CN109721355B - 包含陶瓷烧结体的被动元件 - Google Patents

包含陶瓷烧结体的被动元件 Download PDF

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CN109721355B
CN109721355B CN201810946967.7A CN201810946967A CN109721355B CN 109721355 B CN109721355 B CN 109721355B CN 201810946967 A CN201810946967 A CN 201810946967A CN 109721355 B CN109721355 B CN 109721355B
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ceramic
ceramic phase
phase
sintered body
dielectric
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CN109721355A (zh
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藤本正之
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Yageo Corp
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Abstract

本发明公开了陶瓷烧结体及包含其的被动元件。具体地，本发明提供一种陶瓷烧结体，其具有较佳的介电常数。在本发明的某些实施例中，该陶瓷烧结体包含一半导体陶瓷相分散于一介电陶瓷相中，其中该半导体陶瓷相及该介电常数相共同形成一逾渗复合体，且该半导体陶瓷相的体积分率接近且低于一逾渗阈值。

Description

包含陶瓷烧结体的被动元件
技术领域
本发明涉及一种陶瓷烧结体(ceramic sintered body)及包含其的被动元件(passive component)，特别是一种具有较佳介电常数(dielectric constant)的陶瓷烧结体，及包含该陶瓷烧结体的被动元件。
背景技术
诸如电容器(capacitor)的被动元件通常由介电材料(dielectric material)制成。一般而言，电容器的电容(capacitance)与制成电容器的介电材料的介电常数有关。亦即，介电材料的介电常数较高使得电容器的电容较高。由于理想的电容器应具有较小的尺寸及较高的电容，故需要提供介电常数较高的材料。
发明内容
本发明提供一种被动元件，其包含具有较佳的介电常数的陶瓷烧结体，其中该被动元件为一电阻器、一电容器、一电感器或一变压器。
在本发明的某些实施例中，该陶瓷烧结体包含一半导体陶瓷相(semiconductorceramic phase)分散于一介电陶瓷相(dielectric ceramic phase)中，其中该半导体陶瓷相及该介电陶瓷相共同形成一逾渗复合体(percolative composite)，且该半导体陶瓷相的体积分率(volume fraction)接近且低于一逾渗阈值(percolation threshold)。
附图说明
图1示意性说明根据本发明的一些实施例的陶瓷烧结体的微观结构(microstructure)。图1中符号简单说明：11半导体陶瓷相；12介电陶瓷相。
图2展示实施例1的示意性制造流程。
图3A展示实施例1中的陶瓷烧结体的高角度环形暗场(high-angle annulardark-field，HAADF)图像。
图3B展示对实施例1的陶瓷烧结体中的Sr的STEM-EDX化学分析。
图3C展示对实施例1的陶瓷烧结体中的Ca的STEM-EDX化学分析。
图3D展示对实施例1的陶瓷烧结体中的Ti的STEM-EDX化学分析。
图3E展示对实施例1的陶瓷烧结体中的Zr的STEM-EDX化学分析。
图4A展示自实施例1的陶瓷烧结体中的第一陶瓷相(在STEM-EDX化学分析中呈现Sr、Ca及Ti的较亮的粒子)获得的选区电子绕射(selected area electron diffraction，SAED)图谱。
图4B展示自实施例1的陶瓷烧结体中的第二陶瓷相(在STEM-EDX化学分析中呈现Ti及Zr的较暗的粒子)获得的选区电子绕射(SAED)图谱。
图5展示实施例1中的陶瓷烧结体的X光绕射(x-ray diffraction，XRD)图谱。
图6A展示实施例1中的陶瓷烧结体在几种不同再氧化条件(re-oxidationconditions)下的相对介电常数(relative dielectric constant)。
图6B展示实施例1中的陶瓷烧结体在几种不同再氧化条件下的介电损耗(dielectric loss)。
图6C展示实施例1中的陶瓷烧结体在几种不同再氧化条件下的电阻率(resistivity)。
图7展示实施例2的示意性制造流程。
图8A展示实施例2中的陶瓷烧结体的高角度环形暗场(HAADF)图像。
图8B展示对实施例2的陶瓷烧结体中的Sr的STEM-EDX化学分析。
图8C展示对实施例2的陶瓷烧结体中的Ca的STEM-EDX化学分析。
图8D展示对实施例2的陶瓷烧结体中的Ti的STEM-EDX化学分析。
图8E展示对实施例2的陶瓷烧结体中的Zr的STEM-EDX化学分析。
图9A展示自实施例2的陶瓷烧结体中的第一陶瓷相(在STEM-EDX化学分析中呈现Sr、Ca及Ti的粒子)获得的选区电子绕射(SAED)图谱。
图9B展示自实施例2的陶瓷烧结体中的第二陶瓷相(在STEM-EDX化学分析中呈现Ti及Zr的粒子)获得的选区电子绕射(SAED)图谱。
图9C展示自实施例2的陶瓷烧结体中的第三陶瓷相(在STEM-EDX化学分析中呈现Ca、Zr及Ti的粒子)获得的选区电子绕射(SAED)图谱。
图9D展示(150)CaZrTiO7(钙钛锆石，zirconolite)的选区电子绕射(SAED)的模拟图谱(simulation pattern)。
图10展示实施例2中的陶瓷烧结体的X光绕射(XRD)图谱。
图11A展示实施例2中的陶瓷烧结体在几种不同再氧化条件下的相对介电常数。
图11B展示实施例2中的陶瓷烧结体在几种不同再氧化条件下的介电损耗。
图11C展示实施例2中的陶瓷烧结体在几种不同再氧化条件下的电阻率。
图12展示实施例3的示意性制造流程。
图13A展示实施例3中的陶瓷烧结体的高角度环形暗场(HAADF)图像。
图13B展示对实施例3的陶瓷烧结体中的Zr的STEM-EDX化学分析。
图13C展示对实施例3的陶瓷烧结体中的Ti的STEM-EDX化学分析。
图13D展示对实施例3的陶瓷烧结体中的Sr的STEM-EDX化学分析。
图14A展示自实施例3的陶瓷烧结体中的第一陶瓷相(在STEM-EDX化学分析中呈现Sr、Ca及Ti的粒子)获得的选区绕射(selected area diffraction，SAD)图谱。
图14B展示自实施例3的陶瓷烧结体中的第二陶瓷相(在STEM-EDX化学分析中呈现Zr及Ti的粒子)获得的选区绕射(SAD)图谱。
图15展示实施例3中的陶瓷烧结体的X光绕射(XRD)图谱。
图16A展示实施例3中的陶瓷烧结体在几种不同再氧化条件下的相对介电常数。
图16B展示实施例3中的陶瓷烧结体在几种不同再氧化条件下的介电损耗。
图16C展示实施例3中的陶瓷烧结体在几种不同再氧化条件下的电阻率。
图17展示实施例4的示意性制造流程。
图18A展示实施例4中的陶瓷烧结体的高角度环形暗场(HAADF)图像。
图18B展示对实施例4的陶瓷烧结体中的Ca的STEM-EDX化学分析。
图18C展示对实施例4的陶瓷烧结体中的Ti的STEM-EDX化学分析。
图18D展示对实施例4的陶瓷烧结体中的Zr的STEM-EDX化学分析。
图18E展示对实施例4的陶瓷烧结体中的Sr的STEM-EDX化学分析。
图19A展示自实施例4的陶瓷烧结体中的第一陶瓷相(在STEM-EDX化学分析中呈现Sr及Ti的粒子)获得的选区绕射(selected area diffraction，SAD)图谱。
图19B展示自实施例4的陶瓷烧结体中的第二陶瓷相(在STEM-EDX化学分析中呈现Ca、Zr及Ti的粒子)获得的选区绕射(SAD)图谱。
图19C展示(011)CaZrTiO7的选区电子绕射(SAED)的模拟图谱。
图20展示实施例4中的陶瓷烧结体的X光绕射(XRD)图谱。
图21A展示实施例4中的陶瓷烧结体在几种不同再氧化条件下的相对介电常数。
图21B展示实施例4中的陶瓷烧结体在几种不同再氧化条件下的介电损耗。
图21C展示实施例4中的陶瓷烧结体在几种不同再氧化条件下的电阻率。
具体实施方式
理论上，铁电材料(ferroelectric materials)被预期仅在接近铁电－顺电相变(ferroelectric-paraelectric phase transition)的非常窄的温度范围内可具有极高介电常数。然而，已知获得具有可接受的介电常数的电容器的方法是通过多层结构来实现。特定而言，其是将多个铁电陶瓷材料薄层置放于多个导电层之间，以形成多层陶瓷电容器(multilayered ceramic capacitor，MLCC)。在现有MLCC中，铁电陶瓷层的厚度为影响其电容的关键因素。通过使用较小颗粒尺寸(grain size)的铁电陶瓷材料减小铁电陶瓷层的厚度，可增大MLCC的电容。然而，由于所谓的“尺寸效应(Size-Effect)”，颗粒尺寸较小的铁电陶瓷材料却呈现较小介电常数。通过更薄的电介质层得到MLCC的较高电容的现有准则理论上将陷入僵局。
获得具有可接受的介电常数的电容器的另一种方法是通过逾渗复合体实现，其可根据逾渗理论进行解释。一般而言，“逾渗理论(percolation theory)”是描述随机图(random graph)中连接丛集(connected cluster)的行为。在电容器相关的技术领域中，逾渗理论可用于描述导电粒(conductive grains)形成电流路径以穿过由绝缘粒(insulating grains)所填充的空间的情况。在导电粒与绝缘粒混合时，导电粒足以形成电流路径以穿过由绝缘粒所填充的空间的最低体积分率定义为“逾渗阈值”。换言之，在导电粒的体积分率达至逾渗阈值时，一部分导电粒彼此连接，形成电流路径以穿过由绝缘粒所填充的空间。导电粒的体积分率增加致使复合体所显现的介电常数增加。在导电粒的体积分率恰好处于逾渗阈值之前(此情况意谓逾渗阈值前的最高导电粒体积分率)时，复合物呈现巨大的介电常数。逾渗阈值幂次律(percolative threshold power law)描述如下。
Figure GDA0003040182230000041
前述逾渗复合体分别将金属材料及介电陶瓷材料用作导电粒及绝缘粒。细小的金属粒具有大的表面能(surface energy)。在与介电陶瓷粒混合时，金属粒往往会聚结(agglomerate)在一起，因此无法均匀分散于混合物中。当混合过程以大规模进行时，金属粒的聚集情形甚至可能更为严重。此外，因为金属粒(诸如镍)的熔点通常低于陶瓷粒的熔点，所以在烧结过程中金属粒会早于绝缘粒熔化，导致烧结过程中巨大的粒生长(异常晶粒生长，abnormal grain growth)。可使用由具有高熔点的贵金属(诸如铂)制成的金属粒以避免烧结过程期间的异常晶粒生长，同时成本可能相应地增加。鉴于以上，此类逾渗复合体无法满足工业要求。
为至少解决以上问题，本发明提供一种陶瓷烧结体，其包含半导体陶瓷相分散于介电陶瓷相中，其中半导体陶瓷相及介电陶瓷相共同形成逾渗复合体，且半导体陶瓷相的体积分率接近且低于逾渗阈值。通过使用半导体陶瓷材料代替前述金属材料作为导电相，可避免导电相的聚集及异常晶粒生长。因此，可成功制造出具有良好介电常数的此类逾渗复合体。
如本文中所使用，术语“大致”、“实质上”、“实质的”及“约”用以描述及考虑小变化。当与事件或情形结合使用时，术语可指事件或情形明确发生的情况以及事件或情形极近似于发生的情况。举例而言，当结合数值使用时，这些术语可指小于或等于彼数值的±10％的变化范围，诸如小于或等于±5％、小于或等于±4％、小于或等于±3％、小于或等于±2％、小于或等于±1％、小于或等于±0.5％、小于或等于±0.1％、或小于或等于±0.05％。
另外，有时在本文中按范围格式呈现量、比率及其他数值。应理解，此类范围格式为便利及简洁起见而使用，且应灵活地理解为不仅包括明确指定为范围限制的数值，且亦包括涵盖于彼范围内的所有个别数值或子范围，如同明确指定每一数值及子范围一般。
在本发明中，术语“陶瓷烧结体”是指一烧结体，其是由陶瓷材料制成。该陶瓷烧结体可由两种或更多种陶瓷材料烧结而成。举例而言，该陶瓷烧结体可由复数陶瓷粒(grains)烧结而成，且这些陶瓷粒共同结合而形成一单体结构(monolithic structure)。
在本发明中，术语“相”是指空间区域，在整个该空间区域中的材料的所有物理性质基本上为均匀的。物理性质的示例包括但不限于密度、折射率、磁化强度、导电性、介电常数及化学组成。相优选为物理上及化学上均匀的材料区域，且在物理上区隔(physicallydistinct)。举例而言，在本发明的一些实施例中，陶瓷烧结体包括分散于介电陶瓷相中的半导体陶瓷相。半导体陶瓷相实质上由具有一电导率(conductivity)的材料制成，该材料在半导体陶瓷相内基本上是均匀的。类似地，介电陶瓷相实质上由另一种具有一电导率的材料制成，该材料在介电陶瓷相内基本上是均匀的。此外，半导体陶瓷相的电导率不同于介电陶瓷相的电导率。
在本发明的一些实施例中，在与半导体陶瓷相比较时，介电陶瓷相更类似于连续相(continuous phase)。另一方面，半导体陶瓷相更类似于分散于介电陶瓷相中的分散相(dispersed phase)。出于说明的目的，图1展示根据本发明的一些实施例的陶瓷烧结体的微观结构。陶瓷相11分散于介电陶瓷相12中，形成逾渗复合体。值得注意的是，根据本发明的一些实施例的陶瓷烧结体可包括超过一种半导体陶瓷相和/或超过一种介电陶瓷相。
在本发明的某些实施例中，该介电陶瓷相是指由具有介电性质的陶瓷材料所构成的相。举例而言，该介电陶瓷相距有高于约108Ω-cm的电阻率。
在本发明的某些实施例中，该半导体陶瓷相是指由具有半导体性质的陶瓷材料所组成的相。举例而言，该半导体陶瓷相可为n型半导体，且其电导率高于约0.5S/m，或高于约1.0S/m。
在本发明的一些实施例中，逾渗电容(percolation capacitance)是指半导体陶瓷相的最高体积分率，其恰好在足以形成电流路径穿过介电陶瓷相之前。逾渗阈值是指半导体陶瓷相恰好足以形成电流路径穿过介电陶瓷相的体积分率。逾渗阈值的确切数值可视半导体陶瓷相及介电陶瓷相的材料、材料的颗粒尺寸及陶瓷烧结体的烧结温度而定。逾渗阈值可通过测量或模拟而获得，其可为本领域技术人员所理解。
在本发明中，该逾渗复合体的半导体陶瓷相的体积分率非常接近逾渗阈值。逾渗复合体中的半导体陶瓷相的体积分率可低于逾渗阈值数个百分点。
陶瓷烧结体(包含介电陶瓷相及半导体陶瓷相)的介电常数在逾渗阈值处发散(diverge)。因此，由于介电陶瓷相及半导体陶瓷相共同形成逾渗结构(percolativestructure)，且半导体陶瓷相的体积分率非常接近逾渗阈值，故陶瓷烧结体可具有提升的介电常数。亦即，在半导体陶瓷相的体积分率在接近逾渗阈值的区域中增加时，陶瓷烧结体的介电常数以指数比例增加。
在一些实施例中，逾渗复合体中的半导体陶瓷相的体积分率可低于逾渗阈值约0.05％至约20％。举例而言，若在特定条件下的逾渗阈值为30％，则在相同条件下的亚逾渗复合体(sub-percolative composite)中的半导体陶瓷相的体积分率可为约30-0.05％至约30-20％。在一些实施例中，逾渗复合体中的半导体陶瓷相的体积分率可为低于逾渗阈值约0.05％至约10％、约0.05％至约5％、或约0.05％至约3％。在本发明的一些实施例中，半导体陶瓷相的体积分率接近且低于逾渗阈值。在一些实施例中，半导体陶瓷相的体积分率可为逾渗阈值的精确值的约0.999倍至约0.33倍。举例而言，若在特定条件下的逾渗阈值为30％，则在相同条件下的亚逾渗复合体中的半导体陶瓷相的体积分率可为约(30×0.999)％至约(30×0.33)％。在一些实施例中，半导体陶瓷相的体积分率可为逾渗阈值的精确值的约0.999倍至约0.65倍、约0.999倍至约0.75倍、约0.999倍至约0.85倍、或约0.999倍至约0.9倍。
在某些实施例中，举例而言，在预定情况下的逾渗阈值可被计算。用以计算预定情况下的逾渗阈值的模型至少可见于C.D.Lorenz和R.M.Ziff,J.Chem.Phys.114 3659(2001),S.Kirkpatrick,Rev.Mod.Phys.45 574(1973),D.Stauffer,Phys Rep.54 1(1979),以及T.G.Castner等,Phys.Rev.Lett.34 1627(1975)等文献中。
亚逾渗复合体中的半导体陶瓷相的体积分率的确切数值在很大程度上可视半导体陶瓷相及介电陶瓷相的粒子尺寸及其几何分布而定。举例而言，若介电陶瓷相的颗粒尺寸比半导体陶瓷相的颗粒尺寸小得多，且若其非常均匀地分布，则半导体陶瓷相的体积分率可能较大。另一方面，若介电陶瓷相的颗粒尺寸比半导体陶瓷相的颗粒尺寸大得多，且若其在几何上分布良好，则半导体陶瓷相的体积分率可能较小。然而，在一些实施例中，若半导体陶瓷相的颗粒尺寸为约3.0微米，且介电陶瓷相的颗粒尺寸为约0.2微米，则半导体陶瓷相的体积分率优选为约5％至约60％；更优选为约15％至约40％；再更优选为约20％至约35％。若半导体陶瓷相的颗粒尺寸为约1.0微米，且介电陶瓷相的颗粒尺寸为约0.2微米，则半导体陶瓷相的体积分率优选为约5％至约60％，更优选为约15％至约40％，再更优选为约25％至约35％。且若半导体陶瓷相的颗粒尺寸为约0.2微米，且介电陶瓷相的颗粒尺寸为约0.1微米，则半导体陶瓷相的体积分率为5％至55％，更优选为15％至35％，再更优选为约20％至30％。然而，在一些实施例中，半导体陶瓷相的形状可显著影响逾渗阈值的确切数值。
举例而言，根据本发明的一些实施例的介电陶瓷相的材料包括CaZrTi2O7(钙钛锆石，zirconolite)、CaZrO3、SrZrO3、BaZrO3、TiO2(金红石，rutile)、ZrO2，或其固体溶液(solid solution，例如，其固体溶液可包括Ti1-xZrxO2，其中x为0与1之间的合理数；或Ca1- xSrxZrO3，其中x为0与1之间的合理数)。在介电陶瓷相包括钙钛锆石的情况下，可帮助介电陶瓷相明确地与半导体陶瓷相区隔。
举例而言，根据本发明的一些实施例的半导体陶瓷相的材料包括钙钛矿(perovskite)材料。如本领域技术人员可容易地理解，“钙钛矿材料”是指一类化合物，其具有相同类型的晶体结构XIIA2+VIB4+X2- 3。“A”及“B”为两个尺寸差别极大的阳离子，且“X”为键结至两者的阴离子。“A”原子比“B”原子大。理想的立方对称结构具有6配位的“B”阳离子，其由阴离子的八面体包围的；及12配位立方八面体的“A”阳离子。在本发明的一些实施例中，钙钛矿材料包括钛酸锶(SrTiO3)、钛酸钡(BaTiO3)、钛酸钙(CaTiO3)、钛酸镍(NiTiO3)、钛酸锰(MnTiO3)、钛酸钴(CoTiO3)、钛酸铜(CuTiO3)、钛酸镁(MgTiO3)或其错合物。优选地，钙钛矿材料可呈还原态，诸如由例如还原气氛还原。在本发明的一些实施例中，半导体陶瓷相的材料包括还原的TiO2(金红石)，亦即，TiO2-x；缺氧状态(oxygen deficient state)半导体。还原的TiO2(金红石)可由例如还原气氛还原。
尽管在钙钛矿材料、CaZrTi2O7、TiO2(金红石)及ZrO2当中存在晶格不匹配(lattice mismatch)，但因为在烧结过程期间Ti会在钙钛矿材料(其中XIIA2+VIB4+X2- 3的“B”为Ti)与CaZrTi2O7、TiO2(金红石)之间相互扩散(mutual diffusion)，且Zr会在CaZrTi2O7、CaZrO3、SrZrO3、BaZrO3与ZrO2之间相互扩散，所以可解决此类晶格不匹配的问题。因此，在上列材料用作半导体陶瓷相及介电陶瓷相时，其可烧结在一起而无开裂(crack)、断裂(rupture)、脆性破坏(brittle failure)及破裂(fracture)，从而提供陶瓷烧结体良好的结构强度。
此外，在本发明的一些实施例中，介电陶瓷相进一步掺杂(doped)另一种添加剂(additive)。举例而言，添加剂为受体型(acceptor-type)添加剂，诸如V、Nb、Cr。此外，添加剂可为锰化合物、镁化合物、硅酸盐化合物、钨化合物或氧化铝化合物以提高介电性质。在本发明的一些实施例中，介电陶瓷相可进一步掺杂掺杂剂(dopant)，诸如MnO2、MgO或WO3。此类掺杂剂可增强介电陶瓷相的介电性质，例如，提高介电陶瓷相的电阻率及可靠性。
类似地，在本发明的一些实施例中，半导体陶瓷相进一步掺杂添加剂。举例而言，添加剂为施体型(donor-type)添加剂，诸如Y、Nb或La，因此在半导体陶瓷相中形成Y2O3、Nb2O5、La2O3。此类添加剂可增强半导体陶瓷相的半导性质，例如，提高半导体陶瓷相的电导率。掺杂有施体添加剂且经还原的钙钛矿化合物可形成高施体密度n型半导材料(highdonor density n-type semiconducting material)。
本发明进一步提供一种被动元件，其包含前述陶瓷烧结体。在本发明中，被动元件为除其所连接的可用交流电(alternating current，AC)电路以外不需要能量来操作的电子元件。被动元件不具功率增益(power gain)且非为能量源(energy source)。举例而言，被动元件包括两端元件(two-terminal components)，诸如电阻器(resistors)、电容器、电感器(inductors)及变压器(transformers)。
本发明可涉及一种制造上述陶瓷烧结体的方法。该方法包含混合半导体陶瓷粒及介电陶瓷粒以形成一混合物，以及于中性气氛(neutral atmosphere)下烧结该混合物。
在本发明的一些实施例中，半导体陶瓷粒由与上文所描述的半导体陶瓷相相同的材料制成。然而，值得注意的是，金红石及锐钛矿(anatase)结构两者中均可提供TiO2颗粒。半导体陶瓷粒的尺寸可为约0.1微米至约5微米，优选为约0.2微米至约2微米。类似地，介电陶瓷粒由与上文所描述的介电相相同的材料制成。介电陶瓷粒的尺寸可为约0.1微米至约5微米，优选为约0.2微米至约2微米。半导体陶瓷粒与介电陶瓷粒的混合可通过例如珠磨机(bead miller)来达成。混合后，在诸如N2、He、Ar等的中性气氛下烧结混合物。烧结温度可为例如约1100℃至约1500℃。
在本发明的一些实施例中，该方法进一步包括混合半导体粒、介电粒及粘合剂(binder)于溶剂中，及在烧结前移除粘合剂及溶剂。举例而言，粘合剂包括聚乙烯醇(polyvinyl alcohol，PVA)、聚丙烯酸酯(polyacrylate)及乙基纤维素(ethylcellulose)。溶剂包括乙醇、甲苯(toluene)、甲基乙基酮(methyl ethyl ketone，MEK)、二甘醇单丁醚(diethylene glycol monobutyl ether，BC)及丁基卡必醇乙酸酯(butylcarbitol acetate，BCA)以及其组合。亦可添加其他烧结助剂，诸如SiO2、GeO2、B2O3等，以增大烧结密度且降低烧结温度。溶剂是指用于混合半导体陶瓷粒及介电陶瓷粒的液体。优选地，溶剂不与半导体陶瓷粒、介电陶瓷粒和/或粘合剂反应。举例而言，溶剂包括醇、醚等。
下列实施例仅用于说明本发明，但是本发明的范围并不以此为限。
实施例1：包含TiO2-ZrO2固体溶液作为介电陶瓷相及SrTiO3-CaTiO3固体溶液作为半导体陶瓷相的陶瓷烧结体
图2展示实施例1的示意性制造流程。将0.075摩尔碳酸锶(SrCO3)、0.075摩尔碳酸钙(CaCO3)及0.15摩尔TiO2(金红石)以珠磨机(氧化锆珠粒，直径为0.1mm)在乙醇中混合。混合后在氮气流中干燥混合粉末。将所得混合物进行干磨(dry-ground)并在1,000℃下于N2+H2(95％+5％)气流中煅烧5小时，以获得黑色半导体(Sr0.5Ca0.5)TiO3粉末。将0.5摩尔氧化锆(ZrO2)及0.5摩尔氧化钛(TiO2)(金红石)添加至经干磨的粉末中且再次由珠磨机混合。
将100重量份由此形成的粉末混合于乙醇中并进行研磨，且随后与15重量份PVA粘合剂、0.1重量份SiO2及0.05重量份Al2O3混合以形成研磨浆(slurry)。使用涂布机将研磨浆涂布于聚对苯二甲酸乙二酯(polyethylene terephthalate)载带上以形成生胚片(greensheet)。冲压生胚片以形成复数个胚料(pellet)。在高于0.015atm的氧气分压及550℃的温度下将胚料加热60分钟以移除有机粘合剂。随后于含有N2的气氛下在1250℃的温度下将胚料烧结30分钟以形成陶瓷烧结体。以上条件的理论逾渗阈值为约28.95％，且陶瓷烧结体中的半导体陶瓷相(SrTiO3-CaTiO3)的体积分率为约27％。为验证烧结陶瓷体中的半导体陶瓷粒及介电陶瓷粒的均匀混合状态，在测量介电性质之前分别将样品在800℃、900及1000℃下于空气中再氧化(re-oxidized)30分钟。在再氧化期间，半导体陶瓷粒可通过晶界(grainboundary)处的氧气扩散，自晶界区开始氧化。同时，在介电陶瓷粒中，同样会于晶界处发生氧气扩散。适当的再氧化条件可增强烧结陶瓷体的性质。然而，在较高再氧化温度下，氧气扩散不仅会于晶界处发生，亦会于颗粒的整体(bulk of grain)发生。强烈的氧气扩散导致半导体陶瓷粒降解(degradation)，因此降低其电导率。所得烧结体自两侧抛光100微米深，以沉积用于介电测量的Au电极。
图3A展示实施例1中的陶瓷烧结体的高角度环形暗场(HAADF)图像。图像的对比度差异显示至少一第一陶瓷相(较亮的粒子)及第二陶瓷相(较暗的粒子)。此外，STEM-EDX化学分析(图3B至图3E)证明第一陶瓷相(Sr-Ca-Ti)及第二陶瓷相(Ti-Zr)的存在。
图4A展示自第一陶瓷相(在STEM-EDX化学分析中呈现Sr、Ca及Ti的较亮的粒子)获得的选区电子绕射图谱(SAED)。结果显示第一陶瓷相(较亮的粒子)为(213)(Sr0.5Ca0.5)TiO3。图4B展示自第二陶瓷相(在STEM-EDX化学分析中呈现Ti及Zr的较暗的粒子)获得的选区电子绕射图谱(SAED)。结果显示第二陶瓷相(较暗的粒子)为(001)TiO2(金红石)，且推论为金红石结构TiO2-ZrO2固体溶液。
图5展示实施例1中的陶瓷烧结体的XRD(X射线绕射)。数个波峰亦显示陶瓷烧结体中存在第一陶瓷相(亦即，(Sr0.5Ca0.5)TiO3相)及第二陶瓷相(亦即，金红石结构TiO2-ZrO2固体溶液相)。
图6A、图6B及图6C展示在几种不同再氧化条件下实施例1中的陶瓷烧结体的相对介电常数、介电损耗(dielectric loss)及电阻率(resistivity)。介电常数及介电损耗减小及电阻率提高表明(Sr0.5Ca0.5)TiO3半导体相的再氧化程度上升。所得烧结陶瓷体(在图6A至图6C中标记为“烧结”)的介电常数显著高于(Sr0.5Ca0.5)TiO3及TiO2-ZrO2的介电常数，且介电常数对应于再氧化温度的升高而减小。对应半导体陶瓷相((Sr0.5Ca0.5)TiO3)的氧化程度减小的介电常数显示烧结陶瓷体为亚逾渗复合体。亦即，所呈现的巨大的相对介电常数源自于其亚逾渗结构。
因此，以上分析结果展示实施例1中的陶瓷烧结体包括半导体陶瓷相(亦即，(Sr0.5Ca0.5)TiO3相)分散于介电陶瓷相(亦即，金红石结构TiO2-ZrO2固体溶液相)中，其中半导体陶瓷相及介电陶瓷相共同形成亚逾渗复合体。
实施例2：包含TiO2-ZrO2固体溶液作为介电陶瓷相及SrTiO3-CaTiO3固体溶液作为半导体陶瓷相的陶瓷烧结体
图7展示实施例2的示意性制造流程。将0.11摩尔碳酸锶(SrCO3)、0.046摩尔碳酸钙(CaCO3)及0.154摩尔TiO2(金红石)以珠磨机(氧化锆珠粒，直径为0.1mm)在乙醇中混合。混合后在氮气流中干燥混合粉末。将所得混合物进行干磨并在1,100℃下于N2+H2(95％+5％)气流中煅烧5小时，以获得黑色半导体(Sr0.7Ca0.3)TiO3粉末。将0.7摩尔氧化锆(ZrO2)及0.3摩尔氧化钛(TiO2)(金红石)添加至经干磨的粉末中且再次由珠磨机混合。
将100重量份由此形成的粉末于包含20％MEK及80％BCA(v/v)的溶液中进行研磨，且随后与15重量份乙基纤维素、0.3重量份CaSiO3、0.1重量份GeO2及0.05重量份Al2O3混合以形成研磨浆。使用涂布机将研磨浆涂布于聚对苯二甲酸乙二酯(PET)载带上以形成生胚片。冲压生胚片以形成复数个胚料。在高于0.015atm的氧气分压及450℃的温度下将胚料加热60分钟以移除粘合剂。随后于含有N2的气氛下在1300℃的温度下将胚料烧结30分钟以形成陶瓷烧结体。以上条件的理论逾渗阈值为约28.95％，且陶瓷烧结体中的半导体陶瓷相(SrTiO3-CaTiO3)的体积分率为约27.3％。为验证烧结陶瓷体中的半导体陶瓷粒及介电陶瓷粒的均匀混合状态，在测量介电性质之前分别将样品在800℃、900及1000℃下于空气中再氧化30分钟。所得烧结体自两侧抛光100微米深，以沉积用于介电测量的Au电极。
图8A展示实施例2中的陶瓷烧结体的高角度环形暗场(HAADF)图像。图像的对比度差异显示数个陶瓷相。此外，STEM-EDX化学分析(图8B至图8E)证明第一陶瓷相(Sr-Ca-Ti)、第二陶瓷相(Ti-Zr)及第三陶瓷相(Ca-Zr-Ti)的存在。
图9A展示自第一陶瓷相(在STEM-EDX化学分析中呈现Sr、Ca及Ti的粒子)获得的选区电子绕射图谱(SAED)。结果显示第一陶瓷相为(212)(Sr0.7Ca0.3)TiO3。图9B展示自第二陶瓷相(在STEM-EDX化学分析中呈现Ti及Zr的粒子)获得的选区电子绕射图谱(SAED)。结果显示第二陶瓷相为(311)TiO2(金红石)，且推论为金红石结构TiO2-ZrO2固体溶液。图9C展示自第三陶瓷相(在STEM-EDX化学分析中呈现Ca、Zr及Ti的粒子)获得的选区电子绕射图谱(SAED)。比对图9D所示的(150)CaZrTiO7(钙钛锆石)的模拟图谱结果，相信第三陶瓷相为(150)CaZrTiO7(钙钛锆石)。
图10展示实施例2中的陶瓷烧结体的XRD(X射线绕射)。数个波峰亦显示陶瓷烧结体中存在第一陶瓷相(亦即，(Sr0.5Ca0.5)TiO3相)、第二陶瓷相(亦即，金红石结构TiO2-ZrO2固体溶液相)及第三陶瓷相(亦即，CaZrTiO7相)。
图11A、图11B及图11C展示在几种不同再氧化条件下实施例2中的陶瓷烧结体的相对介电常数、介电损耗及电阻率。介电常数及介电损耗减小及电阻率提高表明(Sr0.5Ca0.5)TiO3半导体相的再氧化程度上升。所得烧结陶瓷体(在图11A至图11C中标记为“烧结”)的介电常数显著高于(Sr0.5Ca0.5)TiO3、CaZrTiO7及TiO2-ZrO2的介电常数，且介电常数对应于再氧化温度的升高而减小。对应半导体陶瓷相((Sr0.5Ca0.5)TiO3)的氧化程度减小的介电常数显示烧结陶瓷体为亚逾渗复合体。亦即，所呈现的巨大的相对介电常数源自于其亚逾渗结构。
因此，以上分析结果展示实施例2中的陶瓷烧结体包括半导体陶瓷相(亦即，(Sr0.5Ca0.5)TiO3相)分散于介电陶瓷相(亦即，金红石结构TiO2-ZrO2固体溶液相及CaZrTiO7相)中，其中半导体陶瓷相及介电陶瓷相共同形成亚逾渗复合体。
实施例3：包含TiO2-ZrO2固体溶液作为介电陶瓷相及SrTiO3固体溶液作为半导体陶瓷相的陶瓷烧结体
图12展示实施例3的示意性制造流程。将0.25摩尔碳酸锶(SrCO3)及0.25摩尔TiO2(锐钛矿)以珠磨机(氧化锆珠粒，直径为0.1mm)在乙醇中混合。混合后在氮气流中干燥混合粉末。将所得混合物进行干磨并在1,000℃下于N2+H2(95％+5％)气流中煅烧5小时，以获得黑色半导体SrTiO3粉末。将0.5摩尔氧化锆(ZrO2)及0.5摩尔氧化钛(TiO2)(锐钛矿)添加至经干磨的粉末中且再次由珠磨机混合。
将100重量份由此形成的粉末于包含35％甲苯及65％MEK(v/v)的溶液中进行研磨，且随后与15重量份聚丙烯酸酯、0.3重量份SrSiO3、0.1重量份GeO2及0.1重量份MnO2混合以形成研磨浆。使用涂布机将研磨浆涂布于PET载带上以形成生胚片。冲压生胚片以形成复数个胚料。在高于0.015atm的氧气分压及450℃的温度下将胚料加热60分钟以移除有机粘合剂。随后于含有N2的气氛下在1300℃的温度下将胚料烧结30分钟以形成陶瓷烧结体。以上条件的理论逾渗阈值为约28.95％，且陶瓷烧结体中的半导体陶瓷相(SrTiO3)的体积分率为约27.8％。为验证烧结陶瓷体中的半导体陶瓷粒及介电陶瓷粒的均匀混合状态，在测量介电性质之前分别将样品在800℃、900及1000℃下于空气中再氧化30分钟。所得烧结体自两侧抛光100微米深，以沉积用于介电测量的Au电极。
图13A展示实施例3中的陶瓷烧结体的高角度环形暗场(HAADF)图像。图像的对比度差异显示数个陶瓷相。此外，STEM-EDX化学分析(图13B至图13D)证明第一陶瓷相(Sr-Ti)及第二陶瓷相(Ti-Zr)的存在。
图14A展示自第一陶瓷相(在STEM-EDX化学分析中呈现Sr及Ti的粒子)获得的选区电子绕射图谱(SAED)。结果显示第一陶瓷相为(112)SrTiO3。图14B展示自第二陶瓷相(在STEM-EDX化学分析中呈现Ti及Zr的粒子)获得的选区电子绕射图谱(SAED)。结果显示第二陶瓷相为(101)TiO2(金红石)，且推论为金红石结构TiO2-ZrO2固体溶液。
图15展示实施例3中的陶瓷烧结体的XRD(X射线绕射)。数个波峰亦显示陶瓷烧结体中存在第一陶瓷相(亦即，SrTiO3相)及第二陶瓷相(亦即，金红石结构TiO2-ZrO2固体溶液相)。
图16A、图16B及图16C展示在几种不同再氧化条件下实施例3中的陶瓷烧结体的相对介电常数、介电损耗及电阻率。介电常数及介电损耗减小及电阻率提高表明SrTiO3半导体相的再氧化程度上升。所得烧结陶瓷体(在图16A至图16C中标记为“烧结”)的介电常数显著高于SrTiO3及TiO2-ZrO2的介电常数，且介电常数对应于再氧化温度的升高而减小。对应半导体陶瓷相((Sr0.5Ca0.5)TiO3)的氧化程度减小的介电常数显示烧结陶瓷体为亚逾渗复合体。亦即，所呈现的巨大的相对介电常数源自于其亚逾渗结构。
实施例4：包含CaZrTi2O7固体溶液作为介电陶瓷相及SrTiO3固体溶液作为半导体陶瓷相的陶瓷烧结体
图17展示实施例4的示意性制造流程。将0.56摩尔碳酸锶(SrCO3)、0.56摩尔TiO2(锐钛矿)及0.015摩尔Y2O3以珠磨机(氧化锆珠粒，直径为0.1mm)在乙醇中混合。混合后在氮气流中干燥混合粉末。将所得混合物进行干磨并在1,000℃下于N2+H2(95％+5％)气流中煅烧5小时，以获得黑色半导体SrTiO3粉末。将1摩尔钙钛锆石(CaZrTi2O7)添加至经干磨的粉末中且再次由珠磨机混合。
将100重量份由此形成的粉末于包含甲苯及MEK的溶液中进行研磨，且随后与15重量份乙基纤维素粘合剂、0.3重量份SrSiO3、0.1重量份GeO2及0.1重量份MnO2混合以形成研磨浆。使用涂布机将研磨浆涂布于PET载带上以形成生胚片。冲压生胚片以形成复数个胚料。在高于0.015atm的氧气分压及550℃的温度下将胚料加热60分钟以移除有机粘合剂。随后于含有N2的气氛下在1300℃的温度下将胚料烧结30分钟以形成陶瓷烧结体。以上条件的理论逾渗阈值为约28.95％，且陶瓷烧结体中的半导体陶瓷相(SrTiO3)的体积分率为约28％。为验证烧结陶瓷体中的半导体陶瓷粒及介电陶瓷粒的均匀混合状态，在测量介电性质之前分别将样品在800℃、900及1000℃下于空气中再氧化30分钟。所得烧结体自两侧抛光100微米深，以沉积用于介电测量的Au电极。
图18A展示实施例4中的陶瓷烧结体的高角度环形暗场(HAADF)图像。图像的对比度差异显示数个陶瓷相。此外，STEM-EDX化学分析(图18B至图18E)证明第一陶瓷相(Sr-Ti)及第二陶瓷相(Ca-Zr-Ti)的存在。
图19A展示自第一陶瓷相(在STEM-EDX化学分析中呈现Sr及Ti的粒子)获得的选区电子绕射图谱(SAED)。结果显示第一陶瓷相为(102)SrTiO3。图19B展示自第二陶瓷相(在STEM-EDX化学分析中呈现Ca、Ti及Zr的粒子)获得的选区电子绕射图谱(SAED)。结果显示第二陶瓷相为(011)CaZrTi2O7(钙钛锆石)。比对图19C所示的(011)CaZrTiO7(钙钛锆石)的模拟图谱结果，相信第二陶瓷相为(011)CaZrTiO7(钙钛锆石)。
图20展示实施例4中的陶瓷烧结体的XRD(X射线绕射)。数个波峰亦显示陶瓷烧结体中存在第一陶瓷相(亦即，SrTiO3相)及第二陶瓷相(亦即，CaZrTi2O7(钙钛锆石))。
图21A、图21B及图21C展示在几种不同再氧化条件下实施例4中的陶瓷烧结体的相对介电常数、介电损耗及电阻率。介电常数及介电损耗减小及电阻率提高表明SrTiO3半导体相的再氧化程度上升。所得烧结陶瓷体(在图11A至图11C中标记为“烧结”)的介电常数显著高于SrTiO3及CaZrTi2O7的介电常数，且介电常数对应于再氧化温度的升高而减小。对应半导体陶瓷相(SrTiO3)的氧化程度减小的介电常数显示烧结陶瓷体为亚逾渗复合体。亦即，所呈现的巨大的相对介电常数源自于其亚逾渗结构。
尽管已参看本发明的特定实施例描述并说明本发明，但这些描述及说明并不作为限制。本领域技术人员应理解，在不脱离如由所附权利要求书所界定的本发明的真实精神及范畴的情况下，可作出各种改变且可替代等效物。说明可不必按比例绘制。归因于制造程序及容限，本发明中的艺术再现与实际设备之间可存在区别。可存在并未明确说明的本发明的其他实施例。应将本说明书及附图视为说明性而非限制性的。可作出修改，以使特定情形、材料、物质组成、方法或制造方法适应于本发明的目标、精神及范畴。所有此类修改均意欲处于此处所附的权利要求书的范畴内。尽管已参看按特定次序执行的特定操作描述本文中所揭示的方法，但应理解，在不脱离本发明的教示的情况下，可组合、再细分，或重新定序这些操作以形成等效方法。因此，除非本文中明确指示，否则操作的次序及分组并非本发明的限制。

Claims (7)

1.一种被动元件，包含一陶瓷烧结体，其中该被动元件为一电阻器、一电容器、一电感器或一变压器，该陶瓷烧结体包含一半导体陶瓷相分散于一介电陶瓷相，该陶瓷烧结体以1100℃至1500℃的烧结温度制得，其中该介电陶瓷相的材料选自：CaZrTi2O7、CaZrO3、SrZrO3、BaZrO3、TiO2、ZrO2及其固体溶液，该介电陶瓷相的尺寸为0.1微米至5微米，该半导体陶瓷相的材料选自钙钛矿材料及还原的TiO2金红石，该半导体陶瓷相的尺寸为0.1微米至5微米，该半导体陶瓷相及该介电陶瓷相共同形成一逾渗复合体，且该半导体陶瓷相的体积分率为逾渗阈值的0.999倍至0.33倍。
2.根据权利要求1所述的被动元件，其中该半导体陶瓷相的体积分率低于该逾渗阈值0.05%至20%。
3.根据权利要求1所述的被动元件，其中该钙钛矿材料选自：钛酸锶、钛酸钡、钛酸钙、钛酸镍、钛酸锰、钛酸钴、钛酸铜、钛酸镁及其化合物。
4.根据权利要求1所述的被动元件，其中该半导体陶瓷相掺杂一添加剂。
5.根据权利要求4所述的被动元件，其中该添加剂为施体型添加剂，其选自钇、铌及镧。
6.根据权利要求1所述的被动元件，其中该介电陶瓷相掺杂一添加剂。
7.根据权利要求6所述的被动元件，其中该添加剂为受体型添加剂，其选自钒、铌、铬、锰化合物、镁化合物、硅酸盐化合物及氧化铝化合物。
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