201110159 六、發明說明： 【發明所屬之技術領域】 本發明是關於電極，尤其是關於在晶片電阻器中之前電 極及/或背電極。 【先前技術】 晶片電阻器通常具有基板、前電極及背電極，且亦具有 提供前電極與背電極間之電連接的端子。可使用例如導電 膏來形成前電極、背電極及端子。 關於晶片電阻器的技術文件包括下列文件。 曰本專利第2008-218022號揭示一具有高電鍍電阻的陶 瓷電容器端子，其包括作為銅導體膏之玻璃熔塊之兩種類 型的硼矽辞玻璃熔塊。此端子包括含有從3至10重量百分 比之Si02、從25至35重量百分比之B203、從50至65重量 百分比之ZnO、從0至5重量百分比之A1203及從1至5重量 百分比之Na20+Li20+K20的第一玻璃；及含有從30至45 重量百分比之Si02、從7至15重量百分比之B203、從20至30 重量百分比之ZnO、從0至5重量百分比之CaO、從0至5重 量百分比之A1203、從0至5重量百分比之Ti02、從3至10重 量百分比之Zr02及高達15重量百分比之Na20+Li20+ K208的第二玻璃。 曰本專利第H07(1995)-201506號揭示一具有抗焊錫浸析 性的晶片電阻器端子。此端子由以具有不良的焊接可濕性 且與電阻薄膜接觸之材料所製成的第一電極及以具有好焊 接可濕性且設置成重疊至少一部分的第一電極並與電阻薄 148560.doc 201110159 膜分離之材料所製成之第二電極所構成。 日本專利第ig(1998)韻419號揭示—具有絕佳抗焊錫浸 析性的晶片電阻n端子4料包括銀粉末、絲末、玻 璃熔塊及選自锡、隹乙、鍺、釕及銖之金屬的氧化物、焦綠 石（pyrochlore)或硼化物。 ' 曰日片電阻态之前電極係由玻璃塗層及樹脂塗層所覆蓋。 …' 而田在樹月曰塗層及端子之間形成間隙時或在玻璃塗層201110159 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to electrodes, and more particularly to prior electrodes and/or back electrodes in a wafer resistor. [Prior Art] A wafer resistor generally has a substrate, a front electrode, and a back electrode, and also has a terminal for providing electrical connection between the front electrode and the back electrode. The front electrode, the back electrode, and the terminal can be formed using, for example, a conductive paste. Technical documents on wafer resistors include the following documents. A ceramic capacitor terminal having a high plating resistance, which includes two types of boron enamel glass frits as a glass frit of a copper conductor paste, is disclosed in Japanese Patent Publication No. 2008-218022. The terminal comprises from 3 to 10 weight percent SiO 2 , from 25 to 35 weight percent B 203, from 50 to 65 weight percent ZnO, from 0 to 5 weight percent A 1203 and from 1 to 5 weight percent Na 20 + Li 20 +K20 of the first glass; and containing from 30 to 45 weight percent of SiO 2 , from 7 to 15 weight percent of B203, from 20 to 30 weight percent of ZnO, from 0 to 5 weight percent of CaO, from 0 to 5 weight A1203 of a percentage, TiO2 from 0 to 5 weight percent, Zr02 from 3 to 10 weight percent, and a second glass of up to 15 weight percent Na20+Li20+ K208. A wafer resistor terminal having solder leaching resistance is disclosed in Japanese Patent Laid-Open No. H07(1995)-201506. The terminal is made of a first electrode made of a material having poor solder wettability and in contact with the resistive film, and a first electrode having good solder wettability and disposed to overlap at least a portion and is thin with a resistor 148560.doc 201110159 The second electrode made of the membrane separation material. Japanese Patent No. ig (1998) No. 419 Reveals - Wafer Resistance n-terminal 4 material with excellent solder leaching resistance includes silver powder, silk powder, glass frit and selected from tin, antimony, bismuth, antimony and bismuth. An oxide of a metal, pyrochlore or boride. The electrode is covered by a glass coating and a resin coating before the resistance of the film. ...' while Tian is forming a gap between the coating and the terminal of the tree, or in the glass coating
或樹脂塗層中形成穸絡拉 ^ . α , B 褽縫時，削電極在晶片電阻器實施電鍍 或焊錫期間:因電銀溶液或焊錫而招致不利的影響。^ 如’來自已貫施之鎳電鍍的酸可透過該間隙或該等裂縫到 達電極’造成電極接合強度變差。亦有已知為「焊錫浸 析」的問題，”當實行焊接時，電極内之導電粉末⑽ :銅)透過間隙或裂縫溶出至炼化的焊錫中，造成電極之 電阻率上升。已提出之關於抗酸性或抗焊錫浸析性的揭示 内容包括上述的專糸丨令彼 从、y ^ 寻利文件。然而，這些專利文件所揭示的 '、關於，、有抗酸性或抗蟬錫浸析性的端子，且因此難以 直接應用在前電極，豆係由盥 ，、你田興製k鳊子之程序不同的程 斤裝成同樣地’在抗料浸析性與抗酸性間有所取捨。 亦即’增加抗焊錫浸析性會降低抗酸性，且相反地，增加 抗酸性會降低抗焊錫浸析性。 【發明内容】 因此，需要電極 者之晶片電阻器電 有這類性質之晶片 尤”疋賦有抗輝錫浸析性及抗酸性兩 極。因此，本發明之一目標在於提供具 電阻器電極。 I48560.doc 201110159 本發明是關於電極，尤其是關於晶片電阻器電極。此電 極係由包括導電粉末、無鉛玻璃熔塊及樹脂黏合劑之導電 膏所形成。用於形成電極之導電膏中的導電粉末為選自由 金、銀、鉑、鈀和其合金所組成之群組之金屬粉末的至少 一種類型。玻璃熔塊之特徵在於以介於1 : 3至5 :丨間的重 量比包括一至少含有二氧化矽（Si02)的第一玻璃熔塊及一 至少含有二氧化鈦（Ti〇2)的第二玻璃熔塊。第一玻璃熔塊 較佳的是具有包括從60至95重量百分比之Si〇2、從1〇至3〇 重量百分比之氧化硼（B203)及從0.5至10重量百分比之氧 化鋁（A1203)的組成物。第二玻璃熔塊較佳的是具有包括 從5至15重量百分比之Ti〇2、從4至20重量百分比之 B203、從5至25重量百分比之A1203及從5至25重量百分比 之氧化鋅（ZnO)的組成物。此外，用來形成本發明之電極 的導電膏較佳的是進一步包括選自由錫、銦、铑、釕及鍊 所組成之群组之金屬的氧化物。 形成本發明之晶片電阻器電極的方法包含以下步驟： (a)以一導電膏塗佈一絕緣基板，該導電膏係由下列所 組成： (I) —導電粉末，其為選自由金、銀、鉑、鈀和其 合金所組成之群組之金屬粉末的至少一種類 型； (II) —無鉛玻璃熔塊，其以介於1 : 3至5 : 1間的重 量比包括含有至少60重量百分比之Si02的一 第一玻璃熔塊及含有至少5重量百分比之Ti02 148560.doc 201110159 的一第二玻璃熔塊；及 (Π〇 —樹脂黏合劑；及 (b)以800至9〇(TC燒製已施加至兮奶祕並此L认斗 主该％緣基板上的該導電 膏。 由於藉由這類步驟形成的晶片電阻器電極具有抗焊錫浸 析性及抗酸性兩者’即使在電極上之—玻璃塗層與電阻器 上之-端子間出現間隙，仍可抑制對晶片電阻器之 的不利影響。 【實施方式】 當本發明中之導電膏如此處所指定般包括一導電粉末 一玻璃熔塊及一選用的金屬氧化物時，發現藉由燒製此導 =所得的電極具有改善的抗焊錫浸析性及改善的抗 兩者。下文敘述本發日月之W電阻器f極及形成這 極之方法。 貝电 L電極 本發明是關於電極，尤其是關於晶片電阻器電極 明之電極係由一導電膏形成，該導電膏包括 =玻璃溶塊及一樹脂黏合劑，並可進一步包括二 的金屬氧化物。 遠用 首先’敛述使用一導雷喜*报士认φ 導雷於古 ^ $ ^成的電極，該導電膏包括— 勺^末、-無料魏塊及—樹㈣合劑，並可進^ 匕選用的金屬氧化物。本發明之f極， 乂 阻器電極，即不受任何關於形狀、電極厚度及复：：片電 特殊限制。一特定實 ”他條件的 '例為—類似圖1所示的晶片電阻器電 148560.doc 201110159 極。本發明之電極使用圖}的晶片電阻器作為一實例敘 述。 舉例來說，晶片電阻器電極為一類似圖丨所示之前電極2 及背電極3的電極。前電極2及背電極3設置在基板2之頂側 及月側上的相對位置。接著，參照圖〗，敘述晶片電阻器 除了電極外的元件。晶片電阻器具有基板卜如上文所提 及’前電極2及背電極3係設置在基板}之頂側及背側上， 並乂电阻薄膜4覆盍部分的前電極2。用於電連接前電極2 =背電極3的端子5係以覆蓋部分的這些電極的這—類方式 又置在基板1的-側壁上。玻璃塗層6及樹脂塗層7係設置 在電阻薄膜4之表面上，以覆蓋電阻薄膜4。此外，設置一 鎳電鍍層或錫電鐘層（未圖示）’以覆蓋暴露的端子5。晶片 電阻器以熔化的焊錫接合至電路基板上放置端子之一端子 =域。在本發明中’將一包括-導電粉末、-無錯玻璃熔 鬼及一樹脂黏合劑以及逸—牛七ee. 汉進步包括一選用之金屬氧化物的 導電膏用作電極材料。除了晶片電阻器中之電極外的材料 H習用材料，且不受任何特殊_。舉例純，倘若基 板1為一絕緣基板，則盆爲 /、又任何特殊限制。經由說明， 用-濛土基板、陶竟基板或玻璃基板。電阻薄膜何 错由印刷並燒製一習用含釘氧化物的電阻膏而形成，端子 5了藉由印刷並燒製一習 -s , 一 為用導电T而形成，且玻璃塗層6及 曰塗層7可藉由分別印刷並燒製_ @ 膏而形成。 ^ I用玻璃膏及一樹脂 使用本發明之導電奮所和+ & & 所形成的電極可用作晶片電阻器上 148560.doc 201110159 处月J ^極2及月電極3兩者。由於前電極之比背電極3更有可 焊錫接觸，較佳的是至少使用本發明之電極作為前電 極2 〇 下文敘述用於本發明之導電膏的組成物。 (1) 導電粉末 用於本發明的導電粉末為選自由金、銀、鉑、鈀和其人 金組成之群組之貴金屬粉末的至少—種類型。較佳的是使 u低傳導電阻及良好焊錫可濕性的銀粉末，尤其是可 氧化性燒製之銀粉末與抑制銀遷移之鈀粉末的混合物。導 電粉末可為片狀、球狀或非晶質的形式。當導電粉末用在 音通導電膏中_，導電粉末的粒度對粉末的燒結性質有影 響。舉例來說，具有大粒度之銀粉末比具有較小粒度之銀 粉末更慢燒結。導電粉末之粒度因而根據燒結輪廓來選 擇。然而，考量到可分散性及可印刷性，平均粒度（D5〇， 雷射散射型粒度分布分析器）較佳的是從〇丨至^ μηι。小於 〇·1 μπι的粒度使電極材料内的可分散性變差，結果便無法 達到足夠電極強度。另一方面，超過5 的粒度可使導電 膏在例如網版印刷期間導致堵塞發生。倘若導電膏内之導 電粉末的含量為能夠達成本發明目標的量，則該含量不受 任何特殊限制。然而，當導電粉末為銀及鈀粉末之混合物 時’基於導電膏重量的導電粉末含量較佳的是從65至9〇重 量百分比，更佳的是從70至80重量百分比。 (2) 玻璃熔塊 本發明所用的玻璃熔塊作用如一無機黏合劑，幫助在燒 148560.doc 201110159 衣乂驟d間燒結導電膏，亦有助於抗谭錫浸析性。本發明 的玻璃炼塊於燒結時會液化，且藉由將之納人—具有不規 則表面之礬土基板上的本地凹部中並固化，其作用如導致 電極與基板黏著的楔子，除此之外，其亦有助於抗酸性。 因此可在所用的燒結溫度下使用—具有足夠黏度和玻璃 流動性的玻璃熔塊。在導電膏燒結前的狀態下，本發明的 電極包括具有不同組成物之—第-玻璃炫塊和-第二玻璃 熔塊。這些玻璃為氧化物玻璃，且包括至少一種類型之選 自本身能夠玻化之稱為「玻璃成形氧化物」者，亦即，Or when the resin coating is formed, the α, B quilting, the electrode is subjected to electroplating or soldering during the wafer resistor: adverse effects are caused by the silver oxide solution or the solder. ^ If the acid from the nickel plating that has been applied can pass through the gap or the cracks reach the electrode, the electrode bonding strength is deteriorated. There is also a problem known as "solder leaching". When the welding is performed, the conductive powder (10): copper in the electrode is eluted into the refining solder through the gap or the crack, resulting in an increase in the resistivity of the electrode. The disclosures on acid resistance or solder leaching include the above-mentioned specializations, and the documents disclosed in the patent documents, however, are resistant to acid or anti-smear leaching. Sexual terminals, and therefore difficult to apply directly to the front electrode, the bean system is made of 盥, and the process of your Tian Xing k 鳊 不同 装 装 装 装 装 装 同样 同样 同样 同样 同样 同样 同样 同样 同样 取 取 取 取 取 取 取 取 取 取 取 取 取That is, increasing the solder leaching resistance reduces the acid resistance, and conversely, increasing the acid resistance reduces the solder leaching resistance. [Invention] Therefore, the wafer resistor of the electrode is required to have a wafer of such a property. The special "endowment" has anti-purin leaching and acid resistance. Accordingly, it is an object of the present invention to provide a resistor electrode. I48560.doc 201110159 The invention relates to electrodes, in particular to wafer resistor electrodes. This electrode is formed of a conductive paste including a conductive powder, a lead-free glass frit, and a resin binder. The conductive powder in the conductive paste for forming the electrode is at least one type selected from the group consisting of metal powders composed of gold, silver, platinum, palladium, and alloys thereof. The glass frit is characterized by comprising a first glass frit containing at least cerium oxide (SiO 2 ) and a second glass containing at least titanium dioxide (Ti 2 ) in a weight ratio of 1:3 to 5:丨Frit. The first glass frit preferably has from about 60 to 95 weight percent of Si 2 , from 1 to 3 weight percent of boron oxide (B203), and from 0.5 to 10 weight percent of alumina (A1203). Composition. The second glass frit preferably has from 5 to 15 weight percent Ti 2 , from 4 to 20 weight percent B203, from 5 to 25 weight percent A 1203, and from 5 to 25 weight percent zinc oxide ( The composition of ZnO). Further, the conductive paste used to form the electrode of the present invention preferably further comprises an oxide of a metal selected from the group consisting of tin, indium, antimony, bismuth and chains. The method of forming the wafer resistor electrode of the present invention comprises the steps of: (a) coating an insulating substrate with a conductive paste, the conductive paste being composed of: (I) - a conductive powder selected from the group consisting of gold and silver. At least one type of metal powder of the group consisting of platinum, palladium and alloys thereof; (II) - lead-free glass frit comprising at least 60 weight percent in a weight ratio between 1:3 and 5:1 a first glass frit of SiO 2 and a second glass frit containing at least 5 weight percent of Ti02 148560.doc 201110159; and (Π〇-resin binder; and (b) 800 to 9 〇 (TC burnt) The conductive paste has been applied to the 兮 milk secret and this L is the main edge of the substrate. Since the wafer resistor electrode formed by such a step has both solder leaching resistance and acid resistance, even at the electrode The gap between the glass coating and the terminal on the resistor can still suppress the adverse effect on the chip resistor. [Embodiment] The conductive paste in the present invention includes a conductive powder-glass as specified herein. Frit and a metal of choice In the case of the compound, it was found that the electrode obtained by firing the lead had improved solder leaching resistance and improved resistance. The following describes the f-pole of the resistor and the method of forming the pole. L Electrode The present invention relates to an electrode, and particularly to an electrode of a wafer resistor electrode, which is formed of a conductive paste comprising a glass frit and a resin binder, and further comprising a metal oxide of two. First of all, 'consider the use of a guide Lei Xi * reporter recognizes φ lead to the ancient ^ ^ ^ into the electrode, the conductive paste includes - spoon ^ end, - no material Wei block and - tree (four) mixture, and can be selected Metal oxide. The f-electrode of the present invention, which is not subject to any special restrictions on shape, electrode thickness and complex: sheet power. A specific example of "the condition" is similar to that shown in Figure 1. The chip resistor is 148560.doc 201110159. The electrode of the present invention is described as an example using the wafer resistor of Fig. 1. For example, the chip resistor electrode is a similar electrode 2 and the back electrode 3 as shown in the figure. Electrode. Front electrode 2 and The back electrode 3 is disposed at a relative position on the top side and the moon side of the substrate 2. Next, an element other than the electrode of the wafer resistor will be described with reference to the drawing. The wafer resistor has a substrate as described above for the 'front electrode 2 and The back electrode 3 is disposed on the top side and the back side of the substrate, and the front electrode 2 of the resistive film 4 is covered. The terminal 5 for electrically connecting the front electrode 2 = the back electrode 3 is covered with these electrodes. This type is placed on the sidewall of the substrate 1. A glass coating 6 and a resin coating 7 are provided on the surface of the resistive film 4 to cover the resistive film 4. Further, a nickel plating layer or tin plating is provided. A clock layer (not shown) is used to cover the exposed terminals 5. The wafer resistors are bonded with molten solder to one of the terminal terminals of the terminal on the circuit substrate. In the present invention, a conductive paste comprising a conductive powder, a --free glass frit and a resin binder, and Yi-Niuqie ee. Material H is used in addition to the electrodes in the wafer resistor and is not subject to any special _. For example, if the substrate 1 is an insulating substrate, the basin is / and any special limitation. By way of illustration, a -montene substrate, a ceramic substrate or a glass substrate is used. What is wrong with the resistive film is formed by printing and firing a conventional resistor containing a nail oxide, the terminal 5 is formed by printing and firing, and the conductive layer T is formed, and the glass coating 6 and The ruthenium coating 7 can be formed by separately printing and firing a _@ paste. ^ I Use Glass Paste and a Resin The electrode formed using the conductive device of the present invention and + && can be used as both a JJ pole 2 and a moon electrode 3 at the wafer resistor 148560.doc 201110159. Since the front electrode is more solderable than the back electrode 3, it is preferred to use at least the electrode of the present invention as the front electrode 2 下文 The composition of the conductive paste used in the present invention will be described below. (1) Conductive powder The electroconductive powder used in the present invention is at least one type selected from the group consisting of precious metal powders composed of gold, silver, platinum, palladium, and its human gold. Preferred are silver powders having a low conductive resistance and good solder wettability, especially a mixture of an oxidizable fired silver powder and a silver-reactive palladium powder. The conductive powder may be in the form of a sheet, a sphere or an amorphous. When the conductive powder is used in the acoustic conductive paste, the particle size of the conductive powder affects the sintering property of the powder. For example, a silver powder having a large particle size is sintered more slowly than a silver powder having a smaller particle size. The particle size of the conductive powder is thus selected according to the sintering profile. However, considering the dispersibility and printability, the average particle size (D5 〇, laser scattering type particle size distribution analyzer) is preferably from 〇丨 to ^ μηι. A particle size smaller than 〇·1 μm makes the dispersibility in the electrode material worse, and as a result, sufficient electrode strength cannot be obtained. On the other hand, a particle size of more than 5 causes the conductive paste to cause clogging during, for example, screen printing. If the content of the conductive powder in the conductive paste is an amount capable of achieving the object of the present invention, the content is not subject to any particular limitation. However, when the conductive powder is a mixture of silver and palladium powder, the content of the conductive powder based on the weight of the conductive paste is preferably from 65 to 9 weight percent, more preferably from 70 to 80 weight percent. (2) Glass frit The glass frit used in the present invention acts as an inorganic binder to help sinter the conductive paste during the firing of 148560.doc 201110159, and also contributes to the resistance to tan leaching. The glass refining block of the present invention liquefies upon sintering and is cured by a local recess on a bauxite substrate having an irregular surface, such as a wedge that causes the electrode to adhere to the substrate, in addition to In addition, it also contributes to acid resistance. It is therefore possible to use at the sintering temperature used - a glass frit with sufficient viscosity and glass flow. The electrode of the present invention comprises a first-glass block and a second glass frit having different compositions in a state before the conductive paste is sintered. These glasses are oxide glasses and include at least one type selected from the group consisting of "glass-forming oxides" which can be vitrified by themselves, that is,
Si02 B203、P205及Ge02 ’或本身不玻化但在用於多成 刀^/式中玻化的輔助玻璃成形氧化物，亦即，Ti〇2、Si02 B203, P205 and Ge02' or auxiliary glass forming oxides which are not vitrified but are used for vitrification in multi-forms, ie Ti〇2
Te〇2、A1203、B203、V205、Sb203、Cu〇 及 Zn〇。此 外，亦可包括不玻化但使玻璃特性產生變化之稱為「改良 劑」之至少一種類型的氧化物，其選自Li〇、Na2〇、 K20、MgO、Ba〇、Ca0及Sr〇。本發明之玻璃溶塊不包括 鉛。 基於第一玻璃熔塊之重量，本發明之第一玻璃熔塊含有 至少60重量百分比的Si〇2。基於第一玻璃炫塊之重量，包 括在第一玻璃熔塊中之Si02的量較佳的是從6〇至95重量百 分比’更佳的是從65至90重量百分比。如下文敘述之實例 中所示，使用含有大量Si02之玻璃作為電極材料可獲得抑 制因電鍍造成之電極剝離的效應。除了 Si〇2之外，第一坡 璃熔塊亦包括上述玻璃成形劑及輔助玻璃成形劑。B2〇3 為最佳的玻璃成形劑。A1203為較佳的輔助玻璃成形劑。 148560.doc 201110159 基於第一玻璃熔塊之重量，B2〇3的含量較佳的是從1〇至 3〇重量百分比，更佳的是從15至25重量百分比。基於第一 玻璃熔塊之重量，A1203的含量較佳的是從0.5至10重量百 分比’且更佳的是從1至5重量百分比。第一玻璃熔塊可包 括至少一種類型之來自Li〇、Na20及K20的鹼金屬氧化 物’以作為改良劑。基於第一玻璃熔塊之重量，改良劑含 量較佳的是從1至10重量百分比，且更佳的是從3至8重量 百分比。不過，第一玻璃熔塊不包括Ti〇2。 基於第二玻璃熔塊之重量，本發明之第二玻璃熔塊含有 至少5重量百分比的ή〇2。包括在第二玻璃熔塊中之Ti〇2 的董較佳的是從5至15重量百分比，且更佳的是從6至1〇重 量百分比。若玻璃中的Ti02含量低，則可削弱防止銀從電 極浸析的效應。另一方面，由於Ti〇2本身不會玻化，包括 太多會阻礙玻璃熔塊的形成。除了 Ti02外，第二玻璃熔塊 亦可包括上述玻璃成形劑及輔助玻璃成形劑。B203為最 佳玻璃成形劑。基於第二玻璃熔塊之重量，B203的含量 較佳的是從4至20重量百分比，且更佳的是從5至15重量百 分比。A1203及ZnO為最佳的輔助玻璃成形劑。基於第二 破璃熔塊之重量，A1203的含量較佳的是從5至25重量百分 比’且更佳的是從8至15重量百分比。基於第二玻璃熔塊 之重量，ZnO的含量較佳的是從5至25重量百分比，且更 佳的是從10至20重量百分比。第二玻璃熔塊可包括選自 LiO、Na20、K20、MgO、BaO及 CaO 的至少一個，以作 為改良劑。基於第二玻璃熔塊之重量，改良劑含量從1至 148560.doc • 10 - 201110159 30重1百分比。第二玻璃溶塊可包括μ〇2作為玻璃成形 劑。在這一類情況下，第二玻璃熔塊與第一玻璃熔塊的區 別在於基於第二玻璃熔塊的重量，Si〇2的含量不超過40重 量百分比。 第一玻璃熔塊對第二玻璃熔塊的重量比係從1 : 3至5 : 1，且較佳的是從1 : 1至4 : 1。如實例所示，單獨使用第 一玻璃熔塊或第二玻璃熔塊難以達成電極中之抗焊錫浸析 性及抗酸性兩者。不過，發現當以1 : 3至5 : 1的重量比一 起使用這些玻螭時，抗焊錫浸析性及抗酸性兩者傾向於可 達成。導電膏内之玻璃熔塊的含量不受任何特殊限制。如 κ例所示，藉由使用第一玻璃熔塊及第二玻璃熔塊的摻和 物甚至疋不同玻璃熔塊含量也可達成抗焊錫浸析性及抗 酸性兩者°在本發明中，基於導電膏的重量，較佳的玻璃 ^含量係、從^重量百分比4導電膏内之玻璃溶塊 含量小於1重量百分比時’ #由燒製導電f所形成之電極 有^會與基板分離。另—方面，在玻㈣塊含量超過⑺ 重S百分比時’有可能將阻礙電極的導電性。欲進一步增 強抗焊錫浸析性及抗酸性’基於導電膏之玻璃熔塊含量^ 佳的是田從⑴重量百分比。在實例中（表3)，當玻璃含量為 重量百刀比時，抗烊錫浸析性及抗酸性傾向為差。 在本發明中，玻璃熔塊的粒度不受任何特殊限制。狭 L希望玻璃熔塊粒子之平均粒度（⑽，雷射散射型粒度 二分析器)位於從_的範圍中。在小於❹… 時，導電膏内不輕易發生均勾分散。另_方面，在大於1〇 148560.doc 201110159 μιη的粒度下，導電膏在例如 胃你』網版印刷期間可導致堵塞發 生。 如上文所述，本發明之特徵在於使用具有Μ組成物的 玻璃炫塊掺和物來增強晶片電阻器電極的抗焊錫浸析性及 抗酸性。 (3)金屬氧化物 本發明的電極可進一步包括一金屬氧化物，該金屬選自 錫、銥、铑、釕和鍊。由於這些金屬氧化物不輕易遭受焊 錫浸析並具有導電性，在一添加這—類金屬氧化物的電極 中’即使導電粉末因焊錫浸析溶出，亦可使導電性下降最 小化。用在本發明中的金屬氧化物包括例如下列。 (1) 銥氧化物：Ir203、Ir〇2(銥焦綠石：Pb2Ir207、 Bi2Ir207、Lu2Ir207); (2) 铑氧化物：Rh203、Rh02、Rh03(铑焦綠石： Pb2Rh207、Bi2Rh207、T12Rh207); (3) 釕氧化物：Ru02 ' Ru03、Ru04(釕焦綠石： Pb2Ru207、Bi2Ru207、T12Ru207); (4) 銖氧化物：Re203、Re03、Re207 ; (5) 錫氧化物：SnO、Sn〇2 ; (6) 硼化物：LaB6、Ni3B、Ni2B。 其他釕焦綠石氧化物在日本專利第2006·054495號及美 國專利說明書第3,583，93 1號中詳細陳述。 可單獨添加這些金屬氧化物或可添加二或多個這些金屬 氧化物的摻和物。使用相對便宜錫氧化物（Sn〇或Sn〇2)為 148560.doc 12 201110159 最佳的。金屬氧化物可為 同上述導mQ 球肤或非晶質的形式。如 物二到可分散性及可印刷性，金屬氧化 物的平均粒度（D50，雷 至屬巩化 是從mo μιη，更佳的、型粒度分布分析器）較佳的 粒度下，導電客在例如6 X 0.5至5 Mm。在超過10 —之 n h n 馮版印刷期間可導致堵塞發生。倘 :金屬氧化物的含量為能夠達成本發明目標的量，列.含 ::受任何特殊限制。然而，基於導電膏之重量，= ==佳的是從1至5·。重量百分比。藉由添加至少! 刀b即使發生焊錫浸析仍可維持導電性。缺而， 旦於：純化物可干擾導電粉末之燒結，當添加超過$重 里百分比時’會有電極之電阻率升高的風險。從導電性的 觀點來看，基於導雷息夕舌旦 泠电月之重莖，更佳的是金屬氧化物含量 不超過3重量百分比。 (4)樹腊黏合劑 在本發明中’導電粉末、玻璃熔塊之類係分散在一樹脂 黏合射，以產生具有半流體黏度之稱為「膏」的分散 物。藉由變成膏的形式，可印刷分散物，從而將之施加至 一礬土基板上。在本發明中，「樹脂黏合劑」一詞嚴格來 說指的是樹脂。然而，有時候會將__料調整黏度之溶劑 添加至樹脂，在此情況下，「樹脂黏合劑」的概念亦涵蓋 一樹脂與溶劑的混合物。雖然較佳的是通常用於膏中的乙 基纖維素（EC)，但用於本發明之樹脂不受任何特殊限制。 亦可使用諸如乙基羥乙基纖維素（ethyl hydfQxyethyi cellulose)、木松香（w〇〇d r〇sin)、乙基纖維素… 148560.doc 13 201110159 cellulose)和酹酸樹脂（phen〇lic resins)的混合物、低級醇的 聚甲基丙稀酸酯（polymethacrylates of lower alcohols)及乙 —醇單乙酸酯的單 丁基醚（mon〇butyl ethers of ethylene glycol monoacetate)。為了調整黏度，可將一溶劑添加至 樹脂。泛用於膏中的溶劑包括萜烯（例如，α_或β_松脂 醇）、煤油、鄰苯二甲酸二丁酯、丁基卡必醇、二丁基卡 必醇、卡必醇醋酸鹽、丁基卡必醇醋酸鹽、己二醇及高沸 點醇和醇酯。結合並配製這些與其他不同溶劑，以達成特 定應用所需的黏度及揮發度。 較佳的是用於本發明之導電膏中的導電粉末'玻璃熔塊 及樹脂黏合劑的含量分別從59至9〇重量百分比、從1至ι〇 重置百分比及從9至40重量百分比。 接著’敘述一使用上述電極材料製造一導電膏的方法。 在本發明中，將上述導電粉末、第一玻璃熔塊、第二玻 璃熔塊及其他無機填充劑分散於藉由混合一樹脂及一溶劑 戶^寻之一樹脂黏合劑中，㈣能一具有半流體黏度之稱為 月」的刀政物產生。包括在導電膏組成物中之樹脂黏合 劑之重置與導電粉末、玻璃熔塊及金屬氧化物之結合重量 的比例可依所用的膏塗佈方法與樹脂黏合劑類型而變化。 —般而言，欲獲得良好覆蓋，導電膏將含有從6〇至91重量 百刀比的導電粉末、玻璃熔塊和金屬氧化物以及從9至 重量百分比的樹脂黏合劑。 接著，敛述形成本發明之電極的方法。I發明之電極形 成方法包含以下步驟： 148560.doc -14· 201110159 (a)以一導電膏塗佈一絕緣基板，該導電膏包含： (1)—導電粉末，其為選自由金、銀、鉑、鈀和其 合金所組成之群組之金屬粉末的至少一種類 型； (U)—無鉛玻璃熔塊，其以介於1 : 3至5 : !間的重 量比包括一含有至少60重量百分比之Si〇2的 第一玻璃熔塊及一含有至少5重量百分比之 Ti〇2的第二玻璃熔塊；及 (出）一樹脂黏合劑；及 ()乂 800至900 C燒製已施加至該絕緣基板上的該導電 膏。 本發明之電極可藉由將上述導電f塗佈至_給定基板或 ”物上，並將該導電膏與該基板或其前驅物共同燒 製而得到。電極的構造和其他必要的特徵結構係像上文針 對晶片電阻器電極所舉例的一樣。 電極形成方法的特定序列如下。本發明之方法首先包括 以導電膏塗佈-絕緣基板的步驟。塗佈導電膏之技術包括 例如網版印刷（其在印刷後產生從1〇至2〇 4瓜的薄膜厚 度）。倘若絕緣基板的材料為電絕緣，則其不受任何特殊 限制。舉例來說，可使用礬土基板或為馨土基板前驅物 生胚帶。 ^’以約咖至約刪以溫度在—氧化大氣中藉㈣ —電膏及絕緣基㈣燒結施加在絕緣基板上的電極材料 (導電膏）。燒製可使用諸如-能夠設定溫度輪摩之帶型連 148560.doc •15- 201110159 續爐或一箱型爐來實行。 將= 明之電極可最常用作-晶片電阻器電極。因此， 明之電極用作晶片電阻器 法係針對圖！所示的晶片電阻以 |例中的形成方 在其上具有本發明之電極丁裂造 例。 电K曰曰片電阻器之步驟的—實 本發明之方法包括將上述導電膏塗佈至 ^步驟。絕緣基板的材料具有電絕緣性質，則^ -壬何特殊限制。舉例來說，可使 其 前驅物的生胚帶。首先，特定舍佑皮 W土基板 相… 疋塗佈序列包括在基板1之頂 = 電極2(圖2A)。接著，形成電阻薄膜4,以便覆 盍此前電極2之一部分（圖2B)。接著，在基❸之背側上， 於-相對前電極2的位置上形成背電極3_。本發明可 用於前電極2及背電極3兩者。前電極2及背電泊可藉由例 ^網版印刷（於印刷後達到從1〇至2〇帅的薄膜厚度）上述 導電膏來形成。或者’形成可藉由首先將導電膏塗佈至聚 苯二甲酸乙二醋（ΡΕΤ)薄膜上達1〇至2〇 μιη的薄膜厚度缺 後將導電膏轉移至基板來實行。電阻薄膜4係藉由使用二、 諸如網版印刷的技術塗佈一電阻膏而形成。或者，電阻薄 膜4可藉由首先將-電阻膏塗佈至_ρΕΤ薄膜上，然後將電 阻膏轉移至基板來形成。 接著，燒結施加至絕緣基板上之電極與電阻薄膜❶具體 說來，在形成電連接前電極2及背電極3的端子5後（圖 2D)，兩個電極2和3、電阻薄膜4與端子5係以約8〇〇至約 148560.doc -16· 201110159 900 C在一氧化大氣中燒製。由於前電極2比背電極^更可 能與焊錫接觸，較佳的是將本發明的電極至少用作前電極 2 °端子5係藉由例如網版印刷、浸潰、滾輪塗佈或賤射導 電膏之技術來形成。端子5是以覆蓋部分的前電極2與部分 的背電極3 ’從而使兩個電極電連接的這一類方式形成。 結果的晶片電阻器電極接著藉由形成玻璃塗層6與樹脂 塗層7’以便覆蓋至少電阻薄膜4的表面而受到保護（圖 2E)。習用方法可用於形成玻璃塗層6與樹脂塗層7(參見例 如日本專利第刪叫加號的_5]段和日本專利第細4_ 33號的_〇]段）。接著，為了防止當焊接在谭錫流動 或回流步驟中於暴露的電極上實行時的電極浸析以及確保 焊接可靠性，-錦錄層之類係藉由電鑛形成（未顯示）。經 由上述步驟，可獲得本發明之晶片電阻器。 完成的晶片電阻器係以熔化焊錫固定在放置端子$之電 路基板的端子區域部。 攸上述日日片電阻器製造方法的每_操作亦可明白，本 明的電極係藉由下列步驟形成：⑷將本發明的導電膏塗佈 至一絕緣基板（例如，礬土基板或其前驅物）上；及 800至90(TC燒製已施加至該絕緣基板上的該導電膏。 藉由使用本發明的電極作為前電極2或背電極3，甚至a 這些電極已暴露至電鍍或焊接時，由於絕佳的抗酸性^ 佳的抗焊錫浸析性之故，可使所產生之缺陷 ㈣ 數目最小化。 电阻器的 實例 148560.doc -17· 201110159 本發明在下文經由實例更完整說明，然而該等實例並非 打算限制本發明的範圍。除非另加註解，指示成分比例的 數字代表重量百分比（wt%)。 導電膏之製備 表1所用的導電粉末、玻璃熔塊和金屬氧化物係在實例 中使用。膏内之第一玻璃熔塊和第二玻璃熔塊的個別含量 示於表2。導電膏中之導電粉末、玻璃熔塊及金屬氧化物 的結合含量係設定為80.0重量百分比，但玻璃熔塊含量及 銀粉末含量在不同膏中有所不同。因此，其他成分，即鈀 粉末、Sn02粉末及樹脂黏合劑的含量在所有膏中皆為相 同。具體說來’把粉末含置設定為〇·5重量百分比、sn〇 2 粉末含量設定為1 ‘5重量百分比且樹脂黏合劑含量設定在 2〇重量百分比。第一玻璃熔塊組成物含有713重量百分比 之Si〇2、2.1重量百分比之A1203及19.8重量百分比之 B203。第二玻璃熔塊組成物含有35 4重量百分比之Si〇2、 13.9重量百分比之A1203、8.2重量百分比之B2〇3、1〇 4重 量百分比之ZnO及8.9重量百分比之Ή〇2。量出個別特定量 的銀粉末、鈀粉末、玻璃熔塊、Sn02及樹脂黏合劑，並混 合為一混合物，然後在輥磨機中予以分散，從而製備導電 膏1至5。 148560.doc •18· 201110159 表1 組成物 性質 導電粉末 銀粉末 形狀：片狀，平均粒度(D50) : 1.5 μηι I巴粉末 形狀：片狀，平均粒度(D50) : 1.5 μηι 玻璃熔塊 平均粒度(D50) : 1.5 μηι Sn02粉末(3975, J.T. Baker Inc.) 平均粒度(D50) : 1.5 μιη 樹脂黏合劑 乙基纖維素和松脂醇的混合物 評估方法 參照圖3 ’敘述評估抗焊錫浸析性的方法。以圖3所示的 圖案8(線寬，〇.5 mm ;薄膜厚度’ 17 μιη)將導電膏1至5各 自網版印刷在96%的礬土基板9之上（25 mm長x25 mm寬 X0.64 mm厚）上，進行乾燥’然後燒製，從而形成電極1至 5。乾燥條件為15 0 °C、1 〇分鐘。燒製係以124 mm/分鐘的 帶速度在一電帶爐中實行。溫度輪廓為10分鐘低於 850°C、10分鐘850°C以及10分鐘高於850°C。結果的圖案8 與馨土基板9 一起浸沒在保持約220°C之溶化共炫體（Sn : Pb=62 : 36)中30秒。在浸沒之後’工件從熔化的焊錫移 除，電極1至5的電阻率則使用電阻率測量方法來測量，該 方法包括類似圖3所示之常用的4點探針技術。一數位多用 電表（R6581，由Advantest製造）係用作電阻率測量設備 10。結果示於表2。 參照圖4，敘述評估抗酸性及抗焊錫浸析性之方法。以 圖4所示的正方形圖案11(2.〇11111：1寬><2.〇111111長><17 0111厚）將 148560.doc -19- 201110159 導電膏1至5各自網版印刷在96%的礬土基板9(25 mm長χ25 mm寬χ〇.64 mm厚）之上’進行乾燥，然後燒製，從而提供 電極1至5。乾燥及燒製條件與上述相同。結果的正方形圖 案11與馨土基板9 一起浸沒在5%的硫酸水溶液中30分鐘。 在浸沒之後，將從水溶液移除的導體以水清洗，然後以 100°C進行15分鐘的乾燥。接著，為了測試接合強度，將 電線焊接至電極表面。在焊接之後，將焊接電線端和相對 多而附接至一張力測5式機器（Force Analyzer Explorer 2 FA1015A 1605NHTP ; Aiko Engineering)，以 12 mm/分鐘 的速率垂直拉動電線，並在電線分離時測量拉動值（接合 強度’ N)。結果示於表2。 將具有小於0.8歐姆之電阻率的電極評定為具有抗焊錫 改析性。將導體在浸沒於5%硫酸水溶液後的接合強度超 過20 N的電極評定為具有抗酸性。電極2及電極3具有抗焊 錫浸析性及抗酸性兩者。電極丨、4及5缺少抗焊錫浸析性 及抗酸性兩者的結合。 表2 電極編號 第一玻璃熔塊 (重量百分比） 第二玻璃熔塊 (重量百分比） 電阻率 (歐姆） 接合強度 (N) 1 3.4 0 0.7 19.6 4.0 1.0 0.8 25.0 3 2.0 2.0 0.7 28.1 4 1.0 4.0 0.7 4.1 5 0 3.4 0.4 0 148560.doc •20· 201110159 接著如電極3，使用以1 : 1比例混合第一玻璃熔塊和 第二玻璃炫塊所得的玻璃熔塊，變化導電膏中的玻璃溶塊 3量，並3乎估抗焊錫浸析性及抗酸性。電極6至9之導電膏 中的玻璃炼塊含量及銀粉末含量示於表3。其他成分與電 極1至5相同。電極6至9的電阻率及接合強度係藉由上述針 對電極1至5實行的個別評估方法來測量。結果顯示，無論 玻璃溶塊含量是多少，電極6至9皆有抗烊錫浸析性及抗酸 性兩者（表3)。 表3 電極編號 第一玻璃熔塊 (重量百分比） 銀粉末 (重量百分比） 電阻率 (歐姆） 接合強度 (N) 6 2.0 76.0 0.6 27 6 7 3.4 74.6 0.7 30 6 8 9 4.0 6.6 74.0 71.4 0.7 0.8 28.1 20.9 電路基板中的晶片電阻器電 電極之一晶片電阻器的示意 本發明之電極可用作電子 極0 【圖式簡單說明】 圖1為使用一根據本發明之 橫剖面圖； 電阻器電極之 圖2A至2E為繪示根據本發明製造—晶片 方法的示意圖； 中°平估抗焊錫浸析性之測量電路 圖3顯示一用於在實例 的圖；及 148560.doc •21 · 201110159 圖4顯示一用於在實例中評估一電極在浸沒於一酸後之 接合強度之測量電珞的圖。 【主要元件符號說明】 1 基板 2 前電極 3 背電極 4 電阻薄膜 5 端子 6 玻璃塗層 7 樹脂塗層 8 圖案 9 基板 10 電阻率測量設備 11 正方形圖案 148560.doc -22-Te〇2, A1203, B203, V205, Sb203, Cu〇 and Zn〇. Further, it is also possible to include at least one type of oxide called "improving agent" which is not vitrified but which changes the characteristics of the glass, and is selected from the group consisting of Li 〇, Na 2 〇, K 20 , MgO, Ba 〇, Ca 0 and Sr 〇. The glass block of the present invention does not include lead. The first glass frit of the present invention contains at least 60 weight percent Si 〇 2 based on the weight of the first glass frit. The amount of SiO 2 included in the first glass frit is preferably from 6 Torr to 95% by weight, based on the weight of the first glass blister, and more preferably from 65 to 90% by weight. As shown in the examples described below, the effect of suppressing electrode peeling due to electroplating can be obtained by using a glass containing a large amount of SiO 2 as an electrode material. In addition to Si〇2, the first slope frit also includes the above glass forming agent and auxiliary glass forming agent. B2〇3 is the best glass forming agent. A1203 is a preferred auxiliary glass forming agent. 148560.doc 201110159 The content of B2〇3 is preferably from 1 〇 to 3 〇 by weight, more preferably from 15 to 25% by weight, based on the weight of the first glass frit. The content of A1203 is preferably from 0.5 to 10% by weight 'and more preferably from 1 to 5% by weight based on the weight of the first glass frit. The first glass frit may comprise at least one type of alkali metal oxides from Li, Na20 and K20 as modifiers. The modifier content is preferably from 1 to 10% by weight, and more preferably from 3 to 8% by weight, based on the weight of the first glass frit. However, the first glass frit does not include Ti〇2. The second glass frit of the present invention contains at least 5 weight percent bismuth 2 based on the weight of the second glass frit. Preferably, the amount of Ti 2 included in the second glass frit is from 5 to 15% by weight, and more preferably from 6 to 1% by weight. If the content of TiO2 in the glass is low, the effect of preventing silver from leaching from the electrode can be impaired. On the other hand, since Ti〇2 itself does not vitrify, including too much hinders the formation of glass frits. In addition to Ti02, the second glass frit may also include the above glass forming agent and auxiliary glass forming agent. B203 is the best glass forming agent. The content of B203 is preferably from 4 to 20% by weight, and more preferably from 5 to 15% by weight, based on the weight of the second glass frit. A1203 and ZnO are the best auxiliary glass forming agents. The content of A1203 is preferably from 5 to 25 wt% and more preferably from 8 to 15 wt%, based on the weight of the second frit. The content of ZnO is preferably from 5 to 25% by weight, and more preferably from 10 to 20% by weight, based on the weight of the second glass frit. The second glass frit may include at least one selected from the group consisting of LiO, Na20, K20, MgO, BaO, and CaO as a modifier. Based on the weight of the second glass frit, the modifier content ranges from 1 to 148560.doc • 10 - 201110159 30 by 1 percentage. The second glass block may include μ〇2 as a glass forming agent. In this case, the second glass frit is different from the first glass frit in that the content of Si 2 is not more than 40% by weight based on the weight of the second glass frit. The weight ratio of the first glass frit to the second glass frit is from 1:3 to 5:1, and preferably from 1:1 to 4:1. As shown in the examples, it is difficult to achieve both solder leaching resistance and acid resistance in the electrode by using the first glass frit or the second glass frit alone. However, it has been found that when these glass matries are used in a weight ratio of 1:3 to 5:1, both solder leaching resistance and acid resistance tend to be achieved. The content of the glass frit in the conductive paste is not subject to any particular limitation. As shown in the κ example, both the solder leaching resistance and the acid resistance can be achieved by using the blend of the first glass frit and the second glass frit or even the different glass frit content. The preferred glass content is based on the weight of the conductive paste, and the content of the glass block in the conductive paste is less than 1% by weight. The electrode formed by firing the conductive f is separated from the substrate. On the other hand, when the content of the glass (four) block exceeds (7) the weight percentage of S, it is possible to hinder the conductivity of the electrode. To further enhance the solder leaching resistance and acid resistance, the content of the glass frit based on the conductive paste is better than that of the field (1). In the examples (Table 3), when the glass content is 100 parts by weight, the anti-rhenium leaching property and the acid resistance tendency are poor. In the present invention, the particle size of the glass frit is not subject to any particular limitation. Narrowly, the average particle size of the glass frit particles ((10), laser scattering type particle size analyzer) is located in the range from _. When it is less than ❹..., it does not easily occur in the conductive paste. On the other hand, at a particle size greater than 1 〇 148560.doc 201110159 μιη, the conductive paste can cause clogging during, for example, stomach printing. As described above, the present invention is characterized in that a glass bump blend having a ruthenium composition is used to enhance the solder resist leaching property and acid resistance of the wafer resistor electrode. (3) Metal oxide The electrode of the present invention may further comprise a metal oxide selected from the group consisting of tin, ruthenium, osmium, iridium and a chain. Since these metal oxides are not easily subjected to solder leaching and are electrically conductive, in the electrode to which such a metal oxide is added, the conductivity can be minimized even if the conductive powder is eluted by solder leaching. The metal oxide used in the present invention includes, for example, the following. (1) 铱 oxide: Ir203, Ir〇2 (铱 pyrochlore: Pb2Ir207, Bi2Ir207, Lu2Ir207); (2) 铑 oxide: Rh203, Rh02, Rh03 (铑 pyrochlore: Pb2Rh207, Bi2Rh207, T12Rh207); (3) Antimony oxide: Ru02 'Ru03, Ru04 (pyrochlorite: Pb2Ru207, Bi2Ru207, T12Ru207); (4) Antimony oxide: Re203, Re03, Re207; (5) Tin oxide: SnO, Sn〇2 (6) Boride: LaB6, Ni3B, Ni2B. Other yttrium pyrochlore oxides are described in detail in Japanese Patent No. 2006-054495 and U.S. Patent Specification No. 3,583,93. These metal oxides may be added alone or a blend of two or more of these metal oxides may be added. Use a relatively inexpensive tin oxide (Sn〇 or Sn〇2) for 148560.doc 12 201110159 Best. The metal oxide may be in the form of the above-mentioned mQ sphere or amorphous. Such as the second to dispersibility and printability, the average particle size of the metal oxide (D50, the genus is from the mo μιη, better, the type particle size distribution analyzer), the preferred particle size, the conductive For example 6 X 0.5 to 5 Mm. Blockage can occur during more than 10 - n h n von printing. If the content of the metal oxide is an amount capable of achieving the object of the present invention, the inclusion of :: is subject to any particular limitation. However, based on the weight of the conductive paste, === is preferably from 1 to 5. Weight percentage. Conductivity can be maintained by adding at least a knife b even if solder leaching occurs. In the absence of, the purified material can interfere with the sintering of the conductive powder, and there is a risk that the resistivity of the electrode will increase when added over a percentage of the weight. From the viewpoint of electrical conductivity, it is more preferable that the metal oxide content is not more than 3% by weight based on the heavy stem of the stagnation. (4) Tree wax binder In the present invention, a conductive powder, a glass frit or the like is dispersed in a resin to form a dispersion having a semi-fluid viscosity called "paste". By turning into a paste form, the dispersion can be printed to be applied to an alumina substrate. In the present invention, the term "resin binder" strictly refers to a resin. However, sometimes a solvent for adjusting the viscosity of the material is added to the resin. In this case, the concept of "resin binder" also covers a mixture of a resin and a solvent. Although ethyl cellulose (EC) which is usually used in the paste is preferred, the resin used in the present invention is not subject to any particular limitation. It is also possible to use, for example, ethyl hydfQxyethyi cellulose, wood rosin (w〇〇dr〇sin), ethyl cellulose... 148560.doc 13 201110159 cellulose) and phen〇lic resins. Mixtures, polymethacrylates of lower alcohols and monobutyl butyl ethers of ethylene glycol monoacetate. To adjust the viscosity, a solvent can be added to the resin. Commonly used solvents in pastes include terpenes (eg, alpha or beta rosinol), kerosene, dibutyl phthalate, butyl carbitol, dibutyl carbitol, carbitol acetate , butyl carbitol acetate, hexane diol and high boiling alcohols and alcohol esters. Combine and formulate these and other solvents to achieve the desired viscosity and volatility for your specific application. It is preferable that the content of the conductive powder 'glass frit and the resin binder used in the conductive paste of the present invention is from 59 to 9 Å by weight, from 1 to ι 重置, and from 9 to 40% by weight, respectively. Next, a method of manufacturing a conductive paste using the above electrode material will be described. In the present invention, the conductive powder, the first glass frit, the second glass frit and other inorganic fillers are dispersed in a resin binder by mixing a resin and a solvent, and (4) The semi-fluid viscosity is called the moon. The ratio of the reset of the resin binder included in the conductive paste composition to the combined weight of the conductive powder, the glass frit, and the metal oxide may vary depending on the paste application method and the type of the resin binder to be used. In general, for good coverage, the conductive paste will contain conductive powder, glass frit and metal oxide from 6 〇 to 91 重量重量, and from 9 to weight percent of the resin binder. Next, a method of forming the electrode of the present invention will be described. The electrode forming method of the invention comprises the following steps: 148560.doc -14· 201110159 (a) coating an insulating substrate with a conductive paste, the conductive paste comprising: (1) a conductive powder selected from the group consisting of gold, silver, At least one type of metal powder of the group consisting of platinum, palladium, and alloys thereof; (U) - lead-free glass frit having a weight ratio between 1:3 and 5:: including at least 60 weight percent a first glass frit of Si〇2 and a second glass frit containing at least 5% by weight of Ti〇2; and (out) a resin binder; and () 乂800 to 900 C firing has been applied to The conductive paste on the insulating substrate. The electrode of the present invention can be obtained by coating the above-mentioned conductive f onto a given substrate or "object", and firing the conductive paste together with the substrate or its precursor. The structure of the electrode and other necessary features The method is as exemplified above for the wafer resistor electrode. The specific sequence of the electrode forming method is as follows. The method of the present invention first includes the step of coating the insulating substrate with a conductive paste. The technique of applying the conductive paste includes, for example, screen printing. (It produces a film thickness from 1 〇 to 2 〇 4 after printing.) If the material of the insulating substrate is electrically insulating, it is not subject to any particular limitation. For example, an alumina substrate or a sinitic substrate can be used. Precursor embryonic band. ^ 'From about 10,000 to about the temperature in the oxidizing atmosphere (4) - the electric paste and the insulating base (4) sinter the electrode material (conductive paste) applied on the insulating substrate. It is possible to set the temperature type of the belt type 148560.doc •15- 201110159 to continue the furnace or a box type furnace. The electrode of the = can be used most often as a wafer resistor electrode. Therefore, the electrode is used as a wafer. The resistor method is directed to the wafer resistor shown in Fig. ???wherein the formation of the electrode has the electrode cleavage example of the invention. The steps of the electric 曰曰 chip resistor - the method of the invention includes The above conductive paste is applied to the step. The material of the insulating substrate has electrical insulating properties, and is specifically limited. For example, the precursor of the insulating material can be made. First, the specific material of the W-substrate phase The 疋 coating sequence is included at the top of the substrate 1 = electrode 2 (Fig. 2A). Next, a resistive film 4 is formed to cover a portion of the front electrode 2 (Fig. 2B). Then, on the back side of the substrate, - forming a back electrode 3_ at a position relative to the front electrode 2. The present invention can be applied to both the front electrode 2 and the back electrode 3. The front electrode 2 and the back electrophoresis can be printed by way of example (up to 1 after printing) The film thickness of the film is formed by the above-mentioned conductive paste. Or 'formation can be achieved by first applying the conductive paste to the film of polyethylene phthalate (ΡΕΤ) film to a thickness of 1 〇 to 2 〇 μηη. The conductive paste is transferred to the substrate for implementation. The resistive film 4 is used by using A technique such as screen printing is formed by applying a resistor paste. Alternatively, the resistive film 4 can be formed by first applying a resistor paste to the film and then transferring the resistor paste to the substrate. To the electrode and the resistive film on the insulating substrate, specifically, after forming the terminal 5 of the front electrode 2 and the back electrode 3 electrically connected (FIG. 2D), the two electrodes 2 and 3, the resistive film 4 and the terminal 5 are approximately 8〇〇至约148560.doc -16· 201110159 900 C is fired in an oxidizing atmosphere. Since the front electrode 2 is more likely to be in contact with the solder than the back electrode ^, it is preferred to use the electrode of the present invention at least as the front electrode The 2 ° terminal 5 is formed by a technique such as screen printing, dipping, roller coating or sputtering of a conductive paste. The terminal 5 is formed in such a manner as to cover the front electrode 2 of the portion and the back electrode 3' of the portion so that the two electrodes are electrically connected. The resulting wafer resistor electrode is then protected by forming a glass coating 6 and a resin coating 7' so as to cover at least the surface of the resistive film 4 (Fig. 2E). The conventional method can be used to form the glass coating layer 6 and the resin coating layer 7 (see, for example, Japanese Patent Laid-Open No. _5) and Japanese Patent No. 4_33 _〇]. Next, in order to prevent electrode leaching and to ensure soldering reliability when soldering is performed on the exposed electrode in the tan tin flow or reflow step, the Kam recording layer or the like is formed by electric ore (not shown). Through the above steps, the wafer resistor of the present invention can be obtained. The completed wafer resistor is fixed to the terminal region portion of the circuit substrate on which the terminal $ is placed by melting the solder. It is also understood that the electrodes of the present invention are formed by the following steps: (4) applying the conductive paste of the present invention to an insulating substrate (for example, an alumina substrate or a precursor thereof) And 800 to 90 (TC fires the conductive paste that has been applied to the insulating substrate. By using the electrode of the present invention as the front electrode 2 or the back electrode 3, even a these electrodes have been exposed to plating or soldering In the meantime, the number of defects (4) generated can be minimized due to excellent resistance to solder leaching of acid resistance. Examples of resistors 148560.doc -17· 201110159 The present invention is more fully described below by way of example However, the examples are not intended to limit the scope of the invention. Unless otherwise noted, the numbers indicating the proportions of the components represent weight percentages (wt%). Preparation of Conductive Paste Conductive powder, glass frit and metal oxide system used in Table 1 Used in the examples. The individual contents of the first glass frit and the second glass frit in the paste are shown in Table 2. The conductive content of the conductive powder, the glass frit and the metal oxide in the conductive paste are set. It is set at 80.0% by weight, but the glass frit content and the silver powder content are different in different pastes. Therefore, the contents of other components, namely palladium powder, Sn02 powder and resin binder are the same in all pastes. To set the powder content to 〇·5 weight percent, sns2 powder content set to 1 '5 weight percent and resin binder content set to 2 〇 weight percent. The first glass frit composition contains 713 weight percent Si〇2, 2.1% by weight of A1203 and 19.8% by weight of B203. The second glass frit composition contains 354% by weight of Si〇2, 13.9% by weight of A1203, 8.2% by weight of B2〇3, 1〇4 3% by weight of ZnO and 8.9 wt% of Ή〇2. A specific amount of silver powder, palladium powder, glass frit, Sn02 and resin binder are measured and mixed into a mixture, which is then dispersed in a roll mill. Thus, conductive pastes 1 to 5 were prepared. 148560.doc •18· 201110159 Table 1 Composition properties Conductive powder Silver powder Shape: flake, average particle size (D50): 1.5 μηι I Powder shape: flake, average particle size (D50): 1.5 μηι glass frit average particle size (D50): 1.5 μηι Sn02 powder (3975, JT Baker Inc.) average particle size (D50): 1.5 μιη resin binder ethyl cellulose Method for evaluating the mixture of rosin and alcohol The method for evaluating the solder leaching resistance is described with reference to Fig. 3'. The conductive paste 1 to 5 is shown in the pattern 8 (line width, 〇.5 mm; film thickness '17 μιη) shown in Fig. 3. The respective screen printing was performed on 96% of the alumina substrate 9 (25 mm long x 25 mm wide X 0.64 mm thick), dried and then fired to form electrodes 1 to 5. The drying conditions were 15 0 ° C for 1 〇 minutes. The firing system was carried out in a belt furnace at a belt speed of 124 mm/min. The temperature profile is 10 minutes below 850 ° C, 10 minutes 850 ° C and 10 minutes above 850 ° C. The resulting pattern 8 was immersed together with the scented substrate 9 in a molten co-throat (Sn: Pb = 62: 36) maintained at about 220 ° C for 30 seconds. After immersion, the workpiece is removed from the molten solder, and the resistivity of the electrodes 1 to 5 is measured using a resistivity measurement method including a conventional 4-point probe technique similar to that shown in FIG. A multi-digit multimeter (R6581, manufactured by Advantest) is used as the resistivity measuring device 10. The results are shown in Table 2. Referring to Fig. 4, a method of evaluating acid resistance and solder leaching resistance will be described. The square pattern 11 shown in Fig. 4 (2. 〇 11111:1 width >< 2. 〇 111111 length >< 17 0111 thick) will be 148560.doc -19- 201110159 conductive paste 1 to 5 respective screen The printing was carried out on a 96% alumina substrate 9 (25 mm long χ 25 mm wide χ〇 64 mm thick) and dried, and then fired to provide electrodes 1 to 5. The drying and firing conditions are the same as described above. The resulting square pattern 11 was immersed in a 5% aqueous solution of sulfuric acid with the scented substrate 9 for 30 minutes. After immersion, the conductor removed from the aqueous solution was washed with water and then dried at 100 ° C for 15 minutes. Next, in order to test the joint strength, the wire was welded to the electrode surface. After soldering, the solder wire ends and relatively many are attached to a Force 5 machine (Force Analyzer Explorer 2 FA1015A 1605 NHTP; Aiko Engineering), pulling the wires vertically at a rate of 12 mm/min and measuring when the wires are separated Pull value (joint strength 'N). The results are shown in Table 2. An electrode having a resistivity of less than 0.8 ohm was rated as having solder resist reversibility. The electrode having a joint strength of more than 20 N after immersion in a 5% sulfuric acid aqueous solution was evaluated as having acid resistance. The electrode 2 and the electrode 3 have both solder resist leaching resistance and acid resistance. Electrodes 丨, 4 and 5 lack a combination of solder leaching resistance and acid resistance. Table 2 Electrode number First glass frit (% by weight) Second glass frit (% by weight) Resistivity (ohm) Bonding strength (N) 1 3.4 0 0.7 19.6 4.0 1.0 0.8 25.0 3 2.0 2.0 0.7 28.1 4 1.0 4.0 0.7 4.1 5 0 3.4 0.4 0 148560.doc •20· 201110159 Next, as electrode 3, use a glass frit obtained by mixing the first glass frit and the second glass bump in a ratio of 1:1 to change the glass soluble mass in the conductive paste. 3 amount, and 3 estimated resistance to solder leaching and acid resistance. The glass crude content and silver powder content in the conductive paste of the electrodes 6 to 9 are shown in Table 3. The other ingredients are the same as those of electrodes 1 to 5. The resistivities and joint strengths of the electrodes 6 to 9 were measured by the individual evaluation methods carried out by the above-mentioned pin electrodes 1 to 5. The results showed that both of the electrodes 6 to 9 were resistant to antimony tin leaching and acid resistance regardless of the glass block content (Table 3). Table 3 Electrode number First glass frit (% by weight) Silver powder (% by weight) Resistivity (ohm) Bonding strength (N) 6 2.0 76.0 0.6 27 6 7 3.4 74.6 0.7 30 6 8 9 4.0 6.6 74.0 71.4 0.7 0.8 28.1 20.9 Chip Resistor Electrode in Circuit Substrate One of the Chip Resistors The electrode of the present invention can be used as an electron pole 0 [Schematic Description] FIG. 1 is a cross-sectional view according to the present invention; 2A to 2E are schematic views showing a method of fabricating a wafer according to the present invention; a measuring circuit for flattening solder resist leaching performance; FIG. 3 shows a diagram for use in an example; and 148560.doc • 21 · 201110159 FIG. A diagram for measuring the electrical conductivity of an electrode after immersion in an acid in an example. [Main component symbol description] 1 Substrate 2 Front electrode 3 Back electrode 4 Resistive film 5 Terminal 6 Glass coating 7 Resin coating 8 Pattern 9 Substrate 10 Resistivity measuring device 11 Square pattern 148560.doc -22-