476733 五、發明說明（1) ~---- 鈦酸鋇是一種重要的陶瓷材料，長久以盔於 ，應用上一直是一種熱門的材料。雖然這種材料早 人世界大戰期間及已被發現，且被廣泛地研究發 展，t隨者科技的發展，儘管電子陶究科技日新月異，而 以鈦I鋇為主體的陶瓷體還是要符合電子輕、薄、短、小 的要求才鲍被用在電子產品上。而這些產品包括圓片 ，、積層式、半導體式等電容器、及正溫度係數熱變阻器 欽酸鎖通常是以鈣鈦礦（perovskite)，ab03，的晶體 結構存在，其中離子（Ba2+)與氧離子（02_)共同組成面 心立方結構（face center cubic )，而β4+離子（丁i4”則位 於立方體體心（body center)的位置，也就是氧離子所構 成的八面體（octahedral)的中心。隨著溫度的改變，鈦酸 鎖的躬鈦礦結構還有許多形態上的變化。在丨3 〇艺以上， 欽fee鎖疋屬於立方結構為順電性（p a r e 1 e C t r i C i t y );從 相’I:化的居4豆溫度1 3 〇 C到〇 c，則為正方晶（t e t r a g ο n a 1 ) 、”。構’到了 〇 C以下’又轉變為單斜晶（mon〇 i丨n丨c )或斜方 晶（orthorhombic);最後當溫度低於_9〇〇c時，則呈現菱 形晶（rhombohedral)結構。130°C以下的BaTi03均具鐵電性 (feirroelectricity)。鈦酸鋇的三個相轉變使原本位於立 方體中心的Ti“離子分別朝<100>方向，<110>方向及<ln> 方向偏移’於是乎每一個單位晶胞均產生一電偶極 (electric dipole)。這些電偶極能沿一定的方向順序排 列使付材料中某一區域有電偶極矩（dipole moment)的 476733 五、發明說明（2) 現象稱為自發極化（spontaneous polarizati〇n)。自發極 化所產生的極矩由於產生各極矩的分域（d〇main)方向不一 而相互抵消’因此試片之總和淨極矩為零。 在晶體結構發生變化時’介電率^別大。尤其在為 130°C附近，鈦酸鋇的介電率可高達1〇,〇〇〇以上/係為e鐵 電材料，就是這個特性，使得鈦酸鋇成為高介電率電容器 中不可或缺的材料。 當BaTi03中的Ba2+以較小（pp、Ca2+、Sr2+)離子置換 時’產生的結果是居禮相轉換溫度的移動。C#及化2+因'有 較小離子半徑，造成在八面體内Ti4+活動空間減少，而傾 向形成不扭曲的立方晶結構，因此其添加擴大立方晶順電 性區域，產生鐵電-順電（ferroelectric— paraelectric) 相轉換的居禮溫度就降低了。BaTi〇3中的Ti“可被較大離 子如Sn4+及Zr4+取代，有穩定鈣鈦礦結構、降低順電—鐵電 居里溫度之效用。隨著Zr4+置換量的增加，三項居里相轉 換溫度不再分離而互相靠近，產生變寬的介電率曲線。476733 V. Description of the invention (1) ~ ---- Barium titanate is an important ceramic material. It has been used as a helmet for a long time, and has always been a popular material in application. Although this material has been discovered during the World War and has been widely researched and developed, t follows the development of science and technology, despite the rapid development of electronic ceramics science and technology, but the ceramic body based on titanium I barium still has to meet the electronic light , Thin, short, small requirements before being used in electronic products. These products include wafers, multilayer, semiconductor and other capacitors, and positive temperature coefficient thermal rheostats. Qin acid locks usually exist in the crystal structure of perovskite, ab03, among which ions (Ba2 +) and oxygen ions (02_) collectively form a face center cubic structure, and β4 + ions (Ding i4 ”are located at the position of the body center of the cube, that is, the center of the octahedral formed by oxygen ions. With the change of temperature, there are still many morphological changes in the titanate structure of the titanate. In more than 300 arts, Qin fee lock belongs to the cubic structure and is paraelectric (pare 1 e C tri City); From the phase 'I:' at a temperature of 130 ° C to 0 ° C, it is tetrag ο na 1, ". The structure is below 0 ° C, and it is transformed into a monoclinic (monial). n 丨 c) or orthorhombic; finally, when the temperature is lower than _900c, it presents a rhombohedral structure. BaTi03 below 130 ° C all have ferroelectricity. Titanic acid The three phase transitions of barium are originally in the cube Ti "ions are shifted respectively in the direction of < 100 >, < 110 > and < ln > so that each unit cell generates an electric dipole. These electric dipoles can 476733 is arranged in a certain direction in order to have an electric dipole moment in a certain area of the material. V. Description of the invention (2) The phenomenon is called spontaneous polarization (polarization). The moments are different due to the difference in the direction of the domain of each pole moment. Therefore, the total net pole moment of the test piece is zero. When the crystal structure is changed, the dielectric constant is large. Especially it is 130. Near ° C, the dielectric constant of barium titanate can be as high as 10,000 or more / is an e-ferroelectric material, which is this characteristic, which makes barium titanate an indispensable material for high-dielectric capacitors. When Ba2 + in BaTi03 is replaced with smaller (pp, Ca2 +, Sr2 +) ions, the result is the shift of the Curie phase transition temperature. C # and H2 + have a smaller ion radius, which causes Ti4 + in the octahedron. Reduced activity space and tend to form undistorted cubic structures Therefore, its addition expands the cubic paraelectric region and reduces the courtesy temperature of the ferroelectric-paraelectric phase transition. The Ti in BaTi〇3 can be replaced by larger ions such as Sn4 + and Zr4 +. It has the effect of stabilizing the perovskite structure and reducing the paraelectric-ferroelectric Curie temperature. As the amount of Zr4 + displacement increases, the three Curie phase transition temperatures no longer separate and approach each other, resulting in a broadened dielectric curve.
Zr4+的添加造成組成擾動也是曲線變寬的原因之一。於介 電率曲線變寬上，利用Ca2+的置換也是主要的方法之三。 此外’可以利用帶正三價電荷的陽離子來取代，或是 用正三價及五價的離子取代Ti4+，進行半導體化p型或n型 異價摻雜。一般而言，半導體化時取代Ba2+的有、以3+ 、Y3+、Sb3+、Bi3+以及鑭系稀土元素等；取代Ti4+的有 Nb5+、Ta5+、Bi5+、Mn2+ 以及Mn3+ 等。 許多電子陶莞的研究在於等價或異價添加來提高/溫The addition of Zr4 + caused the composition disturbance to be one of the reasons for the broadening of the curve. For the widening of the permittivity curve, replacement with Ca2 + is also the third method. In addition, it is possible to substitute positively charged trivalent cations, or to replace Ti4 + with positively trivalent and pentavalent ions for semiconductor p-type or n-type heterovalent doping. In general, Ba2 + is replaced by 3+, Y3 +, Sb3 +, Bi3 +, and lanthanide rare earth elements during semiconductorization; Nb5 +, Ta5 +, Bi5 +, Mn2 +, and Mn3 + are replaced by Ti4 +. Much of the research on electronic pottery is based on equivalence or addition of
476733 五、發明說明（3) 述之BaTi〇3於利用推雜後可獲得 5 此^ 的介電率Am. Cerain· sQc.，81 ( 1 998) 稱之為延緩型介電材料（reiax〇r)，以 鈮文釔鎂（lead magnesium ni〇bate，Pb(M 仙）〇 簡 ，為PMN)為代表。此PMN於〇QC的居禮溫度有‘寬=介3電一 溫度曲線，利用摻雜可使居禮溫度往 達29,0〇〇[J· Mater· Res.，4(1989)93〇]。乃正"電羊了 依EIA (Electronic Industries of Association)的 分類，陶瓷電容器可分為三類，第一類是屬低介電率 (k’<100)、低介電損失及低溫度敏感係數者；第二類是屬 鐵電f料有高介電率（k，<1 5,00 0 )者；第三類有極高電容 值’疋屬表面位障型或晶界位障型電容器。表面或晶界位 障型電f器都須經半導化前處理，有時於（112 + %)混合氣氛 下進行還原處理促進半導化。表面位障型電容器是於還原 的電子陶瓷於表面氧化形成薄的絕緣層。晶界位障型電容 器由 WaKu 發明[U.S· Patent 3,473,958，1 9 69 ]，是利用鹼 金族氧化物（如NaJ、LhO)、CuO或硼鉛玻璃等低熔點材 料，經擴散包覆於被還原晶粒周圍而形成。以Nb2〇5摻雜的 SrTi〇3為例，於還原處理後以Na2〇使晶界絕緣可得介電率 50，000〜230，000 ’隨晶粒增大介電率增大[Ceramic476733 V. Description of the invention (3) The BaTi〇3 mentioned in the invention can obtain a dielectric constant of 5 ^^ after using dopant Am. Cerain · sQc., 81 (1 998) is called a retarded dielectric material (reiax. r), represented by lead magnesium niobate (Pb (M), PMN). The curie temperature of this PMN at 0QC has a 'broadness = dielectric-dielectric-temperature curve. By using doping, the curie temperature can reach 29,00 [J. Mater. Res., 4 (1989) 93.] . Nai Zheng " Electric Sheep is classified according to the EIA (Electronic Industries of Association). Ceramic capacitors can be divided into three categories. The first category is low dielectric constant (k '< 100), low dielectric loss and low temperature. Sensitivity coefficients; the second category is those of ferroelectric f materials with high dielectric constant (k, < 15, 00 0); the third category has extremely high capacitance values. 疋 belongs to surface barrier type or grain boundary location Barrier capacitors. Surface or grain boundary barrier-type electrical devices must be pre-semiconducted, and sometimes reduced in a (112 +%) mixed atmosphere to promote semiconductivity. Surface barrier capacitors are oxidized on the surface of reduced electronic ceramics to form a thin insulating layer. Grain boundary barrier capacitors were invented by WaKu [US · Patent 3,473,958, 1 9 69], which are low melting point materials such as alkali gold group oxides (such as NaJ, LhO), CuO or boro-lead glass, which are diffused and coated on the substrate. Formed by reducing around the grains. Taking Nb205-doped SrTi〇3 as an example, after reduction treatment, the grain boundaries are insulated with Na2〇 to obtain a dielectric constant of 50,000 ~ 230,000 ′. As the grain size increases, the dielectric constant increases [Ceramic
Bulletin，62 ( 1 983 ) 698 ]。晶界位障型之BaTi03亦可得到 50，000-100，000 的高介電率[Advanced in Ceramics， 1 (1981)215] 〇 ’ 此發明的材料屬於多重摻雜的Β a Τ i 〇3，此材料的組成 476733 五、發明說明（4) 式如下： [(BahSi^hLaJCTiHMgy：^ y - χ/2, χ<0·〇3，〇<ζ<〇·2。當X值專於或高於〇·〇3時，介 電率迅速降低。當ζ值等於或高於〇· 2時，居禮溫度移往;’ 〇°C以下，使室溫介電率降低。為得到均勻的組成，本發 明採用化學溼法製程。實驗中秤量所需化學藥品，將秤得 的醋酸鋇、硝酸勰、硝酸鑭、硝酸鎂溶於去離子水中，在 加入檸檬酸以及乙二醇於其中形成溶液A，溶液b是由正丁 基醇氧鈥（titanium n-but oxide)溶於乙二醇後再加入棒 檬酸與乙二醇形成的酯而組成。溶液A及b混合經 250-400QC的加溫後可形成泡芙狀的高分子前驅體，經煆 燒、球磨、乾燥及過篩得到多重摻雜的BaTi〇3陶瓷粉體。 利用酸與醇形成的酯類除了 一般擰檬酸的鉗合盘 酸與乙二醇的採用亦可避免正丁基醇氧鈦於水； 盥1 ? r (1 -1 =解反應，導致組成不均的缺點。此粉體經壓片 I， 〇°c的空氣中燒結，得到緻密圓片塊材。圓片 = 4:f、拋光與電極製作後，將試樣置於可調溫的爐 ，中（-40C - 140。〇 ’以HP 4263A型的LCR介電量測設 備，在直流偏壓1伏特/微米、 >、ώ 咕 订做木下，頻率10 KHz及1〇〇 KHz的 父 訊旒下，量測介電率與介電損失。Bulletin, 62 (1 983) 698]. The grain boundary barrier type BaTi03 can also obtain a high dielectric constant of 50,000 to 100,000 [Advanced in Ceramics, 1 (1981) 215] 〇 'The material of this invention belongs to multiple doped Β a Τ i 〇3 The composition of this material is 476733 V. Description of the invention (4) The formula is as follows: [(BahSi ^ hLaJCTiHMgy: ^ y-χ / 2, χ < 0 · 〇3, 〇 < ζ < 〇 · 2. When X value is specialized in When it is higher than 0.03, the dielectric constant decreases rapidly. When the zeta value is equal to or higher than 0.2, the Curie temperature is shifted to; '0 ° C or lower, so that the dielectric constant at room temperature is reduced. In order to obtain uniformity In the experiment, the chemical wet process is used. In the experiment, the required chemicals are weighed, and the barium acetate, europium nitrate, lanthanum nitrate, and magnesium nitrate obtained in the scale are dissolved in deionized water, and citric acid and ethylene glycol are added thereto. Solution A is formed, and solution b is composed of titanium n-but oxide dissolved in ethylene glycol and then added with citric acid and ethylene glycol to form an ester. Solutions A and b are mixed by 250- After heating at 400QC, a puff-like polymer precursor can be formed. After doping, ball milling, drying and sieving, a multi-doped BaTi〇3 ceramic powder is obtained. In addition to the general use of citric acid and the use of clamping acid and ethylene glycol, the esters formed from acids and alcohols can also avoid the use of titanium n-butyloxide in water; 1? R (1 -1 = decomposition reaction, This results in the disadvantage of uneven composition. This powder is sintered in the air at a pressure of 0 ° C to obtain a compact disc. The disc is 4: f. After polishing and electrode fabrication, the sample is placed in an adjustable Warm furnace, medium (-40C-140. 〇 HP 4263A type LCR dielectric measurement equipment, under DC bias 1 volts / micron, >, free custom made wood, frequency 10 KHz and 100 KHz's father measured the dielectric rate and dielectric loss.
代夺MS為t匕cf明相關的組成，試樣符號以L代表La，M 面戶ΐ & @ ^ ^後面所接的數字為百分位數字， 斂宋。FM r、A 、、數子’ S後面所接的數字為拾分位 回a /、（）為鳃含量為〇· 1時的介電率-溫度及介 4/6733 五、發明說明（5) 電損失正切-溫度的關係。介電率與損失正切的乘積定義 為介電損失因子（loss factor of dielectrics)。於低鑭 含量時，〜37, 〇〇〇的居禮峰值及〇· 26的損失正切出現在居 禮，度〜40%卜34,〇〇〇的介電率及〇·19的損失正切則出現 在至溫。當鑭及鎂含量增加時，介電峰值急劇下降。介電 f是量測頻率的函數，隨頻率增高，介電率 出現於圖1。 圖2(a)與（b)為锶含量為〇2時的介電率-溫度及介電 Ιίϊ切-溫度的關係。於低鑭含量時，〜120,〇〇〇的居禮 峰值出現於一20〇C附近；損失正切有0.38的極大值。 的tl率及°.54的損失正切出現於室Η 日t電峰高/下電率。當鋼及鎮含量增加 率增高，介電率降低亦出現於圖2疋。里測頻率的函數，心頻 可達二合1言，Ba，系的介電率可達〜2〇, _，而·系 了違30，〇〇〇，位障型雷交目女 明的多重摻雜BaTi〇3系!二71的介電率。而此發 處理u &曰π π # i @ +電材枓，無需經過特別的氣氛Substitute MS is the relevant component of t. The sample symbol is L for La, and M followed by ΐ & @ ^ ^ The numbers following the percentile are the percentiles. The numbers following FM r, A, and the number 'S are the pick-up a /, () is the dielectric constant-temperature and dielectric 4/6733 when the gill content is 0.1. V. Description of the invention (5 ) Electrical loss tangent-temperature relationship. The product of dielectric rate and loss tangent is defined as the loss factor of dielectrics. At low lanthanum content, the peak of Curie ~ 37,000 and the loss tangent of 0.26 appear in Curie, the degree of dielectricity of ~ 40%, the dielectric constant of 34,00, and the loss tangent of .19 Appears in the extreme temperature. When the lanthanum and magnesium content increases, the dielectric peak drops sharply. The dielectric f is a function of the measured frequency. As the frequency increases, the dielectric constant appears in Figure 1. Figures 2 (a) and (b) show the relationship between the dielectric constant-temperature and the dielectric cut-temperature when the strontium content is 02. At low lanthanum content, the curiosity peak of ~ 120,000 appears near -200C; the tangent of the loss has a maximum value of 0.38. The tl rate and the loss tangent of ° .54 appear at the peak t / power rate of the room t day. When the increase rate of steel and town content increases, the decrease of dielectric rate also appears in Figure 2 疋. As a function of the measured frequency, the heart rate can reach 2 in 1 speech, and the dielectric rate of Ba and Department can reach ~ 20, _, while the Department of Deformation is a multiple of 30, 000, which is a barrier-type Thunderbird. The dielectric constant of doped BaTi〇3 system! And this hair processing u & π π # i @ + 电 材 枓, without going through a special atmosphere
BaT二理來形成位障型電容，就可得到 BaT1〇3的最同介電率及與位障型電容相近 。 4/6733 圖式簡單說明 表與圖示說日月 表1 多重推雜 BaTi03 : [(Bal - zSrzM - xLaxKTil - yMgy)03 之組成 圖1入夕重摻雜的[。8〇.93]：0.1)1-又1^又](1^1-71^丫）〇3其 (a) ;|電率及（b)介電損失正切隨溫度變化的關係 圖 2 多重摻雜的[(Ba0.8Sr〇.2)卜 xLax](TU - yMgy)03 其 (a)介電率及（b)介電損失正切隨溫度變化的關係 第10頁 476733 圖式表1 x(La) y(Mg) z(Sr) Sanpfe synbol 0.02 x/2 = 0.01 0.1 0.2 L2-M1-S1 L2-M1-S2 0.03 x/2 = 0.015 0.1 0.2 L3-M1.5-S1 L3-M1.5-S2 0.04 x/2 = 0.02 0.1 0.2 L4-M2-S1 L4-M2-S2BaT can be used to form a barrier capacitor, and BaT103 can have the same dielectric constant as that of a barrier capacitor. 4/6733 Brief description of the table Table and illustration of the sun and the moon Table 1 Multiple doping BaTi03: [(Bal-zSrzM-xLaxKTil-yMgy) 03 Composition Figure 1 [Early doped []. 8〇.93]: 0.1) 1- 1 1 ^] (1 ^ 1-71 ^ ya) 〇3 its (a); | electric capacity and (b) dielectric loss tangent as a function of temperature Figure 2 Multiple Doped [(Ba0.8Sr〇.2) Bu xLax] (TU-yMgy) 03 The relationship between (a) dielectric constant and (b) dielectric loss tangent as a function of temperature Page 10 476733 Schematic Table 1 x (La) y (Mg) z (Sr) Sanpfe synbol 0.02 x / 2 = 0.01 0.1 0.2 L2-M1-S1 L2-M1-S2 0.03 x / 2 = 0.015 0.1 0.2 L3-M1.5-S1 L3-M1. 5-S2 0.04 x / 2 = 0.02 0.1 0.2 L4-M2-S1 L4-M2-S2