shows selected area electron diffraction obtained from the first ceramic phase in the ceramic sintered body of Example 1 (lighter particles exhibiting Sr, Ca, and Ti in STEM-EDX chemical analysis). , SAED) map. </p> <p> Figure 4B shows a selected area electron diffraction (SAED) pattern obtained from the second ceramic phase in the ceramic sintered body of Example 1 (dark particles exhibiting Ti and Zr in STEM-EDX chemical analysis). </p> <p> Figure 5 shows an x-ray diffraction (XRD) pattern of the ceramic sintered body of Example 1. </p> <P> Figure 6A shows the relative dielectric constant of the ceramic sintered body of Example 1 under several different re-oxidation conditions. </p> <P> Figure 6B shows the dielectric loss of the ceramic sintered body of Example 1 under several different reoxidation conditions. </p> <P> Figure 6C shows the resistivity of the ceramic sintered body of Example 1 under several different reoxidation conditions. </p> <p> Figure 7 shows a schematic manufacturing flow of Example 2. </p> <P> Fig. 8A shows a high angle annular dark field (HAADF) image of the ceramic sintered body in Example 2. </p> <P> Figure 8B shows STEM-EDX chemical analysis of Sr in the ceramic sintered body of Example 2. </p> <P> Figure 8C shows STEM-EDX chemical analysis of Ca in the ceramic sintered body of Example 2. </p> <P> Figure 8D shows STEM-EDX chemical analysis of Ti in the ceramic sintered body of Example 2. </p> <P> Figure 8E shows STEM-EDX chemical analysis of Zr in the ceramic sintered body of Example 2. </p> <P> FIG. 9A shows a selected area electron diffraction (SAED) pattern obtained from the first ceramic phase in the ceramic sintered body of Example 2 (particles exhibiting Sr, Ca, and Ti in STEM-EDX chemical analysis). </p> <P> Figure 9B shows a selected area electronic diffraction (SAED) pattern obtained from the second ceramic phase in the ceramic sintered body of Example 2 (particles exhibiting Ti and Zr in STEM-EDX chemical analysis). </p> <p> Figure 9C shows a selected area electron diffraction (SAED) pattern obtained from the third ceramic phase in the ceramic sintered body of Example 2 (particles exhibiting Ca, Zr, and Ti in STEM-EDX chemical analysis). </p> <p>Figure 9D shows (150) CaZrTiO   <sub>7 </sub> (Zirconolite, zirconolite) Selective area electron diffraction (SAED) simulation pattern.   </p> <p> Figure 10 shows an X-ray diffraction (XRD) pattern of the ceramic sintered body in Example 2. </p> <p> Figure 11A shows the relative dielectric constant of the ceramic sintered body of Example 2 under several different reoxidation conditions. </p> <p> Figure 11B shows the dielectric loss of the ceramic sintered body of Example 2 under several different reoxidation conditions. </p> <p> Figure 11C shows the electrical resistivity of the ceramic sintered body of Example 2 under several different reoxidation conditions. </p> <p> Figure 12 shows a schematic manufacturing flow of Example 3. </p> <p> Figure 13A shows a high angle annular dark field (HAADF) image of the ceramic sintered body of Example 3. </p> <P> Figure 13B shows STEM-EDX chemical analysis of Zr in the ceramic sintered body of Example 3. </p> <p> Figure 13C shows STEM-EDX chemical analysis of Ti in the ceramic sintered body of Example 3. </p> <p> Figure 13D shows STEM-EDX chemical analysis of Sr in the ceramic sintered body of Example 3. </p> <p> Figure 14A shows a selected area diffraction (SAD) pattern obtained from the first ceramic phase in the ceramic sintered body of Example 3 (particles exhibiting Sr, Ca, and Ti in STEM-EDX chemical analysis). </p> <p> Figure 14B shows a selected area diffraction (SAD) pattern obtained from the second ceramic phase in the ceramic sintered body of Example 3 (particles exhibiting Zr and Ti in STEM-EDX chemical analysis). </p> <p> Figure 15 shows an X-ray diffraction (XRD) pattern of the ceramic sintered body in Example 3. </p> <P> Figure 16A shows the relative dielectric constant of the ceramic sintered body of Example 3 under several different reoxidation conditions. </p> <p> Figure 16B shows the dielectric loss of the ceramic sintered body of Example 3 under several different reoxidation conditions. </p> <P> Figure 16C shows the electrical resistivity of the ceramic sintered body of Example 3 under several different reoxidation conditions. </p> <p> Figure 17 shows a schematic manufacturing flow of Example 4. </p> <P> Figure 18A shows a high angle annular dark field (HAADF) image of the ceramic sintered body of Example 4. </p> <P> Figure 18B shows STEM-EDX chemical analysis of Ca in the ceramic sintered body of Example 4. </p> <P> Figure 18C shows STEM-EDX chemical analysis of Ti in the ceramic sintered body of Example 4. </p> <P> Figure 18D shows STEM-EDX chemical analysis of Zr in the ceramic sintered body of Example 4. </p> <P> Figure 18E shows STEM-EDX chemical analysis of Sr in the ceramic sintered body of Example 4. </p> <p> Figure 19A shows a selected area diffraction (SAD) pattern obtained from the first ceramic phase in the ceramic sintered body of Example 4 (particles exhibiting Sr and Ti in STEM-EDX chemical analysis). </p> <p> Figure 19B shows a selected area diffraction (SAD) pattern obtained from the second ceramic phase in the ceramic sintered body of Example 4 (particles exhibiting Ca, Zr, and Ti in STEM-EDX chemical analysis). </p> <p>Figure 19C shows (011) CaZrTiO   <sub>7 </sub>Selected area electronic diffraction (SAED) simulation map.   </p> <p> Figure 20 shows an X-ray diffraction (XRD) pattern of the ceramic sintered body in Example 4. </p> <P> Figure 21A shows the relative dielectric constant of the ceramic sintered body of Example 4 under several different reoxidation conditions. </p> <P> Figure 21B shows the dielectric loss of the ceramic sintered body of Example 4 under several different reoxidation conditions. </p> <P> Figure 21C shows the electrical resistivity of the ceramic sintered body of Example 4 under several different reoxidation conditions. </p> </description-of-drawings> <bio-deposit /> <sequence-list-text />

Claims (11)

一種被動元件,包含一陶瓷燒結體,該陶瓷燒結體包含一半導體陶瓷相(semiconductor ceramic phase)分散於一介電陶瓷相(dielectric ceramic phase),其中該半導體陶瓷相及該介電陶瓷相共同形成一逾滲複合體(percolative composite),且該半導體陶瓷相的體積分率接近且低於一逾滲閾值(percolation threshold)。 A passive component comprising a ceramic sintered body comprising a semiconductor ceramic phase dispersed in a dielectric ceramic phase, wherein the semiconductor ceramic phase and the dielectric ceramic phase together form A percolative composite, and the volume fraction of the semiconductive ceramic phase is close to and below a percolation threshold. 一種陶瓷燒結體,包含一半導體陶瓷相分散於一介電陶瓷相,其中該半導體陶瓷相及該介電陶瓷相共同形成一逾滲複合體,且該半導體陶瓷相的體積分率接近且低於一逾滲閾值,該半導體陶瓷相的體積分率低於該逾滲閾值約0.05%至約20%。 A ceramic sintered body comprising a semiconductor ceramic phase dispersed in a dielectric ceramic phase, wherein the semiconductor ceramic phase and the dielectric ceramic phase together form a percolation composite, and the volume fraction of the semiconductor ceramic phase is close to and lower than A percolation threshold, the volume fraction of the semiconducting ceramic phase is from about 0.05% to about 20% below the percolation threshold. 一種陶瓷燒結體,包含一半導體陶瓷相分散於一介電陶瓷相,其中該半導體陶瓷相及該介電陶瓷相共同形成一逾滲複合體,且該半導體陶瓷相的體積分率接近且低於一逾滲閾值,該半導體陶瓷相的體積分率為該逾滲閾值的約0.999倍至約0.33倍。 A ceramic sintered body comprising a semiconductor ceramic phase dispersed in a dielectric ceramic phase, wherein the semiconductor ceramic phase and the dielectric ceramic phase together form a percolation composite, and the volume fraction of the semiconductor ceramic phase is close to and lower than A percolation threshold, the volume fraction of the semiconducting ceramic phase is from about 0.999 to about 0.33 times the percolation threshold. 如請求項2或3之陶瓷燒結體,其中該介電陶瓷相之材料選自由以下所組成之群組:CaZrTi2O7(鈣鈦鋯石)、CaZrO3、SrZrO3、BaZrO3、TiO2(金紅石)、ZrO2及其固體溶液。 The ceramic sintered body of claim 2 or 3, wherein the material of the dielectric ceramic phase is selected from the group consisting of CaZrTi 2 O 7 (calcium titanium zircon), CaZrO 3 , SrZrO 3 , BaZrO 3 , TiO 2 (rutile), ZrO 2 and its solid solution. 如請求項2或3之陶瓷燒結體,其中該半導體陶瓷相的材料選自由鈣 鈦礦材料及還原之TiO2(金紅石)所組成之群組。 The ceramic sintered body of claim 2 or 3, wherein the material of the semiconductive ceramic phase is selected from the group consisting of a perovskite material and reduced TiO 2 (rutile). 如請求項5之陶瓷燒結體,其中該鈣鈦礦材料選自由以下所組成之群組:鈦酸鍶(SrTiO3)、鈦酸鋇(BaTiO3)、鈦酸鈣(CaTiO3)、鈦酸鎳(NiTiO3)、鈦酸錳(MnTiO3)、鈦酸鈷(CoTiO3)、鈦酸銅(CuTiO3)、鈦酸鎂(MgTiO3)及其錯合物。 The ceramic sintered body of claim 5, wherein the perovskite material is selected from the group consisting of strontium titanate (SrTiO 3 ), barium titanate (BaTiO 3 ), calcium titanate (CaTiO 3 ), and titanic acid. Nickel (NiTiO 3 ), manganese titanate (MnTiO 3 ), cobalt titanate (CoTiO 3 ), copper titanate (CuTiO 3 ), magnesium titanate (MgTiO 3 ), and complexes thereof. 如請求項2或3之陶瓷燒結體,其中該半導體陶瓷相摻雜一添加劑。 The ceramic sintered body of claim 2 or 3, wherein the semiconductor ceramic phase is doped with an additive. 如請求項7之陶瓷燒結體,其中該添加劑係為施體型(donor-type)添加劑,其選自由釔、鈮及鑭所組成之群組。 The ceramic sintered body of claim 7, wherein the additive is a donor-type additive selected from the group consisting of ruthenium, osmium and iridium. 如請求項2或3之陶瓷燒結體,其中該介電陶瓷相摻雜一添加劑。 The ceramic sintered body of claim 2 or 3, wherein the dielectric ceramic phase is doped with an additive. 如請求項9之陶瓷燒結體,其中該添加劑係為受體型(acceptor-type)添加劑,其選自由釩、鈮、鉻、錳化合物、鎂化合物、矽酸鹽化合物及氧化鋁化合物所組成之群組。 The ceramic sintered body of claim 9, wherein the additive is an acceptor-type additive selected from the group consisting of vanadium, niobium, chromium, manganese compounds, magnesium compounds, niobate compounds, and alumina compounds. Group. 一種被動元件,包含如請求項2至10任一項之陶瓷燒結體。 A passive component comprising the ceramic sintered body of any one of claims 2 to 10.
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