1272625 A7 B7 五 、發明說明（ :發明係關於一種適用於電容器中高頻導電之陶莞介 电材料組成者。 二今多層陶宽電容器之製作’其係先以一鈦酸鋇基 a ! 3)組成物製成一介電片體，然後將作為内電極之 ，料覆蓋於介電片體之表面，接著在將此帶有電極之 二以空氣在跡讓。c下熱處理燒結 侍到一具有内電極之介電質電容器，最後，將外電 1與内電極結合而成為一最終之多層陶瓷電容哭。 結，^於^乍陶究電容器時’内電極需與介電㈣一起燒 料項且備：5 Woe以上之兩溫燒結，因此内電極的材 料間融點、高溫氧化狀態下不會氧化和在介電材 下妒成：導：應的性質’同時介電材質易在中性氮氣氛圍 下屯成化’因此無法使職溶化性（高溶點） 為内電極’也就無法以低廉的價格製陶 (Mult! Layer Ceramic Capacxtor, MLCC ) 因此，内電極常用惰性金屬如鉑、金、鈀等 為製作材料，雖然這些材料有極佳之特性一…作 她立也很昂貴，因此，内電極材料之成本往 =電容器製作成本之50%以上’為增 ^ 製作成本之最大因素。 彳史电谷益 緣是，本案發明人針對前述之多層陶 :組成，再深入加以積極研究改進之道， 之；二 作而開發出本發明。 W心努力试 本發明之主要目的係提供一種電容器之高頻陶瓷介電 t紙岭鮮（CNS)A4祕咖χ观公髮）1272625 A7 B7 V. INSTRUCTIONS (Inventions) A component of a ceramic dielectric material suitable for high-frequency conduction in capacitors. The production of the second-generation multilayer ceramic capacitors is based on a barium titanate a! 3) composition. A dielectric sheet is formed, and then the inner electrode is covered on the surface of the dielectric sheet, and then the electrode with the electrode is placed in the air. The heat treatment is performed under c, and a dielectric capacitor having an internal electrode is applied. Finally, the external power 1 is combined with the internal electrode to become a final multilayer ceramic capacitor. When the capacitor is used, the internal electrode needs to be burned together with the dielectric (4) and is prepared to be sintered at a temperature of 5 Woe or more. Therefore, the melting point of the material of the internal electrode does not oxidize under high temperature oxidation. Under the dielectric material: guide: the nature of the 'simultaneous dielectric material is easy to sinter in a neutral nitrogen atmosphere' so the inability to dissolve (high melting point) for the internal electrode 'can not be cheap Mult! Layer Ceramic Capacxtor (MLCC) Therefore, the internal electrodes are usually made of inert metals such as platinum, gold, palladium, etc., although these materials have excellent characteristics, and they are expensive, so The cost of the electrode material = 50% or more of the capacitor manufacturing cost is the biggest factor in the production cost.彳史电谷益缘, the inventor of the present invention developed the present invention in response to the aforementioned multi-layered pottery: composition, and then actively researched and improved the way. The main purpose of the present invention is to provide a high frequency ceramic dielectric for a capacitor.
1272625 五、發明說明（z ) 材料組成，其可在低於95(rc之低溫下燒結，同時不會在 氮氣氛圍中被半導化，燒結後之介電組成具有下列特性： 低於20卯m的介電常數溫度係數絕對值、且 甘ZbHz下的 Q值大於2000，㈣可以使用例如銅之類的卑金屬作為 内電極。 _ 為達到上述之發明目的，本發明中所使用之技術手段 為使用如下之燒結介電組成包括有： 主要組成· Ba2Ti9〇2〇 60-95wt% 次要組成：玻璃添加物5-4Gwt% 其中玻璃添加物中包含有B2〇3、ZnO、Si〇2與至 少一種之 CuO、CaC〇3、BaCOs。 為使貴審查委員能進一步瞭解本發明之原理及功 效’兹舉以下之操作實施例及分析實驗說明如下： 說明實施例中使用本發明之非還原性介電材質製作盤 狀電容器。 首先，先準備 BaC〇3、Ti〇2 ' B2〇3、ZnO、CuO、Si〇21272625 V. INSTRUCTIONS (z) Material composition, which can be sintered at temperatures below 95 (rc) without being semi-conducting in a nitrogen atmosphere. The dielectric composition after sintering has the following characteristics: Below 20卯The absolute value of the dielectric constant temperature coefficient of m and the Q value at ZbHz is greater than 2000, and (4) a base metal such as copper may be used as the internal electrode. _ In order to achieve the above object, the technical means used in the present invention The composition for sintering using the following includes: Main composition · Ba2Ti9〇2〇60-95wt% Secondary composition: Glass additive 5-4Gwt% wherein the glass additive contains B2〇3, ZnO, Si〇2 and At least one of CuO, CaC〇3, and BaCOs. To enable the reviewer to further understand the principles and effects of the present invention, the following operational examples and analytical experiments are described as follows: Describe the non-reducing nature of the present invention in the examples. Dielectric capacitors are used to make disc capacitors. First, prepare BaC〇3, Ti〇2 'B2〇3, ZnO, CuO, Si〇2
CaC〇3作為燒結原料，稱重後以濕式法混合BaC〇3和Ti〇2， 再經乾燥後在1150°C下鍛燒4小時，以形成BazTi9〇2。之粗 胚。 接著將玻璃添加物B2O3、ZnO、Si〇2與至少一種之 BaC〇3、CuO和CaCCh稱重後混合組成，其組成重量如表 本、、氏張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -----— — It! — —--- (請先閱讀背面之注意事項再填寫本頁) 1272625 A7 ___B7_ 五、發明說明（> ) 表一：玻璃添加物的組成，其中數字表示為重量百分 比。 系列 B2O3 ZnO Si〇2 CuO CaO BaC〇3 A 42. 1 51.0 6. 9 — B 40.0 40.0 10. 0 10.0 C 36.2 30.0 7.8 13. 5 10. 5 D 32. 0 41.3 8· 7 10. 0 10. 0 E 36. 0 40.5 8.5 8. 0 7· 0 F 30.2 37.6 7.4 12.8 12. 0 —G 31.5 40· 3 9.2 6. 0 4. 0 6-0 (請先閱讀背面之注意事項再填寫本頁) 將選取好之玻璃添加物混合組成在丨別^它炼解5分 鐘，再倒入冷水中冷淬，冷淬後的玻璃添加物再經烘乾、 清洗、篩選、以濕式研磨法研磨，最後得到玻璃添加物粉 末。 將Ba2Ti9〇2。粗胚與上述之玻璃添加物粉末以球磨法 如1卜1^11_)混合，乾燥後以4〇11^11之篩網篩選，得 到如下表二中各組之陶瓷介電材料組成。CaC〇3 was used as a sintering raw material, and after weighing, BaC〇3 and Ti〇2 were mixed by a wet method, dried, and then calcined at 1150 ° C for 4 hours to form BazTi9〇2. The rough embryo. Then, the glass additive B2O3, ZnO, Si〇2 and at least one of BaC〇3, CuO and CaCCh are weighed and mixed, and the composition weight is as shown in the table, and the Chinese standard (CNS) A4 specification ( 210 X 297 mm) ------ — It! — —--- (Please read the notes on the back and fill out this page) 1272625 A7 ___B7_ V. Description of invention (>) Table 1: Glass additives The composition of which is expressed as a percentage by weight. Series B2O3 ZnO Si〇2 CuO CaO BaC〇3 A 42. 1 51.0 6. 9 — B 40.0 40.0 10. 0 10.0 C 36.2 30.0 7.8 13. 5 10. 5 D 32. 0 41.3 8· 7 10. 0 10. 0 E 36. 0 40.5 8.5 8. 0 7· 0 F 30.2 37.6 7.4 12.8 12. 0 —G 31.5 40· 3 9.2 6. 0 4. 0 6-0 (Please read the notes on the back and fill out this page) The selected glass additive is mixed and composed in the screening. It is refining for 5 minutes, and then poured into cold water to be quenched. The cold-quenched glass additive is then dried, washed, screened, and ground by wet grinding. Finally, a glass additive powder was obtained. Ba2Ti9〇2. The coarse embryos were mixed with the above-mentioned glass additive powder by a ball milling method such as 1 bl 11*, dried, and sieved through a 4 〇 11 11 mesh screen to obtain a ceramic dielectric material composition of each group in the following Table 2.
,μ、_— · |匕\ 广 σ 樣本號碼 /70 〜uck 丄 JL 91J20 j 主要組成 ，瓦冗％柯科組成 次要組成（玻璃添加物） (wt°/o) (wt%) 系列 *1 95 5 A —_ 2 80 20 A 本紙張用中國國家標準（CNS)A4規格（210 X 297公爱） A7 _._B7 *3 60 40 A *4 95 5 B 5 70 30 B *6 60 40 B 7 80 20 C 8 65 35 C 9 80 20 D *10 60 40 D *11 95 5 E 12 75 25 E *13 60 40 E 14 80 20 F 15 65 35 F *16 95 5 G 17 90 10 G 18 85 15 G 19 80 20 G 20 75 25 G 21 70 30 G *22 60 40 G *標計為不符合本發明所介定者。 1272625 五、發明說明（斗） (請先閱讀背面之注意事項再填寫本頁) ------- t---------. 將表二中之陶瓷介電材料組成，以5-6wt%的比例與 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 1272625 A7 B7 五、發明說明（f) 6%的聚乙烯醇（PVA)黏結劑溶液混合，讓介電材料粉末如 陶土般可被凝塑，混合後在2ton/cm2的壓力下乾式打錠壓 製（dry press)成直徑16mm、厚度8mm的錠粒，接著將錠 粒中之黏結劑燒除，再以900-950°C氮氣氛圍中燒結2小 時，待燒結完成後量測錠粒之密度，其結果如表三所示， 最後將錠粒之兩面塗佈銀膠後以650°C焙燒，以得到最後 之電容器之高頻陶堯介電材料組成。 ---·1----^--------- (請先閱讀背面之注意事項再填寫本頁) 表三 :低培燒Badi 9〇2〇陶甍介電材， 畔組成之介電性質 樣本號碼 燒結溫度 (°C) 介電常數 (ε ) 2GHz 下 的Q值 溫度係數 (ppm/°C ) 密度 (g/cm3) *1 >950 - — — — 2 920/4hr 25. 6 2300 18. 0 4. 05 *3 920/4hr 21. 8 1550 -50. 0 4. 09 *4 >950 — — — — 5 950/4hr 22. 9 2600 12. 0 4. 08 *6 950/4hr 20. 8 1605 -38.2 4. 10 7 920/4hr 26. 2 2010 10. 0 4. 10 8 900/2hr 22. 1 2300 17. 0 4. 08 9 910/2hr 25. 1 2050 -18. 2 4. 16 *10 900/2hr 24. 3 1905 -37. 0 4. 12 *11 >950 - — - — 12 940/2hr 25.4 2300 -17· 0 4. 02 *13 920/2hr 23. 3 1840 -35 4. 03 14 950/4hr 25. 2 2025 -15.3 4. 12 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 1272625 A7 ______ __— B7 五、發明說明（b ) _ 15 920/2hr 24. 7 2600 -17.2 4. 08 *16 >950 17 920/4hr 27.6 2005 -5. 2__ 4. 3 18 920/2hr 26.5 2330 6 4. 26 19 900/4hr 23.2 3600 7.4 4. 19 20 900/2hr 21.3 4200 8.2 4. 13 21 880/2hr 19.8 2006 -20 4. 05 *22 880/2hr 13. 6 1000 -80 3. 98 *標計為不符合本發明所介定者。 (請先閱讀背面之注意事項再填寫本頁) 之後將量取各組成之介電常數、2GHz下之Q值與 1MHz、lVrms下之介電常數溫度係數，其中介電常數溫度 係數藉由下列之公式可計算出： 溫度係數（PPm/°C ) K(Ci5〇-C-55)/C2〇)*(l/(l5〇-(-55)))*10 6 其結果同樣列於表二中’由表中可知，當玻璃添加劑 少於5wt%時，如樣本1、4、11、16，並無法在950°C下燒 結’另一方面’當玻璃添加劑大於4〇wt%時，如樣本3、 6、10、13、22，其顯示Q值皆小於2〇〇〇同時溫度係數高 於20PPm/ °C，因此決定了玻璃添加物之最適含量為 5wt%〜40wt%，而相對之主要組成物Β^Τί9〇2。之含量為6〇一 95wt% 。 此外，本發明中之電容器之高頻陶瓷介電材料組成， 1 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱） 1272625,μ,__ · |匕\ 广σ Sample number /70 〜 丄 LJL 91J20 j Main composition, wavy % Coco composition secondary composition (glass additive) (wt°/o) (wt%) Series* 1 95 5 A —_ 2 80 20 A This paper uses Chinese National Standard (CNS) A4 specification (210 X 297 public) A7 _._B7 *3 60 40 A *4 95 5 B 5 70 30 B *6 60 40 B 7 80 20 C 8 65 35 C 9 80 20 D *10 60 40 D *11 95 5 E 12 75 25 E *13 60 40 E 14 80 20 F 15 65 35 F *16 95 5 G 17 90 10 G 18 85 15 G 19 80 20 G 20 75 25 G 21 70 30 G *22 60 40 G *The standard is not as defined in the present invention. 1272625 V. Description of the invention (bucket) (Please read the notes on the back and fill out this page) ------- t---------. Make the ceramic dielectric materials in Table 2, Apply the Chinese National Standard (CNS) A4 specification (210 X 297 mm) to the paper scale at a ratio of 5-6 wt%. 1272625 A7 B7 V. Inventive Note (f) 6% Polyvinyl Alcohol (PVA) Adhesive Solution Mix The dielectric material powder can be coagulated like clay, mixed and dry pressed into a pellet of 16 mm in diameter and 8 mm in thickness under a pressure of 2 ton/cm 2 , and then the binder in the pellet is burned. In addition, it is sintered in a nitrogen atmosphere at 900-950 ° C for 2 hours. After the sintering is completed, the density of the pellets is measured. The results are shown in Table 3. Finally, the silver particles are coated on both sides of the pellet at 650 ° C. The calcination is performed to obtain a high frequency ceramic dielectric material of the final capacitor. ---·1----^--------- (Please read the notes on the back and fill out this page) Table 3: Low-boiled Badi 9〇2〇陶甍 dielectric, bank Composition of dielectric properties Sample number Sintering temperature (°C) Dielectric constant (ε) Q value temperature coefficient at 2 GHz (ppm/°C) Density (g/cm3) *1 >950 - — — — 2 920/ 4hr 25. 6 2300 18. 0 4. 05 *3 920/4hr 21. 8 1550 -50. 0 4. 09 *4 >950 — — — — 5 950/4hr 22. 9 2600 12. 0 4. 08 *6 950/4hr 20. 8 1605 -38.2 4. 10 7 920/4hr 26. 2 2010 10. 0 4. 10 8 900/2hr 22. 1 2300 17. 0 4. 08 9 910/2hr 25. 1 2050 -18. 2 4. 16 *10 900/2hr 24. 3 1905 -37. 0 4. 12 *11 >950 - — - — 12 940/2hr 25.4 2300 -17· 0 4. 02 *13 920/2hr 23. 3 1840 -35 4. 03 14 950/4hr 25. 2 2025 -15.3 4. 12 This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1272625 A7 ______ __- B7 V. Invention Description (b) _ 15 920/2hr 24. 7 2600 -17.2 4. 08 *16 >950 17 920/4hr 27.6 2005 -5. 2__ 4. 3 18 920/2hr 26.5 2330 6 4. 26 19 900/4hr 23.2 3600 7.4 4. 19 20 900/2hr 21.3 4200 8.2 4. 13 21 880/2hr 19.8 2006 -20 4. 05 *22 880/2hr 13. 6 1000 -80 3. 98 *The standard is not as defined by the present invention. (Please read the note on the back and fill in this page.) Then we will measure the dielectric constant of each component, the Q value at 2 GHz, and the dielectric constant temperature coefficient at 1 MHz and 1 Vrms, where the dielectric constant temperature coefficient is as follows The formula can be calculated as follows: Temperature coefficient (PPm/°C) K(Ci5〇-C-55)/C2〇)*(l/(l5〇-(-55)))*10 6 The results are also shown in the table. Second, 'from the table, when the glass additive is less than 5 wt%, such as samples 1, 4, 11, 16 and can not be sintered at 950 ° C 'on the other hand' when the glass additive is greater than 4 〇 wt%, For example, samples 3, 6, 10, 13, 22 show that the Q values are less than 2〇〇〇 and the temperature coefficient is higher than 20PPm/ °C, thus determining the optimum content of the glass additive is 5wt%~40wt%, and relative The main composition is Β^Τί9〇2. The content is 6〇95% by weight. In addition, the high frequency ceramic dielectric material of the capacitor of the present invention, 1 paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 public) 1272625
發明說明（ 其在燒結過程中，即使在屬於低溫的950°C、中性低氧度 的乱圍下也不會被半導化，同時燒結後之介電組成具有低 於20ppm的介電常數溫度係數絕對值，且在沉此下的q 值大於2000，㈣可以使用銅等卑金屬作為内電極。 =上所述，本發明之電容器之高頻陶竞介電材料組成 確I為-極具產業上利用性之優良發明，因 明專利。 入T明^ 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 裝---《-----訂------ (請先閱讀背面之注意事項再填寫本頁)DESCRIPTION OF THE INVENTION (In the sintering process, even at a low temperature of 950 ° C, neutral hypoxia, it will not be semi-conductive, and the dielectric composition after sintering has a dielectric constant of less than 20 ppm. The absolute value of the temperature coefficient, and the q value under the sink is greater than 2000, (4) the base metal such as copper can be used as the inner electrode. = As described above, the high frequency Tao Jing dielectric material of the capacitor of the present invention is indeed I-polar Excellent invention with industrial applicability, due to patents. Enter T Ming ^ This paper scale applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) Pack---------订---- -- (Please read the notes on the back and fill out this page)