TW567511B - Ceramic capacitor device, conductive composition and conductive paste - Google Patents
Ceramic capacitor device, conductive composition and conductive paste Download PDFInfo
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- TW567511B TW567511B TW091125216A TW91125216A TW567511B TW 567511 B TW567511 B TW 567511B TW 091125216 A TW091125216 A TW 091125216A TW 91125216 A TW91125216 A TW 91125216A TW 567511 B TW567511 B TW 567511B
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- 239000000203 mixture Substances 0.000 title claims description 46
- 239000003985 ceramic capacitor Substances 0.000 title claims description 36
- 239000011521 glass Substances 0.000 claims abstract description 58
- 239000000919 ceramic Substances 0.000 claims abstract description 48
- 239000002184 metal Substances 0.000 claims abstract description 37
- 229910052751 metal Inorganic materials 0.000 claims abstract description 37
- 239000000758 substrate Substances 0.000 claims abstract description 20
- 229910052745 lead Inorganic materials 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 239000000853 adhesive Substances 0.000 claims abstract description 6
- 230000001070 adhesive effect Effects 0.000 claims abstract description 6
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 229910052709 silver Inorganic materials 0.000 claims abstract description 5
- 239000003990 capacitor Substances 0.000 claims description 55
- 239000003989 dielectric material Substances 0.000 claims description 30
- 239000011133 lead Substances 0.000 claims description 22
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 9
- 239000011230 binding agent Substances 0.000 claims description 8
- 239000005388 borosilicate glass Substances 0.000 claims description 4
- 229910002113 barium titanate Inorganic materials 0.000 claims description 3
- CDMADVZSLOHIFP-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane;decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 CDMADVZSLOHIFP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 230000001568 sexual effect Effects 0.000 claims 1
- 229910016264 Bi2 O3 Inorganic materials 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 27
- 229910000679 solder Inorganic materials 0.000 description 17
- 238000002474 experimental method Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 239000011159 matrix material Substances 0.000 description 7
- 239000004020 conductor Substances 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 210000002784 stomach Anatomy 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005496 eutectics Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- LQBJWKCYZGMFEV-UHFFFAOYSA-N lead tin Chemical compound [Sn].[Pb] LQBJWKCYZGMFEV-UHFFFAOYSA-N 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- 241000428352 Amma Species 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000002344 gold compounds Chemical class 0.000 description 1
- 239000005337 ground glass Substances 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/005—Electrodes
- H01G4/008—Selection of materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/08—Inorganic dielectrics
- H01G4/12—Ceramic dielectrics
- H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
- H01G4/1218—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates
- H01G4/1227—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates based on alkaline earth titanates
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Ceramic Capacitors (AREA)
- Conductive Materials (AREA)
- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
Abstract
Description
567511 五、發明說明(1) 發明所屬之技術領域 本發明與陶究電容元彳半、! 物有關。 電性組合物、及導電糊狀 先前技術 陶兗電容元件之製程裏, BaTi〇3系材料等所構成之陶瓷 以形成電容電極。 向來,構成電容電極之導 化合物等鉛成分,鉛成分對環 此’要從導電糊狀物裏除去鉛 但是,從導電糊狀物除去 玻璃之軟化點上升。該玻璃負 質材料基體之功能,璩璃之軟 石炼融擴散不充分,降低了電 之間的密著性。結果,電容電 著強度低下,導致陶瓷電容元 避免該等電容電極接著強 電糊狀物所含玻璃之組成以極 瓷介質材料基體與電容電極之 陶瓷電容元件之電容低下,及 如上所述,構成電容電極 的情況下,接著強度等信賴度 元件之特性實難兼顧。 將導電糊狀物塗敷於由 介質材料基體之表面,燒接 物晨含有錯玻璃或錯 良影響常遭指摘。因 ,則導電糊 容電極接著 升,造成電 與陶瓷介質 瓷介質材料 賴度低下。 下之方法, 玻璃之軟化 玻璃成分。 耗增大等問 糊狀物裏不 容、介質損 狀物所含 於陶瓷介 極膜燒結 材料基體 基體之接 如改變導 點,則陶 因此產生 題。 含鉛成分 耗等電容567511 V. Description of the Invention (1) Technical Field to Which the Invention belongs Related. Electrical composition and conductive paste. Prior art In the process of manufacturing ceramic capacitors, ceramics made of BaTi03-based materials were used to form capacitor electrodes. Conventionally, lead components such as conductive compounds constituting a capacitor electrode, and the lead components have a ring to remove lead from the conductive paste. However, when the conductive paste is removed, the softening point of the glass increases. The function of the matrix of the glass negative material is that the melting and melting of the soft glass of the glass is insufficient, which reduces the adhesion between electricity. As a result, the capacitor's electrical strength is low, which causes ceramic capacitors to avoid these capacitor electrodes followed by the composition of the glass contained in the strong electric paste. The capacitance of the ceramic capacitor element of the base material of the ceramic dielectric material and the capacitor electrode is low, and as described above, In the case of a capacitor electrode, it is difficult to balance characteristics of a reliability element such as strength. The conductive paste is coated on the surface of the base of the dielectric material, and the fired material contains the wrong glass or the wrong influence is often criticized. Because of this, the conductive paste capacitor electrode then rises, resulting in low reliability of electrical and ceramic dielectric materials. The following method softens the glass composition. Problems such as increased energy consumption, paste intolerance, and dielectric loss contained in the ceramic dielectric film sintered material matrix substrate. If the conductive point is changed, ceramics will cause problems. Lead-containing composition
567511 五、發明說明(2) 發明内容 本發 電容元件 本發 材料基體 性組合物 本發 增大之陶 為達 介質材料 附著於前 及Bi2 03, Ag中至少 上述 基體外面 並且 括Cu及Ag 極對陶瓷 夠避免陶 因此 極對陶瓷 容低下及 電容 =^目的在提供’電容電極裏不含鉛成分之陶瓷 ,其所使用冬導電性組合物。一 f目的在提供’可避免電容電極對陶瓷介質 者強度低下之陶瓷電容元件及其所使用之導電 〇 明再一目 瓷電容元 成上述目 基體及電 述陶瓷介 而不含任 一種。 本發明之 之電容電 ’電容電 中至少一 介質材料 瓷電容元 ,可得電 介質材料 介質損耗 電極之理 的在提供’可避免電容低下及介質損耗 件及其所使用之導電性組合物。 2 ’本發明之陶瓷電容元件,包括陶瓷 容電極’其特徵在於:前述電容電極係 質材料基體之外面,包括金屬、玻璃、 何Pb及Pb化合物,且前述金屬包括Cu及 陶瓷電 極,不 極包括 種。根 基體之 件之電 容電極 基體之 增大之 想組成 容元件裏,附著於陶瓷介質材料 含任何Pb及Pb化合物。 金屬、玻璃、及Bi2 03,金屬則包 據該組成,不僅能夠避免電容電 接著強度之低下,同時確認了能 容低下及介質損耗增大。 裏不含鉛成分,能夠避免電容電 接著強度之低下,且能夠避免電 陶瓷電容元件。 裏,將相對於金屬全量之Bi2〇3之567511 V. Description of the invention (2) Summary of the invention Capacitive element base material composition Base material composition The pottery of the present invention is a dielectric material attached to the front and Bi2 03, Ag at least outside the above substrate and including Cu and Ag electrodes Ceramics are enough to avoid ceramics, so they have low capacitance and capacitance. The purpose is to provide ceramics that do not contain lead in capacitor electrodes, and use winter conductive compositions. The purpose of f is to provide a ceramic capacitor element that can prevent the capacitor electrode from having a low strength against the ceramic dielectric and the electric conduction used by the capacitor. A ceramic capacitor element of the above-mentioned purpose and a ceramic medium are not included. In the capacitor capacitor of the present invention, at least one of the dielectric materials and ceramic capacitor elements can be obtained as a dielectric material. The dielectric loss electrode is provided to prevent low capacitance and dielectric loss components and the conductive composition used therefor. 2 'The ceramic capacitor element of the present invention includes a ceramic capacitor electrode', characterized in that the outer surface of the above-mentioned capacitor electrode matrix material includes metal, glass, Pb and Pb compounds, and the aforementioned metal includes Cu and ceramic electrodes. Including species. Capacitance electrodes of the base body are intended to increase the size of the base body. The capacitor element is attached to the ceramic dielectric material and contains any Pb and Pb compounds. Metal, glass, and Bi203 are based on this composition, which not only avoids the decrease in the capacitance and subsequent strength of the capacitor, but also confirms that the capacitance is low and the dielectric loss is increased. It does not contain lead, which prevents the capacitors from having a low strength and ceramic capacitors. Here, relative to the total amount of Bi203
2〇30-5288-PF(N);Ahddub.ptd 第5頁 567511 五、發明說明(3) 含有量,定於O.lwt% 金屬全量之玻璃之含 内。 甚且,本發明亦 上之電容電極之導電 屬、玻璃、及Bi2 03, 屬包括Cu及Ag中之至 將上述導電性組 製出導電糊狀物。進 料基體之外面,燒接 電容電極,而獲得上 〜10· Owt%之範圍内。 有量,定於0. 1 wt%〜5 揭示,用以形成於陶 性組合物。該導電性 且不含任何Pb及Pb化 少一種 合物、黏結劑、及溶 而將該導電糊狀物塗 之,即可於陶瓷介質 述本發明之陶瓷電容 並且,將相對於 〇wt%之範圍 瓷介質材料基體 組合物包括金 合物”而前述金 劑混合後,可調 敷於陶瓷介質材 材料基體上形成 元件。 實施方式 如第1圖及第2圖所示,本發明之陶瓷電容元件 ^陶^介質材料基體υ、電容電極21及22。圖示之陶 谷元件雖備有2個雷客雷;Κ 9 1 〇 〇 冤 隨意。 4電極21、22,但f容電極之個數為 陶瓷介質材料基體1可以BaTi系 之,惟亦可以其他材料 3何:马主成刀構成 之。並且’圖示之陶咨.入租 3糸材料為主成分構成 為其他形狀,例如,方二板2料=1為圓板狀,惟亦可 度方向τ看有2個互為方二板之狀 nj容=:22附著,竟介質材料基體i之外面 。 個電容電極21附著於陶瓷介質材料基 第6頁 203〇.5288-PF(N);Ahddub.ptd2030-5288-PF (N); Ahddub.ptd Page 5 567511 V. Description of the invention (3) The content is determined to be 0.1% by weight of the total metal content of glass. In addition, the conductive metals, glasses, and Bi203 of the capacitor electrodes of the present invention include Cu and Ag to a conductive paste that forms the above-mentioned conductivity. Capacitor electrodes were fired on the outer surface of the feed base to obtain a range of ~ 10 · Owt%. Amount, set at 0.1 wt% ~ 5 revealed, used to form in ceramic composition. The conductive material does not contain any Pb and Pb, a compound, a binder, and a solvent, and the conductive paste is coated, and the ceramic capacitor of the present invention can be described in a ceramic dielectric. The range of porcelain dielectric material matrix composition includes gold compound ", and after mixing the aforementioned gold agent, it can be applied to the ceramic dielectric material material matrix to form elements. The embodiment is shown in Fig. 1 and Fig. 2, the ceramic of the present invention Capacitor element ^ ceramic ^ dielectric material base υ, capacitor electrodes 21 and 22. Although the Taogu element shown in the figure is equipped with two Rayleigh mines; KK 9 1 00 is unjust. 4 electrodes 21, 22, but f capacitor electrodes The number of the ceramic dielectric material substrate 1 can be BaTi, but it can also be made of other materials 3: Ho: the master is made of a knife. And the 'illustrator of the pottery. The main component is made of other materials, such as , The square two plate 2 material = 1 is a circular plate shape, but it can also be seen in the direction τ that there are two square two plates each other. Nj capacity =: 22 is attached, but the dielectric material substrate i is outside. A capacitor electrode 21 is attached Based on Ceramic Dielectric Materials Page 6 2030. 5288-PF (N); Ahddub.ptd
I 567511 五、發明說明(4) 體1之外面11 ’另1個電容電極22附著於陶瓷介質材料基 體1之外面12 ’該2個電容電極2丨、22隔著陶瓷介質材料 基體1相對。 本發明裏’附著於陶瓷介質材料基體1外面11、1 2之 電容電極21、22 ’構成為不含任何pb及以化合物。 甚且,電容電極21、22之構成,包括有金屬、玻璃、 及Β“〇3。用以構成電容電極21、22之金屬,採用Cu及Ag中 之至少一種。根據該組成,不僅可避免電容電極2丨、2 2對 陶竞介質材料基體1之接著強度之低下,同時確定能夠避 免陶瓷電容元件之電容低下及介質損耗增大。 因此可獲得,電容電極21、22裏不含鉛成分,能夠避 免電容電極21、22對陶瓷介質材料基體}之接著強度之低 下,且能夠避免電容低下及介質損耗增大之陶瓷電容元 件0 . 電容電極2 1、2 2之理想組成裏,將相對於金屬全量之 Β“〇3之含有量,設於〇. iwt°/G〜1 〇· 〇wt%之範圍内。並且,將 相對於金屬全量之玻璃之含有量,設於〇 lwt%〜5. 〇wt%之 範圍内。 用以構成電容電極2 1、2 2之玻璃,可使用例如棚砂玻 璃、硼矽酸亞鉛玻璃、或該等之組合物。硼砂玻璃之具體jp 例’例如,SrO — B2〇3 — Al2〇3 — ZnO系玻璃。而硼矽酸亞鉛 玻璃之具體例’如Ζ η 0 — B2 03 — S i 02 — A 12 03系玻璃。 上述電容電極2 1、2 2,可將導電糊狀物塗敷於陶瓷介 質材料基體1之外面1 1、1 2,燒接之使其形成。此用途之I. 567511 V. Description of the invention (4) The outer surface 11 of the body 1 ′ and another capacitor electrode 22 are attached to the outer surface 12 of the ceramic dielectric material substrate 1 ′ The two capacitor electrodes 2 丨 22 face each other with the ceramic dielectric material substrate 1 interposed therebetween. In the present invention, the capacitor electrodes 21, 22 'which are adhered to the outer surfaces 11, 12 of the ceramic dielectric material base body 1 are constituted so as not to contain any pb or compound. In addition, the capacitor electrodes 21 and 22 are composed of metal, glass, and β ". The metal used to form the capacitor electrodes 21 and 22 is at least one of Cu and Ag. According to this composition, not only can it be avoided Capacitor electrodes 2 丨, 2 2 have a low bonding strength to ceramic dielectric substrate 1, and at the same time, it is determined that the capacitance of ceramic capacitor elements can be reduced and the dielectric loss can be increased. Therefore, it can be obtained that capacitor electrodes 21 and 22 do not contain lead. It can avoid the low bonding strength of the capacitor electrodes 21 and 22 to the ceramic dielectric material matrix}, and can avoid the low capacitance and the increased dielectric loss of the ceramic capacitor element 0. The ideal composition of the capacitor electrodes 2 1, 2 2 will be relatively The content of B "〇3 in the total amount of metal is set within a range of 0.1 wt% / G to 10.0% by weight. And, the content of glass relative to the total amount of metal is set within a range of 0 lwt% to 5.0 wt%. As the glass for forming the capacitor electrodes 21 and 22, for example, sintered glass, lead borosilicate glass, or a combination thereof can be used. A specific jp example of borax glass' is, for example, SrO — B2 03 — Al 2 03 — ZnO-based glass. A specific example of lead borosilicate glass is ‘Z η 0 — B2 03 — S i 02 — A 12 03 series glass. The capacitor electrodes 2 1 and 2 2 can be formed by applying a conductive paste to the outer surfaces 1 1 and 1 2 of the ceramic dielectric material base 1. For this purpose
2030-5288-PF(N);Ahddub.p t d 第7頁 567511 五、發明說明(5) 導電糊狀物,可混合導電性組合物、黏結劑、及溶劑等加 以調製。 導電性組合物之構成,要包括金屬、玻璃、及Bi2〇3, 但不含任何Pb及Pb化合物。上述金屬之構成要包括Cu及“ 中至少一種。 以下,列舉實驗數據以具體說明本發明之效果。 <實驗1> 首先,將金屬粉、玻璃熔塊、及Bi2〇3混合後調製出7 種導電性組合物。金屬粉均使用Cu粉,而玻璃炼塊均使用 SrO — B2〇3 ~a 12 03 — ZnO系玻璃。相對於金屬粉全量之^2〇3 之含有量為0· Owt%,〇· iwt%,2· 〇wt%,3· 5wt%,6· 〇wt%, 1 0 · 0 w t % 以及 1 5 · 0 w t 〇/〇。 進一步,該等種導電性組合物分別與黏結劑及溶劑相 混合以調製出7種導電糊狀物。黏結劑係使用有機展色 劑。 一然後以該等7種導電糊狀物作出試料丨〜7之陶瓷電容 元件陶瓷電谷元件製作時所使用之陶瓷介, 係以BaTi03系材料為主忐八,歷危Λ c ^ 3刊T寸钓王成刀,厚度〇· 5mm之圓板形狀物。 在該陶瓷介質材料基體的9個g a t ^ ^ u m伽φ - ·胃的2個反向外面上燒接導電糊狀物 乂構成2個電谷電極。電容電極之直徑設社—。 再針2試料1〜7之陶瓷電容元件,測定電容、介質損 耗、及電容電極對陶奢介皙好祖I 、、 果示於下列表丄 質4基體之接著強纟。實驗結2030-5288-PF (N); Ahddub.p t d page 7 567511 V. Description of the invention (5) Conductive paste, which can be mixed with conductive composition, adhesive, and solvent to prepare. The composition of the conductive composition includes metal, glass, and Bi203, but does not contain any Pb and Pb compounds. The composition of the above metal should include at least one of Cu and ". The experimental data is listed below to specifically explain the effect of the present invention. ≪ Experiment 1 > First, metal powder, glass frit, and Bi203 were mixed to prepare 7 It is a conductive composition. Cu powder is used for all metal powders, and SrO — B203 — a 12 03 — ZnO glass is used for glass ingots. The content of ^ 203 relative to the total amount of metal powder is 0 · Owt. %, 〇 · wt%, 2.0 wt%, 3.5 wt%, 6.0 wt%, 10.0 wt%, and 15.0 wt% 〇 / 〇. Further, these conductive compositions are respectively It is mixed with a binder and a solvent to prepare 7 kinds of conductive pastes. The binder is an organic color developing agent. Then, the 7 kinds of conductive pastes are used as samples to make ceramic capacitor elements, ceramic trough elements, etc. The ceramic medium used in the production is mainly a BaTi03-based material, which is a circular plate shape with a thickness of 0.5mm. It is endangered Λ c ^ 3 issue T inch fishing king knife. The thickness of the ceramic dielectric material is 9 Each gat ^ ^ 伽 amma φ-· 2 reverse outer sides of the stomach are connected with a conductive paste to form 2 electric valleys 。The diameter of the capacitor electrode is set by the agency. Needle 2 ceramic capacitor elements of samples 1 to 7 to measure the capacitance, dielectric loss, and capacitance electrode pair Tao Shejie Xia good ancestor I, as shown in the following table. Then strong slap. Experimental results
2030-5288-PF(N);Ahddub.ptd 第8頁 567511 五、發明說明(6) 【表1】 試料號碼 * 1 2 3 4 5 6 *7 金屬粉 Cu Cu Cu Cu Cu Cu Cu 玻璃熔塊之含有氳wl%〕 2.5 2.5 2.5 2.5 2.5 2.5 2.5 Bi203之含有量〔祕〕 0.0 0.1 2.0 3.5 6.0 10.0 15.0 電容〔nF〕 0.86 1.11 1.14 1.16 1.15 1.15 1.15 介質損耗〔%〕 5.02 1.86 1.60 1.59 1.60 1.60 1.62 接著強度〔Kgf〕 324 3.11 3.06 1.54 1.32 1.21 0.85 焊料濡濕性 X 〇 〇 〇 〇 〇 〇 合否判斷 不合格 合格 合格 合格 合格 合格 不合格 如上述,相對於金屬粉全量之Bi2 03之含有量以〇· lwt0/〇 以上為佳。第3圖顯示B込〇3之含有量與電容之關係。如圖 示,Bi2〇3之含有量達0· lwt%以上時,電容大致止於一定範 圍(1 · 1 InF〜1· 1 6nF )之内。相對地,Bi2〇3之含有量小於 〇· lwt%時,電容急劇降低。亦即,在Bi2〇3之含有量= 〇· lwt%之附近,可視為存在有電容相關之臨界點。 第4圖顯示B “ 〇3之含有量與介質損耗之關係。如圖 示,BiJ3之含有量達0· lwt%以上時,介質損耗大致止 疋犯圍(1.59%〜1.86%)之内。相對地,Bi2〇3之含有旦; 於0· lwt%時,介質損耗急劇增大。亦即,在Bi2〇3之八里小曰 =〇· lwt%之附近,可視為存在有介質損耗相關之3臨^ ! 如上所述,相對於金屬粉全量之8丨2〇3之含有量以”、。 10· Owt%以下為佳。第5圖顯示BiA之含有量與接著強户 關係。如圖示,電容電極對陶瓷介質材料基體之接著=之 度,隨BiA之含有量之增大而降低。陶瓷電容元件 電極之接著強度,為確保信賴度,最低限度,要求^ '谷 1. OOKgf。Bi2〇3之含有量為10· 0wt%以下時,可垂從 % μ筏得12030-5288-PF (N); Ahddub.ptd Page 8 567511 V. Description of the invention (6) [Table 1] Sample No. * 1 2 3 4 5 6 * 7 Metal powder Cu Cu Cu Cu Cu Cu Cu Glass frit氲 wl%] 2.5 2.5 2.5 2.5 2.5 2.5 2.5 Bi203 content (secret) 0.0 0.1 2.0 3.5 6.0 10.0 15.0 Capacitance (nF) 0.86 1.11 1.14 1.16 1.15 1.15 1.15 Dielectric loss (%) 5.02 1.86 1.60 1.59 1.60 1.60 1.62 Subsequent strength [Kgf] 324 3.11 3.06 1.54 1.32 1.21 0.85 Solder wettability X ○ 〇 〇 〇 〇 Whether to determine whether the pass is qualified Passed qualified Passed unqualified As mentioned above, the content of Bi2 03 is 0. Above lwt0 / 〇 is preferred. Figure 3 shows the relationship between the B 込 03 content and the capacitance. As shown in the figure, when the content of Bi203 is more than 0.1 wt%, the capacitance is approximately within a certain range (1 · 1 InF ~ 1 · 16nF). In contrast, when the content of Bi203 is less than 0.1 wt%, the capacitance decreases sharply. That is, in the vicinity of the content of Bi203 = 0.1 wt%, it can be considered that there is a critical point related to capacitance. Figure 4 shows the relationship between the content of B "〇3 and the dielectric loss. As shown in the figure, when the content of BiJ3 reaches more than 0.1 wt%, the dielectric loss is approximately within the limits (1.59% ~ 1.86%). In contrast, Bi2O3 contains denier; at 0.1 lwt%, the dielectric loss increases sharply. That is, in the vicinity of Bi2O3 = about 0.1 wt%, it can be considered that there is a correlation between dielectric loss 3 Lin ^! As mentioned above, the content of 8 丨 2 0 3 with respect to the total amount of metal powder is ",". 10 · Owt% or less is preferred. Figure 5 shows the relationship between the content of BiA and the subsequent strong accounts. As shown, the degree of adhesion of the capacitor electrode to the substrate of the ceramic dielectric material decreases as the content of BiA increases. For ceramic capacitors, the bonding strength of the electrodes is required to ensure the minimum reliability. 1. Valley 1. OOKgf. When the content of Bi203 is less than 10.0 wt%, 1 can be obtained from the% μ raft.
203〇.5288.PF(N);Ahddub.ptd 第9頁 567511 五、發明說明(7) OOKgf以上之接著強度 以in最佳清况疋-將Bl2〇3之含有量定於2· 0wt%以下。參照203〇.5288.PF (N); Ahddub.ptd Page 9 567511 V. Description of the invention (7) The bonding strength above OOKgf is in the best condition 疋-The content of Bl203 is set to 2.0 wt% the following. Refer to
Bi2〇3之含有$為2· 〇wt%以下時,接著強度大致上 處於較高值(3· 06Kgf〜3 f、 , 昙士认〇 士 g ^24Kgf )。相對地,Bi2〇之含有 ^於,OwtW ’接著強度急劇降低。亦即 ;ϊ=2.〇“%之附近,可視為存在有接著強度相關之臨界 其次’對試料1〜7之陶奢雷六-之焊料漂濕性(參照表件^平估其電容電極 2,C之…晶焊料2秒)鐘,=二生之評估,係浸入 上面積為#錫丘曰煜4:i & 、 §電谷電極全面積中70%以 囬檟马釓錫共日日谇枓所濡濕時, 面積為鉛錫共晶焊料所濡渴時,θ ”、、 僅未滿70/G之 參照表1,則本發明範圍内 件,其電容電極之燁料霜濕性均之陶竟電容元 最後,對試料1〜7之陶瓷雷六_ 否判斷係以滿足下述條件丨者件進行合否判斷。合 者為不合格。 者為合格’不滿足下述條们 電容 以上 介質損耗 _^P2.5% 接著強度 以上 坪料濡濕性 —~1 L_〇 ,…、、、丄 个奴%莩巳固鬥之岬极〇 7 丄 有量為0. lwt^ 0. 0wt%範圍之2〜7之中,Bl2〇3之 八枓2〜6,經判斷為合格When the content of Bi203 is less than 2.0 wt%, the bonding strength is approximately at a relatively high value (3.06 Kgf to 3 f,, and it is recognized that the value is ± 24 Kgf). On the other hand, the content of Bi2O is greater than that of OwtW 'and the strength decreases sharply. That is, ϊ = 2.0% near, it can be considered that there is a criticality related to the bonding strength. Second, the solder wettability of Tao Shelei 6-for samples 1 to 7 (refer to Table ^ Evaluate its capacitor electrode. 2, 2 ... Crystal solder 2 seconds) clock, = evaluation of the second life, is immersed in the upper area of # 锡 丘 Yue Yu 4: i & § 70% of the entire area of the electric valley electrode to return to When the area is wet, the area is equal to that of lead-tin eutectic solder, θ ”, and only less than 70 / G, refer to Table 1, the parts within the scope of the present invention, the capacitor electrode material frost is wet In the end, the ceramic capacitors with uniform properties finally judge whether the ceramics of samples 1 to 7 are qualified. The combination is disqualified. Qualified by 'do not satisfy the above article are the capacitance dielectric loss _ ^ P2.5% strength above the floor then feed the wettability - L_〇 ~ 1, ...,, Shang a slave die of hunger Pat% solids bucket square pole Cape 7 丄 有 量 0. lwt ^ 0. 0wt% Of the range 2 ~ 7, Bl2203 of eight 枓 2 ~ 6, judged to be qualified
2030-5288-PF(Ν);Ahddub.p t d 第10胃 567511 五、發明說明(8) 又,範圍以外之試料號碼均附加木。 <實驗2 > 首先,混合金屬粉、h ^ 導電性組合物。同先前之=塊以調製出5種 璃熔塊均使用S Γ 0 - β2 〇二貫1Τ1 ζ 〇金车屬二均使用c u粉’思玻 k入曰 23 Α12〇3 — ZnO系玻璃。相對於金屬 ^王1之玻璃熔塊之含有量為〇· 〇wt%,〇· ,2· 5wt%, .=及7.〇Wt% ’相對於金屬粉全量之^之含有量均為 Owt% ° 接下來以4 5種導電性組合物調製出5種導電糊狀 物。導電糊狀物之調製方法與先前之實驗丨相同。 然後’以該等5種導電糊狀物製作出試料8〜丨2之陶瓷 電谷το件。陶瓷電容元件之製作方法,與先前之實驗1相 同。 再針對試料8〜1 2之陶瓷電容元件,測定其電容、介質 損耗、及電容電極對陶瓷介質材料基體之接著強度。實驗 結果示於下述表2。 【表2】 S料號碼 — * 8 9 1 0 11 * 1 2 金屬粉 Cu Cu Cu Cu Cu 玻璃溶塊之含有童〔wt% ] 0.0 0.1 2.5 5.0 7Ό Bi2〇3之含有置〔wt% ] 2.0 2.0 2.0 2.0 2Ό 電容〔nF〕 1.18 1.16 1.14 1.10 0.80 傾損耗〔%τ 1.59 1.61 1.60 172 2.21 接著強度〔Kgf〕 0.75 1.95 3.06 3.29 4.32 焊料濡濕性 〇 〇 〇 〇 〇 合否判斷 不合格 合格 合格 合格 不合格2030-5288-PF (N); Ahddub.p t d 10th stomach 567511 V. Description of the invention (8) In addition, the sample numbers outside the range are attached with wood. < Experiment 2 > First, metal powder and h ^ conductive composition were mixed. The same as the previous = block to prepare 5 kinds of glass frit. All use S Γ 0-β2 〇 two consecutive 1T1 ζ 〇 gold car genus two use c u powder 'Sibo kinyu 23 Α12〇3 — ZnO series glass. The content of the glass frit relative to the metal ^ Wang 1 is 0.00% by weight, 〇 ·, 2.5% by weight,. =, And 7.0% by weight. 'The content of ^ relative to the total amount of metal powder is Owt. % ° Next, 5 kinds of conductive pastes were prepared with 4 or 5 kinds of conductive compositions. The modulation method of the conductive paste is the same as the previous experiment. Then, ceramic ceramic valleys το of samples 8 to 2 were made from the five kinds of conductive pastes. The manufacturing method of the ceramic capacitor element is the same as the previous experiment 1. For ceramic capacitor elements of samples 8 to 12, the capacitance, dielectric loss, and adhesion strength of the capacitor electrode to the ceramic dielectric material substrate were measured. The experimental results are shown in Table 2 below. [Table 2] S material number — * 8 9 1 0 11 * 1 2 The content of metal powder Cu Cu Cu Cu Cu glass lumps [wt%] 0.0 0.1 2.5 5.0 7Ό Bi2 03 content [wt%] 2.0 2.0 2.0 2.0 2Ό Capacitance [nF] 1.18 1.16 1.14 1.10 0.80 Dip loss [% τ 1.59 1.61 1.60 172 2.21 Adhesive strength [Kgf] 0.75 1.95 3.06 3.29 4.32 Wetability of solder
567511567511
五、發明說明(9) 如上述,相對於金屬粉全量之玻璃熔塊之含有量以5 〇wt%以下為佳。第6圖顯示玻璃熔塊之含有量與電容之· 係。如圖不,玻璃熔塊之含有量為5. 〇wt%以下時,電六 致止於一定範圍之内。相對地玻I大 熔塊之含有量大於5.0wt%時,電容急劇降低。亦即,在玻 璃熔塊之含有量=5. Owt%之附近,可視為存在有電容相 之臨界點。V. Description of the invention (9) As mentioned above, the content of the glass frit relative to the total amount of the metal powder is preferably 50 wt% or less. Figure 6 shows the relationship between the glass frit content and capacitance. As shown in the figure, when the content of the glass frit is 5.0% by weight or less, the electric six will stop within a certain range. Relative to the ground glass I large frit content is greater than 5.0wt%, the capacitance decreases sharply. That is, in the vicinity of the content of the glass frit = 5.0 wt%, it can be considered that there is a critical point of the capacitive phase.
第7圖顯示玻璃熔塊之含有量與介質損耗之關係。如 圖示,玻璃熔塊之含有量為5· Owt%以下時,介質損耗大致 止於一定範圍(1· 59%〜1 · 72% )之内。相對地,玻璃炫塊 之含有量大於5 · 〇w t %時,介質損耗急劇增大。亦即,在相 璃熔塊之含有量=5· Owt%之附近,可視為存在有介質損教 相關之臨界點。 、 如上所述,相對於金屬粉全量之玻璃熔塊之含有量以 〇 · 1 W t %以上為佳。第8圖顯示玻璃熔塊之含有量與接著強Figure 7 shows the relationship between the glass frit content and the dielectric loss. As shown in the figure, when the glass frit content is less than 5.0 wt%, the dielectric loss is approximately within a certain range (1.59% to 1.72%). In contrast, when the content of the glass block is greater than 5.0wt%, the dielectric loss increases sharply. That is, in the vicinity of the content of the glass frit = 5 · Owt%, it can be considered that there is a critical point related to medium damage education. As mentioned above, it is preferable that the content of the glass frit with respect to the entire amount of the metal powder is not less than 0.1 W t%. Figure 8 shows the glass frit content and adhesion
度之關係。如圖示,接著強度隨玻璃熔塊之含有量之增大 而增大。陶瓷電容元件為確保其信賴度,電容電極對陶竞 介質材料基體之接著強度,最低限度要約1 · 〇 〇 κ g f。當玻 璃熔塊之含有量達〇· 1 wt%以上時,確實可得1 · 〇 〇Kgf以上 之接著強度。 最好的情況是’將玻璃炫塊之含有量定於2 · 5 w t %以 上。當玻璃熔塊之含有量達2.5wt%以上時,可得3.〇6Kgf 以上之高接著強度。 然後,對試料8〜1 2之陶瓷電容元件,評估其電容電極Degree relationship. As shown, the bonding strength increases as the glass frit content increases. In order to ensure the reliability of the ceramic capacitor element, the minimum adhesion strength of the capacitor electrode to the substrate of the ceramic dielectric material is about 1 · 〇 κ g f. When the content of the glass frit reaches 0.1 wt% or more, a bonding strength of 1.0 kgf or more can be obtained. The best case is to ‘set the content of the glass block to 2.5 wt% or more. When the content of the glass frit reaches 2.5 wt% or more, a high adhesive strength of 3.06 Kgf or more can be obtained. Then, for the ceramic capacitors of samples 8 to 12, the capacitor electrodes were evaluated.
第12頁Page 12
567511 五、發明說明(10) 焊料濡濕性之評估方法與先 之焊料濡濕性(參照表 前之實驗1相同。 參照表2 ,本發明笳阁 孕已圍内之試料9〜〗?夕^ 件,其電容電極之焊料濡、胃e 1 2之陶瓷電容 r τ展濕性均為良好。 最後,對試料8〜12之陶瓷 合 -Τ·丨,必七土伽止义《V — 文電谷兀件進订合否判斷 否判斷方法與先刖之貫驗1相同。 J斷 參照,2 ,則本發明範圍内之試料9〜12之中 塊之含有量為〇· lwt%〜5· 〇wt%範圍之試料9〜u,經熔 合格。又,範圍以外之試料號碼均附加*。、’斷為 <實驗3 > 首先,混合金屬粉、玻璃熔塊、及Bi2〇3以調 導電性組合物。金屬粉使用7Cu粉或“粉。破螭熔塊則均 使用了 SrO — B2〇3 — A丨2〇3 — ZnO系玻璃。相對於金屬粉全量 之玻璃熔塊之含有量均為2· 5wt%,相對於金屬粉全77量 Bi2 03之含有量則均為2. Owt%。 β王里 進一步,以該等2種導電性組合物調製了 2種導電糊 狀物。導電糊狀物之調製方法與先前之實驗1相同。 然後,使用該等2種導電糊狀物製作了試料丨3、丨4之 陶瓷電容元件。陶瓷電容元件之製作方法與先前之實驗i 相同。、 再來’對試料1 3、1 4之陶瓷電容元件,測定其電容、 介質損耗、電容電極對陶瓷介質材料基體之接著強度、及 電容電極之焊料濡濕性。最後,作合否判斷。該等^定及 合否判斷之方法均與先前之實驗1相同。實驗結果示於^下 567511 五、發明說明(11) 述表3。 【表3】 试料號碼 13 14 金屬粉 Cu Ag 玻璃纖之含有童〔wt%〕 2.5 2.5 Bl2〇3之含有童〔Wt%〕 2.0 2.0 電容〔nF〕 1.14 1.10 傾損耗〔%〕 1.60 1.70 接著強度〔Kgf〕 3.06 2.35 焊料濡濕性 〇 〇 _ 合否判斷 合格 合格 表3裏,比較使用cu粉之試料1 3及使用Ag粉之試料1 4 可知’即使是Ag粉之試料14,亦可得使ffiCu粉之試料13之 相同結果。 因此=推測’即使是使用Cu粉及Ag粉之混合物之情況 下’亦可付如單獨使用Cu粉之試料1 3,及單獨使用Ag粉之 試料1 4之相同結果^。 —一第9圖^系平面圖,顯示第1圖及第2圖所圖示之陶瓷電 谷凡件之焊接製裎,第1 〇圖係沿著第9圖X — X線之放大 截i面圖。如上 建’由於電容電極2 1、2 2之焊料濡濕性良 好,如第9圖及楚! π门567511 V. Description of the invention (10) The method of evaluating the solder wettability is the same as that of the previous solder wettability (refer to Experiment 1 before the table. Refer to Table 2) The sample 9 ~ in the enclosure of the present invention is included? The solder electrode 电容 of the capacitor electrode and the ceramic capacitor r τ of the stomach e 1 2 have good wettability. Finally, for samples 8 to 12 of the ceramic composite-T · 丨, it must be called "V — Wen Dian The method for determining whether the pieces are in order is the same as that of the previous test 1. J refers to 2, and the content of the blocks in samples 9 to 12 within the scope of the present invention is 0 · lwt% ~ 5 · 〇 Samples 9 to u in the wt% range are qualified after melting. In addition, sample numbers outside the range are appended with *., 'Break < Experiment 3 > First, mix metal powder, glass frit, and Bi203 to adjust Conductive composition. 7Cu powder or "powder" is used for metal powder. SrO — B2O3 — A 丨 2〇3 — ZnO glass is used for broken frit. The content of glass frit relative to the total amount of metal powder Both are 2. 5wt%, and the content of Bi2 03 relative to the total amount of metal powder 77 is 2. Owt%. Two kinds of conductive compositions prepared two kinds of conductive pastes. The method for preparing the conductive pastes was the same as in the previous experiment 1. Then, ceramics of samples 丨 3 and 丨 4 were prepared using these two kinds of conductive pastes. Capacitor element. The manufacturing method of ceramic capacitor element is the same as that of the previous experiment i., Again, for the ceramic capacitor element of samples 1 3, 1 and 4, measure its capacitance, dielectric loss, adhesion strength of capacitor electrode to ceramic dielectric material substrate, And the solder wettability of the capacitor electrode. Finally, make a judgment of suitability. The methods of these determinations and suitability are the same as the previous experiment 1. The experimental results are shown in the following 567511 V. Description of the invention (11) Table 3. Table 3] Sample No. 13 14 Metal powder Cu Ag glass fiber containing children [wt%] 2.5 2.5 Bl2 03 containing children [Wt%] 2.0 2.0 Capacitance [nF] 1.14 1.10 Dip loss [%] 1.60 1.70 Adhesive strength [Kgf] 3.06 2.35 Wetability of solder 〇〇_ Pass or fail In Table 3, compare sample 1 3 using cu powder and sample 1 4 using Ag powder. It can be seen that even with sample 14 of Ag powder, ffiCu can be obtained. The same result was obtained for powder sample 13. Therefore, it is speculated that 'even in the case of using a mixture of Cu powder and Ag powder', the same results can be obtained as for Sample 1 3 using Cu powder alone, and for Sample 14 using Ag powder alone. Results ^. — Figure 9 is a plan view showing the welding system of the ceramic electric valley as shown in Figure 1 and Figure 2. Figure 10 is an enlargement along the X-X line of Figure 9 Section i-plane view. Built as above 'because the solder of the capacitor electrodes 2 1, 2 2 has good wettability, as shown in Figure 9 and Chu! π gate
久第1 〇圖所示,能夠容易地將線導體3 1、32 焊接於電谷電極? 1 〇 〇 ^ ^ 焊接於電容電極乂2二丄,利用焊料41將線導體31 電容電極22之表』之利;9焊料42將線導體32焊接於 衣面。焊料41、42使用例如鉛錫共晶焊料。 本發明之陶咨 〜β 是電谷兀件,可與感應器、電阻、電晶體 等其他電子電路开& &人 ,. ^ ^疋件組合,成為一體化構造。具體例,例As shown in Fig. 10 for a long time, can the wire conductors 3 1 and 32 be easily soldered to the electric valley electrode? 1 〇 ^ ^ Weld to the capacitor electrode 乂 22 乂, use the solder 41 to weld the wire conductor 31 to the capacitor electrode 22; 9 solder 42 to weld the wire conductor 32 to the garment surface. As the solders 41 and 42, for example, a lead-tin eutectic solder is used. The ceramic reference ~ β of the present invention is an electric valley element, which can be combined with other electronic circuits such as inductors, resistors, and transistors to form an integrated structure. Specific example
2030-5288-PF(N);Ahddub.ptd 第14頁 567511 五、發明說明(12) 如電容與感應器組合而成之LC濾波器。 如以上所述,根據本發明,可得下列效果。 (a)可提供,電容電極裏不含鉛成分之陶瓷電容元 件、及其所使用之導電性組合物。 (b )可提供,避免電容電極對陶瓷介質材料基體之 接著強度低下之陶瓷電容元件、及其所使用之導電性組合 物。 (c )可提供,避免電容低下及介質損耗增大之陶瓷 電容元件、及其所使用之導電性組合物。 參2030-5288-PF (N); Ahddub.ptd Page 14 567511 V. Description of the invention (12) LC filter composed of capacitor and inductor. As described above, according to the present invention, the following effects can be obtained. (a) A ceramic capacitor element containing no lead component in the capacitor electrode and a conductive composition used therein can be provided. (b) It is possible to provide a ceramic capacitor element with low strength, which avoids the adhesion of the capacitor electrode to the ceramic dielectric material substrate, and the conductive composition used therefor. (c) A ceramic capacitor element capable of preventing low capacitance and increased dielectric loss, and a conductive composition used therefor can be provided. Participate
2030-5288-PF(N);Ahddub.ptd 第15頁 567511 圖式簡單說明 關於本發明之其他目的、構成及優點,將參照實施型 態之附圖進一部具體說明。此處, 第1圖係顯示本發明陶瓷電容元件之一個實施型態的 平面圖。 第2圖係沿著第1圖I I — I I線之放大截面圖。 第3圖顯示B i2 03之含有量與電容之關係。 , 第4圖顯示Bi2 03之含有量與介質損耗之關係。 第5圖顯示B i2 03之含有量與接著強度之關係。 第6圖顯示玻璃熔塊之含有量與電容之關係。 第7圖顯示玻璃溶塊之含有量與介質損耗之關係。 第8圖顯示玻璃熔塊之含有量與接著強度之關係。 第9圖係平面圖,顯示第1圖及第2圖所圖示之陶瓷電 容元件之焊接製程。 第1 0圖係沿著第9圖X — X線之放大截面圖。 符號說明 1 陶瓷介質材料基體 11 外 面 12 外 面 21 電 容 電極 22 電 容電極 31 線 導 體 32 線 導體 41 焊 料 42 焊 料2030-5288-PF (N); Ahddub.ptd Page 15 567511 Brief description of the drawings With regard to other objects, structures, and advantages of the present invention, a detailed description will be given with reference to the drawings of the implementation mode. Here, FIG. 1 is a plan view showing an embodiment of the ceramic capacitor element of the present invention. Figure 2 is an enlarged cross-sectional view taken along line I I-I I in Figure 1. Figure 3 shows the relationship between the content of B i2 03 and the capacitance. Figure 4 shows the relationship between the content of Bi203 and the dielectric loss. Figure 5 shows the relationship between the content of B i2 03 and the bonding strength. Figure 6 shows the relationship between glass frit content and capacitance. Figure 7 shows the relationship between the content of glass frit and dielectric loss. Figure 8 shows the relationship between the glass frit content and the bonding strength. Fig. 9 is a plan view showing the welding process of the ceramic capacitor element shown in Figs. 1 and 2. Figure 10 is an enlarged sectional view taken along line X-X in Figure 9. DESCRIPTION OF SYMBOLS 1 Matrix of ceramic dielectric material 11 Outer surface 12 Outer surface 21 Capacitance electrode 22 Capacitance electrode 31 Wire conductor 32 Wire conductor 41 Solder 42 Solder
2030-5288-PF(N);Ahddub.ptd 第16頁2030-5288-PF (N); Ahddub.ptd Page 16
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JP4435710B2 (en) * | 2005-03-31 | 2010-03-24 | 日立粉末冶金株式会社 | Panel pin paint for cathode ray tube |
CN102592828A (en) * | 2011-01-11 | 2012-07-18 | 禾伸堂企业股份有限公司 | Ceramic capacitor structure |
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