TWI312770B - A composition for forming a thick film conductor - Google Patents

Description

1312770 九、發明說明： 【發明所屬之技術領域】 本發明係關於-種未含錯之厚膜導體形成用組成物， 心別是製造晶片電阻器、電阻網路及混合積體電路(hybrid ic)等時’為了在陶变基板等形成厚膜導體所使用之厚膜導 體形成用組成物。 【先前技術】 採用厚膜技術而形成厚膜導體時，一般係使導電率高 之：電粉末與玻璃粉末等氧化物粉末一同分散在有：載體 ’而獲得導電膏―duetivepaste)，並利用網板 P刷法相該導電膏塗布在銘基板等㈣基板上，塗布成 預定=狀，II由在靖至900t燒成，而形成厚膜導體。 2粉末係採料電率高之AU、Ag、pd3tpt^t P吏用千均粒徑1G//m以下的粉末，特別是—般係使用廉 4貝之Ag粉末及pd粉末。 玻璃粉末係採用軟化點之控制容易、且化學耐久性高 /彌夕或|g事夕酸錯系。然而，從防止環境污染之以 往觀點來看，期待未含鉛之導電膏。 /、 、日人=用所得之厚膜導體’製造晶片阻抗器、阻抗網路及 心體電路等電子零件時的製造步驟或安裝步驟中，對 厚膜導體進行銲接。在進行該銲接時，AU、Ag、Pd或pt 會溶^在銲料中，而導體部分消失、斷線之情形。此現象 成曰曰片電阻器、電阻網路及混合積體電路等電子零 317770 5 1312770 .......... ‘件之良率降低，或 再者，如前；H 零，之可靠性降低的原因。 63Sn/37Pb之共θ _ 了防止環境污染，銲料逐漸從 -的銲料，由於Sn系^變為未含錯之如含有量高之組合 、高之傾向。伴隨該銲：組：:：二，，此鐸料溫度亦有變 變成銲料腐蝕比欠更、鲜料溫度之上昇，而 肉挪比以彺為更容易發生 用組=:::r方法之-二膜_成 與電子零件之接顧在忒方法中，具有厚膜導體 的探針與厚膜導體全、或用以測定電子零件之特性值 子以體之接觸不完全的問題。 在曰本專利特開 跡Si〇2_Cao_Al2〇3系玻璃粉末、八6號=令，記載將 導=末分散在有機載體，在燒成膏2時=稱==石 (卿伽e，· CaA】2Si办） =j長石 出’而防止銲料細方法二在= 導直體之内部析 璃中、東，以〜°载 貧用組成物係使用含鉛之玻 璃心末，以核境污染之觀點來看並不理相 破 平6-223616號公報中，心 在日本特開 如其所記載之灰長:未=:未滿15質量%， 以防止銲料腐餘。 絲含錯之導電貧中難 直方面’在日本專利特開平7·97269號公報及日本 專利特開平2〇〇M 14556號公報_，藉由1312770 IX. Description of the Invention: [Technical Field] The present invention relates to a composition for forming a thick film conductor without errors, and is manufactured by manufacturing a chip resistor, a resistor network, and a hybrid integrated circuit (hybrid ic) A device for forming a thick film conductor used for forming a thick film conductor on a ceramic substrate or the like. [Prior Art] When a thick film conductor is formed by a thick film technique, the conductivity is generally high: the electric powder is dispersed together with an oxide powder such as glass powder in a carrier to obtain a conductive paste-duetivepaste, and the network is utilized. The plate P brushing method is applied to the (4) substrate of the substrate (4), coated in a predetermined shape, and II is fired at 900 to 900 to form a thick film conductor. 2 Powders are high in AU, Ag, and pd3tpt^t P吏 with a powder having a mass average particle diameter of 1 G/m or less. In particular, Ag powder and pd powder are used. The glass powder is easy to control by the softening point, and has high chemical durability/Yi Xi or |g. However, from the viewpoint of preventing environmental pollution, a conductive paste containing no lead is expected. /, ,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, When this soldering is performed, AU, Ag, Pd, or pt may be dissolved in the solder, and the conductor portion may disappear or be broken. This phenomenon becomes a chip resistor, a resistor network, and a hybrid integrated circuit. The electronic zero 317770 5 1312770 .......... 'The yield of the piece is reduced, or again, as before; H zero, The reason for the reduced reliability. The total θ _ of 63Sn/37Pb is _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Along with the welding: group::: two, the temperature of the material also changed into solder corrosion, and the temperature of the fresh material increased, and the meat ratio was more likely to occur with the group =:::r method. -Secondary film_electronic contact with electronic parts In the crucible method, the probe having a thick film conductor and the thick film conductor are all used, or the problem that the characteristic value of the electronic component is incomplete contact with the body is measured. In the patent special opening, Si〇2_Cao_Al2〇3 series glass powder, No.8-6=, the description will be guided to the end of the dispersion in the organic carrier, in the case of the baking paste 2 = === stone (Qinge e, · CaA 】 2Si Office) = j feldspar out 'and prevent solder fine method two in the inside of the directing body of the glass, east, ~ ° loading composition of the use of lead-containing glass heart, to the nuclear pollution From the point of view, it is not reasonable to break the flat. No. 6-223616, the heart is opened in Japan as described in the gray length: not =: less than 15% by mass to prevent solder residue. In the case of the wire, the conductive and poor in the middle of the fault, the Japanese Patent Application Laid-Open No. Hei 7-97269, and the Japanese Patent Laid-Open No. Hei.

Sl〇2-B2(VAl2〇3-Ca0系玻璃粉末、與Ai2〇粉末之混合β物、 317770 6 1312770 然而，在該等情形下 而使灰長石析出 之灰具$ ^ ^ ^…τ旧瓜「，馮了析出充分大 ^人長石’由於其結減溫度高（賴之軟 此必須要有_t以上之高溫。在·七以上之溫;;)因 電極膏時，電極臈會形成過燒結，在㈣低之“= 成分的電極膏中，電極膜會形：主 電極膜的問題。 ”套形成均質之 6_223616號公報 7-97269號公報 2001-114556 號公報 (專利文獻1)曰本專利特開平Sl〇2-B2 (VAl2〇3-Ca0-based glass powder, mixed with Ai2〇 powder, β 317770 6 1312770 However, in these cases, the gray ash feldspar is precipitated as $ ^ ^ ^...τ old melon "Feng's analysis of the full large ^ people feldspar' due to its high temperature reduction (this must be more than _t high temperature. In the temperature of more than seven;;) due to the electrode paste, the electrode 臈 will form Sintering, in the electrode paste of the "fourth" component, the electrode film is shaped into a problem of the main electrode film. The sleeve is formed into a homogenous film. (Japanese Patent Publication No. 6-223616 (Patent Document 1) Patent special opening

(專利文獻2)曰本專利特開平 (專利文獻3)日本專利特開平 【發明内容】 (發明所欲解決之課題） 本發明係鑑於上述課題而研創者，其目的在於提供一 種焊料錢少且未含錯之厚膜導體形成用Μ成物。 (解決課題之手段） 本發明之厚料體形成用組成物係由導電粉末、氧化 •:粉末及有機载體所構成，前述氧化物粉末係包含 2 2〇3_Al2(VCa〇_Li2〇 系玻璃粉末、及 Al2〇3 粉末。 在此，Si02-B203-Al2〇3_Ca〇_Li2〇系玻璃粉末除了以上 -組成所構成者、該等成分以外，亦包含211〇、如〇、抓、 • Zr〇2、Bi2〇3等其他成分的玻璃粉末。而且，作為氧化2物 粉末，除了該玻璃粉末、Μα粉末以外，添加Bi2〇”⑽、 CuO、ΖηΟ、Μη02等並不造成妨害。 剛述Si(VB2〇3-Al2〇3_ca〇-Li2〇系玻璃粉末之組成比 最好為Si〇2:20至60質量％、B2〇3:2至25質量％、Al2〇3: 317770 7 1312770 2質1二5質量％、Ca〇: 20至50質量％及。2〇: ο·1至 H特別是，前述麵粉末之Li2Q的組成比在0 0重I%的範圍時，即 .破璃粉末的含有量較少的情=導二 含之 .體之耐㈣性，而可使心::：一之厚膜導 二前述導電粉末係^、^、⑽以之至少一種類。 SiO -R r/相對於前料電粉末_ f量份，前述 ’量产2 2」，l2(VCa〇-Li20系玻璃粉末最好為〇·1至15質 述Al2〇3粉末最好為G.u8f量份。5貝 (發明之效果） 、 為困雜形成用組成物，習知技術雖較 【實施方式】 3 料賴少之導體臈。 本發明之厚膜導體形成 _2丸〇3為〇3心〇私〇 ^物的特徵係包含 藉由在燒成導電膏時使破璃粉末、ΓΑ1、〇 末’ 可獲得在該厚臈導體内部 3心末反應’而 使用該厚料體時，少量 =灰長石的厚膜導體。 銲料，藉此使灰長石以荊 '=中的責金屬會溶出於 長石係針狀之結晶，當灰1束 厚膜導體之表面。灰 面時，銲料因表面張力 Ρ刑棘狀露出在厚膜導體表 腐姓。 張力而不會到達貴金屬，而不進行銲料 在本發明之厚膜導體 末混合在前述破螭粉末時，、、且成物中，未將α〗2〇3粉 由於所得之厚膜導體與陶瓷基 317770 8 υ12770 .... ............ 板之界面附近會析出較多的 制銲料腐蝕之效果。亦g ，，長石，因此無法獲得充分抑 到達貴金屬，必須在 為了使1〒料因表面張力而不會 再者，因鮮接而露=石導體内部均勻地析出灰長石。 上。在長度未滿二二：；：；？長度必須為-以 會從厚膜導體中移動至銲料中，而°=中^亥灰長石結晶 腐蝕之效果。 ”，、法獲得充分抑制銲料 如前所述，灰長石亦(Patent Document 2) Japanese Patent Laid-Open (Patent Document 3) Japanese Patent Application Laid-Open (Invention) The present invention has been made in view of the above problems, and an object of the present invention is to provide a solder with less money. A film for forming a thick film conductor that does not contain errors. (Means for Solving the Problem) The composition for forming a thick material according to the present invention is composed of a conductive powder, an oxidation powder, and an organic carrier, and the oxide powder contains 2 2〇3_Al2 (VCa〇_Li2 bismuth glass) Powder and Al2〇3 powder. Here, the SiO 2 -B 203 -Al 2 〇 3 _ _ 〇 Li Li Li Li Li Li Li Li Li Li Li Li Li Li • • • • • • • • • • • • • • • • • • • • • • • • • • • • • Glass powder of other components such as 〇2, Bi2〇3, etc. Further, as the oxidized two-powder powder, addition of Bi2〇(10), CuO, ΖηΟ, Μη02, etc. other than the glass powder and Μα powder does not cause any hindrance. The composition ratio of (VB2〇3-Al2〇3_ca〇-Li2 lanthanide glass powder is preferably Si〇2: 20 to 60% by mass, B2〇3: 2 to 25% by mass, and Al2〇3: 317770 7 1312770 2 1 25% by mass, Ca〇: 20 to 50% by mass and 2〇: ο·1 to H, in particular, when the composition ratio of Li2Q of the above-mentioned surface powder is in the range of 0% by weight of I0, that is, the glass powder The content of the lesser content = the second derivative of the body. The resistance of the body (four), and can make the heart::: a thick film of the second conductive powder system ^, ^, At least one kind of SiO-R r / relative to the pre-charged electric powder _ f, the aforementioned 'production 2 2', l2 (VCa〇-Li20-based glass powder is preferably 〇·1 to 15 described Al2 The 〇3 powder is preferably in the form of G.u8f. 5 lb (effect of the invention), which is a composition for forming a doping, and the conventional technique is more than the embodiment 3. Conductor formation _2 shot 〇 3 is a feature of 〇 3 〇 〇 包含 包含 包含 包含 包含 包含 包含 包含 包含 的 特征 特征 特征 特征 特征 特征 特征 特征 特征 特征 特征 特征 特征 特征 特征 特征 特征 特征 特征 特征 特征 藉 特征 藉 反应 藉 反应 反应 反应 反应'When using this thick material body, a small amount = thick film conductor of gray feldspar. Solder, so that the ash feldspar will dissolve in the feldspar needle-like crystal, and the ash 1 bundle thick film conductor On the surface of the gray surface, the solder is exposed to the surface of the thick film conductor due to the surface tension. The tension does not reach the precious metal, and the solder is not mixed with the broken powder at the end of the thick film conductor of the present invention. In the , , and adult products, α 〇 2 〇 3 powder is not obtained due to the resulting thick film conductor and ceramic base 317770 8 υ 12770 .... ............ There will be more corrosion effect on the solder near the interface of the board. Also g, feldspar, therefore can not get enough to reach the precious metal, must be in order to make 1 material due to the surface Tension and no longer, due to the fresh connection, the inside of the stone conductor evenly precipitates the ash feldspar. The length is less than two or two:;:;? The length must be - to move from the thick film conductor to the solder And ° = medium ^ ash feldspar crystal corrosion effect. ", the law is fully inhibited by the solder. As mentioned above, the gray feldspar is also

CaO Λ1 藉由加熱 Si(VB2CVAl2CV 了析出I: 2〇3粉末之混合物而析出。此時； 了析出充分大之灰長石，必須要# :為 低严下…广®在玻璃粉末含有u2〇,故即使在 低，皿下亦可使灰長石析出。 文在CaO Λ1 is precipitated by heating Si (VB2CVAl2CV to precipitate a mixture of I: 2〇3 powder. At this time; it is necessary to precipitate a large gray feldspar, which must be #: is low-pressure...Guangzhou® contains u2〇 in glass powder, Therefore, even if it is low, the feldspar can be precipitated under the dish.

本發明所使用之si(VB ^ tb ^ Si02:20 ^60 ;0-c;0·-^ ^ ^ ^ tt^Al2〇3：2,25ft% ； τ . 貝里/〇 Ca0 · 20至50質詈ηSi used in the present invention (VB ^ tb ^ Si02: 20 ^ 60 ; 0-c; 0 · - ^ ^ ^ ^ tt ^ Al2 〇 3: 2, 25 ft%; τ . Berry / 〇 Ca0 · 20 to 50詈η

Ll2〇 : 0.1至10質量％。 主π貫以及 在_粉末之組成中，si02少於20質量％時，灰長 、以析出’而有無法防止銲料腐钱之虞。且厚膜導體中 之玻璃耐氣候性、耐水性及耐酸性有降低之傾向。另 面，Si02多於20質量％時， > 方 μ里/οτ圾螭之軟化溫度過高，而灰 X石析出溫度有變高的傾向。 帥3 ^於2貝里％時，玻璃之軟化溫度有過變高的 、。。且厚膜導體之玻璃容易變脆。另一方面，多 於25質量％時’玻璃容易分相’而厚膜導體中之玻璃耐； 317770 9 I312770 候性、耐水性及耐酸性有降低之傾向。 在玻璃粉末之組成中，八〗2〇3少於2質量％時，灰長 石難以析出’且厚臈導體中之玻璃容易分相。另一方面， 八!2〇3多於25質量％時，玻璃之軟化溫度過高，而灰長石 析出之溫度有過高之虞。 而CaO多 增力口 Li2〇 因此，在Ll2〇 : 0.1 to 10% by mass. In the composition of the _ powder, when the si02 is less than 20% by mass, the ash is long and precipitates, and there is no possibility of preventing the solder from rot. Moreover, the weather resistance, water resistance and acid resistance of the glass in the thick film conductor tend to decrease. On the other hand, when the amount of SiO 2 is more than 20% by mass, the softening temperature of the > square μ 里 / ο τ 过 is too high, and the precipitation temperature of the ash X stone tends to become high. Shuai 3 ^ at 2% Berry, the softening temperature of the glass has become too high. . And the glass of the thick film conductor is easy to become brittle. On the other hand, when it is more than 25% by mass, the glass is easily phase-separated and the glass in the thick film conductor is resistant; 317770 9 I312770 has a tendency to lower in weatherability, water resistance and acid resistance. In the composition of the glass powder, when it is less than 2% by mass, the ash feldspar is hard to be precipitated' and the glass in the thick tantalum conductor is easily phase-separated. On the other hand, when 八!2〇3 is more than 25% by mass, the softening temperature of the glass is too high, and the temperature at which the ash feldspar is precipitated is too high. And CaO is more powerful, Li2〇, therefore,

CaO少於20質量％時，灰長石難以析出 於50質量％時，難以玻璃化。When CaO is less than 20% by mass, it is difficult to vitrify when it is difficult to precipitate ash feldspar at 50% by mass.

LhO係具有使玻璃之軟化溫度降低之作用 =含量時，依此可使灰長石之結晶大幅地成長⑽，在 =粉末之組成中，Li2〇少於時，灰長石難以 夕’且所析出之灰長石的大小容易變小。另一方面，咖 :::。質又量广耐氣!錄、耐水性及耐酸性有降 道* 12 4至8質量％之範圍時，即使在厚膜 導體形成用組成物所含之玻璃於古 、 下，含有量較少的情形 I度ΪΓ 料叙耐銲料性，而可使其接著 成比ΐ發了明ί ^〇2佩姆3伽蝴系玻璃粉末之組 ί二入於膏燒成中所析出之灰長石，而固 又化。因此，即使在所形成之電極間有 不會遷移（migration)。 左以蠘子亦 本發明所使用之玻璃粉末係Si(vWhen the LhO system has a function of lowering the softening temperature of the glass = content, the crystal of the ash feldspar can be greatly grown (10), and when the composition of the powder is less than Li2, the ash feldspar is difficult to form and precipitates. The size of the gray feldspar is easy to become smaller. On the other hand, coffee :::. High quality and gas resistance! Recording, water resistance and acid resistance have a lower range * 12 4 to 8 mass%, even if the glass contained in the thick film conductor forming composition is less than the ancient and the lower content In the case of I, the material is resistant to soldering, and it can be made into a combination of ί 〇 佩 佩 佩 3 3 3 3 3 3 3 3 3 3 3 3 3 3 , , , , , , , , , , , , , , , , , , And solid again. Therefore, there is no migration even between the formed electrodes. The left-handed scorpion is also used in the glass powder system Si (v) used in the present invention.

LhO系，在該組成中亦包含1他八 3 2 3_ a _ 性等，可選擇ZnO、Ba0、加依據軟化點或耐酸 並使之含在該組成中。I〇2、Zr〇2、〇说等成分， 317770 10 1312770 本么月之SiCVB2〇3-Al2〇3-CaO-Li2〇系玻璃粉末的平 均粒徑最好為1G/Zm以下。平均粒徑在1()_以上時，玻 璃粉末之軟化變慢，電極膜與基板之接著強度 .向，因此較不理想。 _ f本發明中，相對於導電粉末1GQf量份，分別添加The LhO system also includes 1 八 3 2 3_ a _ or the like in the composition, and ZnO, Ba0 may be selected, and the softening point or acid resistance may be added and contained in the composition. I〇2, Zr〇2, 〇, and other components, 317770 10 1312770 The average particle size of the SiCVB2〇3-Al2〇3-CaO-Li2 lanthanide glass powder of this month is preferably 1G/Zm or less. When the average particle diameter is 1 () or more, the softening of the glass powder is slow, and the bonding strength between the electrode film and the substrate is relatively unfavorable. _ f In the present invention, it is added separately with respect to the amount of the conductive powder 1GQf

Sl〇2_B2(VAl2〇3_Ca〇-Li2〇 系玻璃粉末（U 至 15 質晋广， Al2〇3粉0.1至8質量份。 '刀 ^於導電粉末 100 質量份，Si〇2_B2(VAi2()3_eaQ_ 12;、4粉末比(U質量份少時，與陶莞基板之接著強 :降低。再者，比15 f量份多時，不但厚膜導體之電阻值 2、二而且玻璃浮在厚膜導體之表面，且與電鐘性、銲料 /^及特性評價用的探針的接觸電阻有劣化之虞。 ㈣=在^化物粉末之Al2〇3粉末的平均粒徑最好為3 厚臈導體内^3、粉末之平均粒徑超過3心時，不但在該 面變粗，㈣、""均句地析出灰長石’且有厚膜導體之表 之虞卜、用以測定電子零件特性之探針的接觸電阻變大 αι2(Λ對末於卜導電粉末1〇0質量份，使用在氧化物粉末之 2〇3 4末比〇.丨質量份少 造成銲料射虫。S — ^ 人長石之析“少’且容易 抗合纖士 另方面，比8質量份多時，不但接觸阻 场又，且與陶瓷基板之接著強度降低。 所使用之導電粉末可使用一般厚膜導體的形成 類=例如可使用AU、Ag、…等粉末之僅-種 、…2種以上。導電粉末之平均粒徑最好為10"m 317770 11 1312770 以下，導電粉末之形狀亦可為粒狀或薄片狀等，並無特別 限定。 再者，有機載體係與習知同樣地，可為將乙基纖維素 .(ethylcellulose)或甲基丙烯酸酯（methacrylate)等，溶解在 -松香醇（terpineo1)或丁基卡必醇（butyl carbit〇l)等溶劑者。 .再者，本發明係除了導電粉末、SKVB2〇3_Al2〇3_CaC)_ l12o系玻璃粉末、及从〇3粉末以外，為達成使厚膜導體 之接著強度或銲料之沾濕性等目的，亦可添加習知所使用 ，各種粉末，例如Bi2〇3、Si〇2、Cu〇、Zn〇、或施 氧化物粉末。 (實施例） (實施例1) 相對，平均粒徑15#m之粒狀^粉末㈣質量份、 雷於：粒徑〇.1Um之粒& Pd粉末量份所構成之導 丨A5皙吾於n 之十均粒佐的玻璃粉末 1，平均粒徑〇.5_之A]2〇3粉末1質量份， =二Γ素之松香醇溶液作為载體，並以 將所以鍊’㈣作厚科體形成用膏。 將所製作之厚膜導體形成 板上，且在15(re|^ h 刷在鄕紹基 ,,ν 乾各。在峰值溫度§5〇t，以9分鐘、人 计30分鐘的帶式爐，將乾 里σ 圖案之厚膜導體膜。’'基板予以燒成’而形成預定 所知之厚膜導體的膜厚坪僧 襯墊’以觸針型之膜厚計測定。、…2.〇咖».〇函之 317770 12 J312770 面積電阻值之評價係利用數位 muhimeter)測定寬〇.5_、長編m之導體圖宰的電阻Γ 並將所得之值換算為面積電阻值。 圖案的電阻值， 耐鋅料性之_係以下述方式進行。首先 燒成的厚膜導體，在保持於聰:: 貝里0 n 3貝里％Ag·0.5質量％Cu組成的盔妒銲料 :::浸/ΓΓ少鐘後’進行一次測定電阻值之操作= :==。藉由使所測定之電阻值成為1ΚΩ以上，確 :產生罐钱，將至產生銲料腐料 耐銲料性的評價。 後人數作為 接著強度的評價係藉由使用96 5 f量％^3質量％ 心〇.5質量％Cu組成的無鉛銲料，將直徑㈣職之％ 之又銅線銲接在2.GmmX2 Gmm之圖案的厚膜導體上，並使 月垂直方向引拉、剝離，以測定剝離之引拉力而進行。 所測定之厚膜導體的臈厚、 接著強度示於表3。 面積電阻值、耐銲料性及 3施例之厚膜導體即使浸潰在銲料12次，面積電阻 u在_以下^斷線，㈣銲料性較佳。且其接著強 度亦高，在60N以上。 (貝把例2、3、比較例1、2) '除了如表1及表2所示變更使用量及玻璃粉末的種類 以外’與實施例i同樣地獲得厚膜導體，且與實施例】進 行同樣測定。 所測定之厚膜導體的膜厚、面積電阻值、耐銲料性及 317770 13 1312770 接著強度示於表3。 實施例2之厚膜導體即使浸潰在鮮料以次，面積電阻 值依，在10Ω以下且不斷線，耐銲料性較佳。且其接著強 度亦高，在60N以上。 實施例3之厚膜導體即使浸潰在鮮料12次，面積電阻 且不斷線4其接著強度亦高，在6〇n =更Γ:Τ广溫度係比玻瑪粉末a、或玻璃粉 粉末為少量，得知如使用玻璃粉末c 貫轭例3，所仔之厚膜導體的接著強度較高。 4 A f —方面’比較例1之厚膜導體的接著強度較低，第 -人時面積電阻值成為1ΚΩ以上，造成耐鮮料性劣化。 ::例2=導體係在第4次時，面積 U以上，造成耐銲料性劣化。 (比較例3) 璃2對於減物粉末，除了未添加Al2Q3粉末以外，玻 場粉末之種類（玻璃粉纟Α) 刀禾以外玻 ^'J 5 # ik ^ 1 η 、 七末與破璃粉末之比 係與貝施例！同樣，獲得厚膜導體 仃同樣測定。 且興貝施例1進 所測定之厚膜導體的膜 接著強度㈣表3。 自積電⑽、耐銲料性及 比較例3之厚膜導體係在第3 _以上，造成耐㈣性劣化。、®積電阻值成為 317770 14 1312770 [表i] 組成比（質量％) 軟化 溫度 (°r ί Si02 B2O3 AI2O3 CaO Li20 Ba〇 — 玻璃粉末A 38.0 8.0 15.0 38.0 1.0 . ----- — ---- 2.0 — 660 620 580 720 650 玻璃粉末B 38.0 8.0 15.0 37.0 2.0 玻璃粉末C 40.0 5.0 16.0 33.0 6.0 玻璃粉末D 40.0 12.0 13.0 33.0 — 玻璃粉末E 45.0 13.0 5.0 — 2.0 ^3?7〇~ [表2] 導電粉末 (質量部） _氧化物 Ag粉末 Pd粉末 玻璃粉末 ΑΙ^Οι給太 實施例1 99.0 1.0 玻璃粉末A 5.0 1 π 實施例2 99.0 1.0 玻璃粉末B 4.0 — — 1 .U 1 〇 實施例3 99.0 1.0 玻璃粉末C 3^0, ~y〇~ -^丄·υ _1.0 10 比較例1 「99.0 卜 1.0 ~WWW^~D 比較例2 99.0 1.0 玻璃粉末E 5.0 1 π 比較例3 99.0 1.0 玻璃粉末A 5.0 1 . υ [表3] . 實施例1 實施例2 膜厚（/z m) 〇 r\ 面積電阻值 (m Q ) 耐焊料性 (回） -----— 接著強度 8 0 4.5 >12 ---ViN/ s60 8.5 3.8 >12 — r >12 實施例3 8.0 卜3.0 〜65 比較例1 8.5 4.5 *~~-—— 3 -_75 比較例2 8.0 5.0 —----- -— 〜35 比較例3 8.0 4.0 ^55 如比毕父例1所示，在使用未含l 得之導料中’灰長石並未在厚膜導體中充 317770 15 1312770 ................... 長，因此厚獏導體之八§或1^完全為銲料所腐蝕，因此 明瞭Lh〇促進灰長石之析出及成長。 之導St例：所示’在使用未含Ca〇之玻璃粉末E所得 • β中，灰長石並未析出，厚臈導體之A或pd完 卿。灰長石係Si、Ai、C “崎化物，= ^之賴組成中，未供給〜且灰長石不會析出。未 比較例3係未含Al2〇3粉末的比較Sl〇2_B2(VAl2〇3_Ca〇-Li2 bismuth-based glass powder (U to 15 晋金广, Al2〇3 powder 0.1 to 8 parts by mass. 'Knife ^ 100 parts by mass of conductive powder, Si〇2_B2(VAi2()3_eaQ_ 12;, 4 powder ratio (when the U mass is small, the adhesion to the ceramic substrate is stronger: lower. Further, when the amount is more than 15 f, not only the resistance value of the thick film conductor is 2, but also the glass floats on the thick film. The surface of the conductor is degraded by the contact resistance of the probe for electric clock, solder, and evaluation. (4) = The average particle size of the Al2〇3 powder in the powder is preferably 3 thick. In the inner ^3, when the average particle size of the powder exceeds 3 cores, not only the surface becomes thicker, but also the (4), "" the gray feldspar is precipitated in a sentence, and the surface of the thick film conductor is used to measure the electronic parts. The contact resistance of the probe of the characteristic becomes large αι2 (Λ Λ Λ 导电 导电 导电 导电 导电 导电 导电 导电 导电 导电 导电 导电 导电 导电 导电 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物The analysis of human feldspar is "less" and easy to resist the other side of the fiber. When it is more than 8 parts by mass, it not only touches the resistance field, but also adheres to the ceramic substrate. The conductive powder to be used may be formed by a general thick film conductor. For example, only two or more kinds of powders such as AU, Ag, etc. may be used. The average particle diameter of the conductive powder is preferably 10 "m 317770 11 1312770 Hereinafter, the shape of the conductive powder may be in the form of a granule or a flake, and is not particularly limited. Further, the organic carrier may be ethylcellulose or methacrylic acid as in the conventional art. A methacrylate or the like is dissolved in a solvent such as rosinol (terpineo1) or butyl carbitol (butyl carbit〇l). Further, the present invention is in addition to a conductive powder, SKVB2〇3_Al2〇3_CaC)_l12o In addition to the glass powder and the powder of 〇3, it is also possible to add conventional powders, such as Bi2〇3, Si〇2, Cu〇, for the purpose of achieving the adhesion strength of the thick film conductor or the wettability of the solder. (Zn), or an oxide powder. (Examples) (Example 1) Relatively, granular powder of average particle size 15#m (4) parts by mass, Ray: Particles of 〇1 Um & Pd powder The volume of the composition of the A5 皙 于 于 于At the end 1, the average particle size of 〇.5_A] 2〇3 powder 1 part by mass, = dioxin rosin alcohol solution as a carrier, and the so-called chain '(4) as a thick body forming paste. The thick film conductors are formed on the board, and at 15 (re|^ h brushed in 鄕绍基, ν dry each. At the peak temperature §5〇t, 9 minutes, 30 minutes for people, the belt furnace will Thick film conductor film with dry σ pattern. The film thickness of the predetermined thick film conductor was formed by firing 'the substrate was fired'. The film thickness was measured by a stylus type film thickness meter. 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 The resistance value of the pattern and the zinc resistance are carried out in the following manner. The thick-film conductor that is first fired, and the operation of measuring the resistance value is carried out after the welding of the helmet of the Cong:: Berry 0 n 3 Berry % Ag · 0.5% by mass of Cu::: dip / ΓΓ less clock = :==. By making the measured resistance value 1 Ω or more, it is confirmed that the can is generated, and the solder resist is evaluated for solder resistance. The post-number of people was evaluated as the adhesion strength by using a lead-free solder composed of 96 5 f%%^3 mass% 〇5.5% by mass Cu, and the copper wire of the diameter (fourth) was soldered to the pattern of 2.GmmX2 Gmm. The thick film conductor is pulled and peeled in the vertical direction of the moon to measure the tensile force of the peeling. The thickness of the thick film conductor measured and the subsequent strength are shown in Table 3. The area resistance value, the solder resistance, and the thick film conductor of the third embodiment are evenly immersed in the solder for 12 times, and the area resistance u is broken below _, and (4) solderability is preferable. And its strength is also high, above 60N. (Bei, 2, 3, and Comparative Examples 1 and 2) 'A thick film conductor was obtained in the same manner as in Example i except that the amount of use and the type of glass powder were changed as shown in Tables 1 and 2, and Examples] The same measurement was carried out. The film thickness, area resistance, and solder resistance of the thick film conductor measured and 317770 13 1312770 are shown in Table 3. In the thick film conductor of the second embodiment, even if it is immersed in a fresh material, the area resistance value is preferably 10 Ω or less, and the solder resistance is preferable. And its strength is also high, above 60N. The thick film conductor of Example 3 is evenly immersed in the fresh material 12 times, the area resistance and the continuous line 4 are also high in strength, at 6 〇 n = more Γ: Τ wide temperature is higher than the Boma powder a, or the glass powder powder In a small amount, it was found that if the glass powder c yoke example 3 was used, the thickness of the thick film conductor was higher. 4 A f - Aspect The thickness of the thick film conductor of Comparative Example 1 was low, and the area resistance value at the time of the first person was 1 Κ Ω or more, resulting in deterioration of freshness resistance. ::Example 2 = At the fourth time, the conductive system has an area U or more, which causes deterioration of solder resistance. (Comparative Example 3) Glass 2 For the reduced powder, except for the case where the Al2Q3 powder was not added, the type of the glass field powder (glass powder 纟Α), the other glass, the 'J 5 # ik ^ 1 η , the seventh end and the broken glass powder The ratio is compared with Beishi! Similarly, the thick film conductor was obtained and measured in the same manner. And the film of the thick film conductor measured by Xingbei Example 1 is followed by the strength (4) Table 3. Self-storage (10), solder resistance, and the thick film guiding system of Comparative Example 3 were at or above the third level, resulting in resistance to (four) deterioration. , the product resistance value becomes 317770 14 1312770 [Table i] Composition ratio (% by mass) Softening temperature (°r ί Si02 B2O3 AI2O3 CaO Li20 Ba〇 - Glass powder A 38.0 8.0 15.0 38.0 1.0 . ----- -- -- -- 2.0 — 660 620 580 720 650 Glass powder B 38.0 8.0 15.0 37.0 2.0 Glass powder C 40.0 5.0 16.0 33.0 6.0 Glass powder D 40.0 12.0 13.0 33.0 — Glass powder E 45.0 13.0 5.0 — 2.0 ^3?7〇~ [Table 2 Conductive powder (mass part) _ oxide Ag powder Pd powder glass powder 太 ^ Ο ι too Example 1 99.0 1.0 Glass powder A 5.0 1 π Example 2 99.0 1.0 Glass powder B 4.0 — — 1. U 1 〇 Example 3 99.0 1.0 Glass powder C 3^0, ~y〇~ -^丄·υ _1.0 10 Comparative example 1 "99.0 Bu 1.0 ~ WWW^~D Comparative example 2 99.0 1.0 Glass powder E 5.0 1 π Comparative example 3 99.0 1.0 Glass powder A 5.0 1 . υ [Table 3] . Example 1 Example 2 Film thickness (/zm) 〇r\ Area resistance value (m Q ) Solder resistance (back) ----- - Then strength 8 0 4.5 >12 ---ViN/ s60 8.5 3.8 >12 — r >12 Example 3 8.0 Bu 3.0 ~65 Comparative Example 1 8.5 4.5 *~~-—— 3 -_75 Comparative Example 2 8.0 5.0 —----- --- ~ 35 Comparative Example 3 8.0 4.0 ^55 As shown in the parent example 1, in the use of the guide material that does not contain l, the gray feldspar is not in The thick film conductor is filled with 317770 15 1312770 ................... Long, so the thick 貘 conductor of the eight § or 1 ^ is completely corroded by the solder, so it is clear that Lh〇 promotes Precipitation and growth of ash feldspar. St. Example: As shown in the figure [In the use of glass powder E without Ca •, β, ash feldspar did not precipitate, thick A 臈 conductor A or pd finished. Gray feldspar Si , Ai, C "Sakis, = ^ Dependent composition, not supplied ~ and ash feldspar will not precipitate. Comparative Example 3 is not containing Al2 〇 3 powder comparison

未添加執粉末時，可得知灰長 =匕物屯末 析出’而集中析出在厚膜導體與紹 ^面中不均句 銲料保護厚膜導體。 土板之界面處’不能從 317770 16When the powder is not added, it is known that the gray length = the precipitation of the sputum at the end of the sputum and the concentration of the thick film conductor and the unevenness of the surface of the thick film conductor. The interface of the earth plate is not available from 317770 16

Claims (1)

BIW9 ·. .. ·.. 'Ί· 第951〇5210號專利申 (98年5月'14甲：案 1. 申請專莉範圍： 種居膜導體形成用組成物，係由導 ==成者，其特徵為:前=化=: 匕严S1〇2_B2〇3_Al2(VCa〇_Li2〇系坡蹲粉末及 粉末’且實質上未含鉛，前述Si02-B2CVAl Ω / 3 ^ tb^ : Si02： 20 ^ 60 ty% 所」5貝量％、从〇3:2至25質量％、加：2〇至5〇 貝1/6及Li2〇 : 〇.1至1〇質量％。 2· 2申請專利範圍第1項之厚膜導體形成用組成物，其 中，該玻璃粉末之Li"的組成比為〇 5至6質量％。、 3. ^申請專·御i項之厚料體形成馳成物。，盆 相對於該導電粉末100質量份，該Si〇2，B2〇3_Al2CV =a〇-Ll2〇系玻璃粉末為〇1至15質量份，該ai处粉 末為0.1至8質量份。 4. 如申請專利範圍第1項之厚膜導體形成用組成物，其 中’該導電粉末係Au、Ag、pd及pt之至少一種。 5. :種厚膜導體之製造方法，包括：.在導電粉末中添加包 3 ji02_；B2G)3_Al2G)3_Ca〇_Li2〇 系玻璃粉末及 粉末 且'貝上未含鉛之氧化物粉末，以及有機载體；將藉由 犯練該等材料所得之導電膏塗布在陶€基板，然後在 5〇〇c以上、未滿90(rCi溫度予只燒成，其中，前述 • 2 B2〇3_Al2〇3_Ca〇-Li2〇系玻璃粉末之組成比為： Si〇2 . 20 至 60 質量 ％、&2〇3 : 2 至 25 質量 ％、Al2〇3 : 2至25質置％、Ca〇 : 2〇至％質量％及Li2〇 : 〇」至 】7 (修正本)317770 1312770 第95105210號專利中請案 (98年5月 14日） 10質量％。 6. —種厚膜導體，係在組成中包含Li20者，其特徵為： 在該厚膜導體内部均勻地析出灰長石，前述Li20係固 定於灰長石。BIW9 ·. .. ·.. 'Ί· No. 951〇5210 Patent Application (May 98, '14 A: Case 1. Application for the Lily Range: Composition for the formation of a film-forming conductor, is guided by == The characteristic is: front = chemical =: 匕 strict S1 〇 2_B2 〇 3_Al2 (VCa 〇 _ Li 2 〇 蹲 蹲 蹲 powder and powder ' and substantially no lead, the aforementioned SiO 2 - B2CVAl Ω / 3 ^ tb ^ : Si02 : 20 ^ 60 ty% "5 ft. %, from 〇 3:2 to 25% by mass, plus: 2 〇 to 5 〇 1/6 and Li 2 〇: 〇.1 to 1 〇 mass %. 2· 2 A composition for forming a thick film conductor according to the first aspect of the invention, wherein a composition ratio of Li" of the glass powder is 〇5 to 6% by mass. 3. ^ Application for a thick material forming a special item The pot is 1 to 15 parts by mass, and the powder at the ai is 0.1 to 8 parts by mass with respect to 100 parts by mass of the conductive powder, the Si〇2, B2〇3_Al2CV = a〇-Ll2 lanthanum glass powder. 4. The thick film conductor forming composition according to claim 1, wherein the conductive powder is at least one of Au, Ag, pd and pt. 5. A method for producing a thick film conductor, comprising: Adding package to conductive powder 3 Ji02_;B2G)3_Al2G)3_Ca〇_Li2 〇-based glass powder and powder and 'lead-free oxide powder on the shell, and organic carrier; coating the conductive paste obtained by cultivating the materials on the substrate And then above 5〇〇c, less than 90 (rCi temperature is only fired, wherein the composition ratio of the above 2 B2〇3_Al2〇3_Ca〇-Li2 lanthanide glass powder is: Si〇2. 20 to 60 mass %, &2〇3: 2 to 25 mass%, Al2〇3: 2 to 25 mass%, Ca〇: 2〇 to % mass%, and Li2〇: 〇” to 】7 (Revised) 317770 1312770 Request No. 95105210 (May 14, 1998) 10% by mass. 6. A thick film conductor comprising Li20 in its composition, characterized in that: ash feldspar is uniformly deposited inside the thick film conductor, The aforementioned Li20 system is fixed to ash feldspar. 18 (修正本)31777018 (amendment) 317770