1301854 九、發明說明： 【發明所屬之技彳标領域】 本發明有關於無鉛焊接合金，焊接材料及使用該等之 焊接接頭。 5 【】 近來’錯毒的問題已引發強烈立法動作規定環境中鉛 的處置方法。因此，做為一電子產物零件的接合材料，一 種無鉛焊料已經取代了傳統錫_鉛焊料。 就做為焊料的合金而言，所需的獨特性質有：熔化溫 10度、張力強度、延展性（可延伸的性質）、可濕性、零件接 頭的接合力之類。 焊料的熔化溫度較好設定在2〇〇〇c。若焊料的熔點過 7 ’則在回流焊射溫度會超過零件耐熱度，使用此電回 L焊接法可I會使零件蒙受傷害。另—方面，#焊料的溶 點過低，則如果零件周圍溫度升高，焊料會變成幾乎溶化 以至於零件可能掉下或剝落。 在有使用錯為焊料的回流焊接法中，典型的有錫 錯焊料合金。任擇地，下述的無錯焊料合金已經研究出來，1301854 IX. Description of the Invention: [Technical Field of the Invention] The present invention relates to a lead-free solder alloy, a solder material, and a solder joint using the same. 5 [] Recently, the problem of 'poisoning' has triggered a strong legislative action to regulate the disposal of lead in the environment. Therefore, as a bonding material for an electronic product part, a lead-free solder has replaced the conventional tin-lead solder. As for the alloy as a solder, the unique properties required are: melting temperature of 10 degrees, tensile strength, ductility (extensible properties), wettability, joint strength of the joints of the parts, and the like. The melting temperature of the solder is preferably set at 2 〇〇〇 c. If the melting point of the solder exceeds 7 ′, the reflow temperature will exceed the heat resistance of the part. Using this electric return L welding method can cause damage to the part. On the other hand, if the melting point of the solder is too low, if the temperature around the part rises, the solder will become almost melted so that the part may fall or peel off. In the reflow soldering method in which solder is used as a solder, a tin-displaced solder alloy is typical. Optionally, the following error-free solder alloy has been studied,
20如·叶有錫邊(-銅）為基底的、錫-銅(-鎳）為基底的、錫I 20 I鋼為基底的、錫娜紙_銘)為基底的、錫善銀，為基 底的焊料合金之類。 •其中歸類為第1群的，有：錫-銀(-銅)為基底的、錫, (鎳）為基底的、錫务銅為基底的焊料合金，均具有溶點被 測為21代至2贼的合金組成份，並用於射流焊接法、回 1301854 =焊接法之類。然而，這些合金㈣點仍高出傳統錫名焊 料3〇C至40°C。結果，在使用這些合金於回流焊接法的溫 X下其溶點可忐超過零件的耐熱溫度。要增加對應零件 的耐熱溫度至足以使用上述合金於回流焊接法有技術上的 困難同日寸，錫-鋅(H呂）為基底的、錫_銦_銀-麵為基底 的之類合金（歸為第_)，用於PCB (印刷電路板）組裝 j域，此組裝通常採用回流焊接法。然而第π群合金的溶化 態在空氣中會被高度氧化，在此點合金要提供於射流焊接 法有技術上的困難。雖然糾群合金做為焊料相對於第博 w 2說有許多不利之處，但第π群合金有優勢在其雜可以調 即到溫度範圍接近傳統錫_錯焊料的溶點。再者，一種郎 群合金可被用來調節組成份，由此其溶點可降低到約18叱 至210°C的範圍。 15 ” ，㈠局I底的焊料合金可以被用在 電回流焊接，_魏點是在⑽代至細。c這個接近傳 統錫-;7料料祕的_，有㈣纽合錢無料 料中屬低價的一種。然而，一般認為可濕性對於焊料的接 頭基底材料並不佳。再者，—般已堅信，若 銅為基底之材料的接頭暴露於高溫且高澄度的情況下 至在回流焊接之後，零件的接合力會被顯著地亞化。 進焊料_來 降低電阻。 豕又一些問題，例如移動的發生及 錫H料基底之焊料合金的雜接近錫_錯合金 20 1301854 的熔點，錫-鉛合金相似於錫-鋅為基底之焊料的例子。當接 合此合金系統至以銅為基底之材料，銅卡化合物不會產生 因為鋅沒被使用。依此，不會發生接合表面與銅的接合力 在南溫南屋度狀態下顯著降低的現象。 5 同時’#焊接至-銀電極時’銀銦化合物會產生於接 合表面。-般已堅信’化合物的相態會隨著時間成長變大 且變得脆弱，因而介面力降低。此外，若使用一個熱循環 於零件接合處，可觀察到接獅焊料會變形。PCB科學技 術上的發展已被集中於窄距的基底設計，且已需要更高層 10 次的組裝科學技術。 這樣的一個技術傾向描繪出一件要事：焊料的變形可 能導致短路。再者，若焊料中含有大量稀有又昂貴的姻， 則材料費會很高且不能確定可持續地進一步供應。 炼點在18 0 °C到21G °c範圍的焊料合金被廣泛使用於 15 -種焊接方法：焊接進行數次（回料接後射流焊接、回 流焊接後回流焊接之類），由於溫度特性致此。於此，問題 點在於此次焊接處會在接下來的焊接進程剝落。尤其在大 規模集成電路零件之類，零件會隨著焊料由PCB浮動開。 &現象的原因是：在第二次焊接或其後，前次焊接產生之 2〇接頭'J：干料被部分炫化，接合力因而降低，在這情況，接頭 就曰口PCB弓折或零件變形而剝落。那就是，焊料合金的 ϋ貝中’焊料合金開始溶化之溫度（在下文中以固化線表 不）與焊料合金完全純之溫度（在下文中以液化線表示） 的差異愈大，接頭制落的可能性就愈高。 1301854 在傳統技蟄中，例如：日本專利編號259989〇 (參考 資料1)，外加鋅到錫•銀為基底之焊料中會使機械力或抗蠕 變力增強。 同時，外加鋅或銀會降低熔點這件事已揭露。 5 然而，參考資料1中敘述的銀濃度過高，等於或多於1 %重《百分比。例如··在高銀濃度的焊料（丨％重量百分比） 如錫-6鋅-6銦-1銀，吸熱最大值區域（其頂點在熔點2〇〇艽 附近）擴大，可從第9圖由DSC (差動掃描熱量計）的測量 值看出。結果，在與錫-鉛焊料相同的反流焊接狀況下，似 10乎該焊料無有效率地熔化完全，焊料的流動性變差，因此 接頭無完全形成。在此例，真空焊接仍然因此降低接合力。 又，日本專利早期公開案Heissei編號9_174278(參考資料2) 中’銦被加入一接近錫-辞共晶成分的的合金用以降低熔點 並改善可濕性使零件金屬化。此外，銀被加入該合金以致 15 錫-辞銦中的似固化微結構辞相針狀物變成球狀固化微結 構並精巧地散開它們。因此，鋅濃度被設定在6%到11%重 量百分比，而銀被設定在0.5%到3%重量百分比。 傳統無鉛焊料可能蒙受各式問題例如由於鋅造成的 拙劣的可濕性，鋅是錫-鋅(-鉍，-鋁）為基底之焊料中的一個 20問題，還有傳統無鉛焊料可能蒙受在高溫高濕下會降·低與 銅電極間接合力的問題。此外，使用稀少金屬如銦、銀是 錫-銦-銀-鉍為基底之焊料合金中的一個問題。 【發明内容】 8 1301854 本發明的目標是達到溶化溫度特性與錫士為基底的 焊料的相同，以及解決傳統錫-鋅(_鉍，_鋁）為基底之焊料合 金與錫-銦-銀·鉍為基底之焊料合金的問題。 尤其有_個重要的目標，要改善焊料接頭在高溫高濕 5 環境下之可靠性。 ^為了達到這些目標，依據本發明，一種以錫-鋅-銦-銀 系統為基礎之焊料合金，具有（重量百分比）：〇·3% <鋅 <5.0/G ’0.1% $ 銦 $4·〇%，〇.1% $ 銀 $〇·4%，其餘為錫。 C實施方式】 10 之詳細說明 在下文中，將伴隨參考對應圖例詳細說明本發明之較 佳實施例。 依據本發明，一種錫-鋅-銦-銀焊料合金，其中包含小 U量銀，是為了避免降低交界面結合力當焊料與以銅為基底 之材料的接頭暴露在高温高濕的環境下，依據錫-辞_銦為基 底之焊料的熔點為210°C或稍低。 由熔點與接合可靠性的觀點來看，每個元素的較佳濃 度如下，以重量百分比表示之： 3.0% <鋅<5.〇% ; 20 0·1% S銦 <20.0% ;及 0.1% $銀$0.4%。 在下文中，將會解釋成分範圍。 鋅》辰度從約3.0%到5.0%重量百分比。當鋅濃度低於 /重i百分比時，焊料的溶點不能低於2〇〇它。又，若 1301854 鋅濃度低於3.0%重量百分比時，固化溫度與液化溫度的差 距變大，即使銦濃度增加。結果，在多數次的焊接進程中， 似乎零件接頭會剝落。 另一方面，當鋅濃度高於5.0%重量百分比時，在高溫 5 高濕下，與銅薄片的交界面接合力會降低。再者，若鋅濃 度提高，焊料的可濕性會惡化，結局是焊料氧化以及降低 接頭的電阻。 銦濃度從0.1%到20.0%重量百分比。當濃度低於約0.1 %重量百分比時，熔點無法如預期中降低。若銦濃度高於 10 20.0%重量百分比，焊料熔點的固化溫度會變太低。如錫-20 銦，固化溫度是153°C。若固化溫度降低，當暴露在高溫環 境下焊料會熔解並剝落。 此外，使用設備讓熱產生可能造成同樣的失敗。仍又， 當錫-20銦的固化溫度（153°C)以及液化溫度（199°C)相 15 距過大，會發生焊料在下一次或之後的焊接過程中剝落的 情況。 銀濃度從0.1%到0.4%重量百分比。若濃度低於約0.1 %重量百分比，當焊接後暴露在高溫高濕環境下無法得到 避免接合力降低的效應。 20 若銀濃度超過0.4%重量百分比，則焊料傾向於在溫度 高於焊料熔點時熔化，以致已熔之焊料的流動性變差，在 回流焊接進程。 又，更佳的是，組成範圍如下，以重量百分比表示： 0.3%〈鋅 <5·0〇/〇 ； 10 1301854 υ· 1% ^4.〇〇/〇 :及 0·1% $ 銀$0·4%。 右焊料合金的銦濃度增加’焊料合金的延展性變惡 5的二祕若鋼濃度在4%重量百分比或更低，可確保的30% 釋放_严/因此當有熱衝擊之類的壓力，可因焊料變形而 賴下’若焊料無延錄，計⑶或零件被 擴張或昼士縮時，焊料接頭可能會破裂。20, such as tin with tin (-copper) as the base, tin-copper (-nickel) as the base, tin I 20 I steel as the base, tina paper _ Ming) as the base, tin good silver, a solder alloy of the substrate or the like. • Among them classified as Group 1, there are: tin-silver (-copper)-based, tin, (nickel)-based, tin-copper-based solder alloys, all having a melting point measured as 21 generations To 2 thief alloy components, and used in jet welding, back 1301854 = welding method and the like. However, these alloy (4) points are still higher than conventional tin-name solders from 3 °C to 40 °C. As a result, the melting point of these alloys at the temperature X of the reflow soldering method can exceed the heat resistant temperature of the part. It is necessary to increase the heat resistance temperature of the corresponding parts to the technical difficulty of using the above alloys in the reflow soldering method, and the tin-zinc (Hlu) is a base, tin-indium-silver-surface-based alloy. For the _), for the PCB (printed circuit board) assembly j domain, this assembly is usually done by reflow soldering. However, the melting state of the π-group alloy is highly oxidized in the air, and at this point the alloy is technically difficult to provide for the jet welding method. Although the tempered alloy as a solder has many disadvantages compared to the first, the π-group alloy has an advantage in that its impurity can be adjusted to a temperature range close to the melting point of the conventional tin-wrong solder. Further, a Lang group alloy can be used to adjust the composition, whereby the melting point can be lowered to a range of about 18 至 to 210 °C. 15", (a) the solder alloy of the bottom of the board I can be used in electrical reflow soldering, _ Wei point is in the (10) generation to fine. c this is close to the traditional tin -; 7 material secret _, there are (four) new money without material It is a low-priced one. However, it is generally considered that the wettability is not good for the joint material of the solder. Furthermore, it is generally believed that if the joint of the copper-based material is exposed to high temperature and high degree of stability to reflux After soldering, the bonding force of the part is significantly sub-induced. Into the solder _ to reduce the resistance. 豕 Some problems, such as the occurrence of movement and the solder alloy of the tin H material base, close to the melting point of the tin-alloy alloy 20 1301854, Tin-lead alloys are similar to tin-zinc-based solders. When bonding this alloy system to a copper-based material, the copper-based compound does not form because zinc is not used. Thus, the joint surface does not occur. The bonding force of copper is significantly reduced under the condition of South Wennan. 5 At the same time '# soldering to - silver electrode' silver indium compound will be produced on the joint surface. - It is believed that the phase of the compound will be with time. Growing bigger And it becomes fragile, so the interface force is reduced. In addition, if a thermal cycle is used at the joint of the part, it can be observed that the lion solder will be deformed. The development of PCB science has been concentrated on the narrow-base design and has been needed 10 times of assembly science at a higher level. Such a technology tends to portray one thing: the deformation of the solder may cause a short circuit. Moreover, if the solder contains a large number of rare and expensive marriages, the material cost will be high and cannot Determining sustainable further supply. Solder alloys with a melting point in the range of 18 0 ° C to 21 G ° C are widely used in 15 kinds of welding methods: welding several times (reflow welding after reflow, reflow soldering after reflow soldering) Class), due to temperature characteristics. The problem is that the solder joint will peel off during the next soldering process. Especially in large-scale integrated circuit parts, the parts will float with the solder floating from the PCB. The reason for the phenomenon is: in the second welding or after, the second joint produced by the previous welding 'J: the dry material is partially stunned, and the joint force is thus reduced. In this case, the joint The edge of the PCB is folded or the part is deformed and peeled off. That is, the temperature at which the solder alloy begins to melt in the mussel of the solder alloy (hereinafter referred to as the solidified line) and the temperature at which the solder alloy is completely pure (hereinafter referred to as the liquefaction line) The greater the difference, the higher the possibility of joints falling. 1301854 In traditional techniques, for example, Japanese Patent No. 259989〇 (Reference 1), plus zinc to tin/silver-based solder will cause machinery The force or creep resistance is enhanced. At the same time, the addition of zinc or silver reduces the melting point. 5 However, the silver concentration described in Reference 1 is too high, equal to or more than 1% by weight. For example. In high silver concentration solder (丨% by weight) such as tin-6Zn-6 indium-1 silver, the endothermic maximum region (the apex of which is near the melting point of 2〇〇艽) is expanded from Figure 9 by DSC (difference) The measured value of the dynamic scanning calorimeter is seen. As a result, in the same reverse flow soldering condition as the tin-lead solder, it seems that the solder is completely melted inefficiently, and the fluidity of the solder is deteriorated, so that the joint is not completely formed. In this case, vacuum welding still reduces the joint force. Further, in Japanese Patent Laid-open Publication Heissei No. 9_174278 (Reference 2), 'indium is added to an alloy close to the tin-eutectic composition to lower the melting point and improve the wettability to metallize the part. In addition, silver is added to the alloy so that the solidified microstructured needles in the 15 tin-indium turn into spherical solidified microstructures and finely disperse them. Therefore, the zinc concentration is set at 6% to 11% by weight, and the silver is set at 0.5% to 3% by weight. Traditional lead-free solders may suffer from various problems such as poor wettability due to zinc, zinc is a 20-star problem in tin-zinc (-铋, -aluminum)-based solder, and traditional lead-free solders may suffer from high temperatures. Under high humidity, it will lower the bonding force between the copper electrode and the copper electrode. Further, the use of a rare metal such as indium or silver is a problem in a tin-indium-silver-iridium-based solder alloy. SUMMARY OF THE INVENTION 8 1301854 The object of the present invention is to achieve the same melting temperature characteristics as tin-based solder, and to solve the traditional tin-zinc (_铋,_aluminum)-based solder alloy and tin-indium-silver The problem of solder alloys that are bases. In particular, there is an important goal to improve the reliability of solder joints in high temperature and high humidity environments. In order to achieve these objectives, according to the present invention, a solder alloy based on a tin-zinc-indium-silver system has (% by weight): 〇·3% <zinc<5.0/G '0.1% $ indium $4 ·〇%,〇.1% $ Silver$〇·4%, the rest is tin. C. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the corresponding drawings. According to the present invention, a tin-zinc-indium-silver solder alloy containing a small amount of silver in order to avoid lowering the interface bonding force when the joint of the solder and the copper-based material is exposed to a high temperature and high humidity environment, The melting point of the solder based on tin-indium-indium is 210 ° C or lower. From the standpoint of melting point and bonding reliability, the preferred concentration of each element is as follows, expressed as a percentage by weight: 3.0% <zinc<5.〇%; 20 0·1% S indium <20.0%; And 0.1% $silver $0.4%. In the following, the range of ingredients will be explained. Zinc" is from about 3.0% to 5.0% by weight. When the zinc concentration is lower than / weight i percentage, the melting point of the solder cannot be lower than 2 〇〇. Further, if the zinc concentration of 1301854 is less than 3.0% by weight, the difference between the curing temperature and the liquefaction temperature becomes large, even if the indium concentration is increased. As a result, in most of the welding process, it seems that the joint of the part peels off. On the other hand, when the zinc concentration is higher than 5.0% by weight, the interface bonding force with the copper flakes is lowered at a high temperature of 5 high humidity. Furthermore, if the zinc concentration is increased, the wettability of the solder is deteriorated, and the result is solder oxidation and a decrease in the resistance of the joint. The indium concentration is from 0.1% to 20.0% by weight. When the concentration is less than about 0.1% by weight, the melting point cannot be lowered as expected. If the indium concentration is higher than 10 20.0% by weight, the curing temperature of the melting point of the solder becomes too low. Such as tin-20 indium, the curing temperature is 153 ° C. If the curing temperature is lowered, the solder will melt and peel off when exposed to a high temperature environment. In addition, using equipment to allow heat generation can cause the same failure. Still, when the solidification temperature (153 ° C) and the liquefaction temperature (199 ° C) of the tin--20 indium are too large, the solder may peel off during the next or subsequent soldering process. The silver concentration ranges from 0.1% to 0.4% by weight. If the concentration is less than about 0.1% by weight, the effect of avoiding the decrease in the bonding force cannot be obtained when exposed to a high temperature and high humidity environment after welding. 20 If the silver concentration exceeds 0.4% by weight, the solder tends to melt at a temperature higher than the melting point of the solder, so that the flowability of the melted solder deteriorates during the reflow soldering process. Further, more preferably, the composition range is as follows, expressed as a percentage by weight: 0.3% <zinc<5·0〇/〇; 10 1301854 υ·1% ^4.〇〇/〇: and 0·1% $ silver $0·4%. The concentration of indium in the right solder alloy increases. 'The ductility of the solder alloy becomes worse. The second steel has a concentration of 4% by weight or less, which ensures a 30% release _ severe. Therefore, when there is pressure such as thermal shock, It can be caused by solder deformation. If the solder is not extended, the solder joint may be broken when the gauge (3) or the part is expanded or the warp is contracted.
: 本I明中的尚溫商濕，，意味一 85。(：及85%RH (相對溼度）的環境。 10 實例 實例1 夕^中疋重里百分比3°/。銦和0_6%辞（其餘部分為 下不ΠίήΓ的剝洛力測量值，與關於暴露於高溫高壓環境 下不同的接合力。 15 ^ " $ Α斤之焊料合金約保持在230°C，該焊料 2已混合至預定組成。接著叫著劑將間狐&毫米的 严氣#=料平）/件與議個釘子料至附著銅之玻璃 =^ °11個樣本有使用助焊劑，接著，該樣本 2㈣開料接。使職波清洗機叫_清洗已焊接之 以致助知劑的殘留被移除。焊接且清洗過的PCB樣 本被放人-恤溫㈣（衫料妓_子），保持在％ 〇C 及 85% RH，接著，备 , 士 ㈣250小時測量錯接合力的剝落力。 弟1圖顯不不同的錯接合力，其中以焊料焊接QFP零 件，該焊料含重量百分比3%銦’〇，#，其餘部分為錫。 20 1301854 在此，0-6%鋅意為鋅的濃度在從〇到6%這個範圍内。又， 可庄思到當暴露在高溫高濕環境下，辞濃度增加，接合力 顯著下降。再者，當辞濃度為6%重量百分比，在暴露時間 500小時的時候，接合力變成1公斤力或更低。 5 也就是，在高温高濕環境下，當焊料中的鋅濃度增加 時，零件的接合力傾向降低。在高溫高濕環境下，焊料中 的鋅相散佈至接合表面與以銅為基底之物質作用，因此形 成一銅-鋅化合物層。在進程進行時，由於高濕造成鋅被氧 化的效應，以致接合表面的銅_鋅化合物層與的焊料的接合 10力顯著降低。可由第1圖看出，鋅濃度低於5%重量百分比 是較佳的。 同時，第2A圖到第2E圖描述了以DSC測量焊料的結 果’該焊料該焊料含重量百分比3%銦，2-6%鋅，〇·3%銀， 其餘部分為錫。若鋅濃度低於3%重量百分比，金屬的熔點 15會超過21〇 c。因此，鋅濃度高於3%重量百分比是較佳的。 又’若鋅濃度大於5%重量百分比，在高温高濕環境下 接合力會逐漸降低。因此，鋅濃度低於5%重量百分比是較 佳的。 實例二 20 實例二顯示結構的觀察，其中小量的銀外加入錫-4鋅 銦。每一焊料約0.6公克’具有重量百分比4%鋅，3%銦， 〇·1-0.5%銀，其餘為錫。該焊料溶解在陶瓷板上形成球形， 並在該狀況在空氣中冷卻。每個焊料粒子的切面被拋光亮 並以掃描電子顯微鏡觀察之。其結果描繪於圖3Α到3C。 12 1301854 已知由第3A圖到第3C圖，針狀物如鋅相減少當銀濃度 增加。又，可注意到球狀的鋅_銀相在第3B圖及第3C圖中增 加。仍又’已證實焊料的精細結構。鋅相精巧地散開，以 致鋅相間的連結消失。照這情況，造成接合力降低的鋅之 5氧化作用，在高溫高濕下並未散佈至焊料的内部，亦並未 降低接合力。 此例中銀濃度是〇·1%重量百分比，許多針狀物如鋅相 被觀察到，顯示於第3Α圖。然而，以確實證實一球狀鋅_ 銀層。 10 實例3 實例3中解釋了不同的電化學腐蝕能，例中小量的銀外 加入錫-4辞-3姻。 每一焊料，具有重量百分比4%鋅，3%銦，〇_〇·5%銀， 其餘為錫，配置成切面為5毫米χ5毫米的條狀。條狀樣本的 15 一面以1200孔防水拋光紙拋光，接著以氧化鋁懸浮液緩衝 之。隨後，樣本被浸入重量百分比3·5%之氣化鈉水溶液， 於25°C。又，利用一使用銀電極的標準電極，氣化銀電極， 以及飽和氯化鉀水溶液，可測量出產生於標準電極與焊料 2樣本之間的銀之電動勢差。測量結果顯示於第4圖。又，描 2〇述了未包含鋅之錫銦的電化學腐蝕能，做為參考樣本。田 已知由第4圖，當電動勢接近辞.3銦谭料的電動勢，焊 料夕令辞的氧化變得困難。亦即，外加重量百分比〇1%銀或 更多，可得到在進程中避免氧化的效應。 實例4 13 1301854 在貫例4中’焊接錫鋅-3銦-〇·3銀至一銅盤的接合表面 的觀察結果可被解釋。〇·3克的錫_4鋅_3銦_〇 3銀焊料被放置 於一銅盤上並提供助焊劑。接著，以加熱盤加熱至23〇〇c& 焊接。在此樣本被注入至一樹脂，拋光，使蒸發後，可使 5用SEM及X射線顯微分析（XMA)觀察到接合表面的切面。 SEM及XMA的觀察結果，可觀察到一辞層與一銀層產生於 焊料與銅盤間的接合表面。亦即，可以知道辞_銀相形成於 焊料與銅盤間。若辞_銅化合物相形成於接合表面，焊料與 鋅-銅化合物的交界面進行氧化，以致接合力降低。亦即， 10藉由避免辞-銅化合物層的形成，可以避免接合力降低。 實例5 實例5中，解釋了不同的炼點，例中小量的銀被外加入 錫-4鋅-3銦中。第5A圖到第测顯示以Dsc測量焊料溶點 的測量結果，其中該焊料為重量百分比4%鋅，3%銦， 15 %銀，其餘為錫。可在第5A圖到第5E圖看出，可注意到當 銀濃度增加，顯示熱吸收頂點在2G5t：至21代附近㈣^ 變大’且此範圍内焊料溶化量增加。若銀濃度變成〇放重 量百分比…讀值獅在2机至⑽⑽近成長至同樣 的情況在190。〇結果，例中當使用為焊料時，非常難溶化。 換句話說，焊料會先在較低溫度（約193亡）熔化' Ί 高溫度再-次、熔化。又，焊料的可濕性或細 由前述的測量結果，外加重量百分比G i%銀 電化學雜能改善。另-方面，料加超過重量百分比銀 〇.5%，以DSC測量合金，較高的溫度頂點提高。據此，烤 20 1301854 料難熔解’㈣可濕性或流動性因此惡化。 d、再者#銀外加入包含鋅的焊料中，名十狀物如鋅相減 夕且球狀的鋅_銀相增加。結果，焊料的精細結構可藉由結 5 構觀:破ϋ觀察到針狀物如鋅相，其巾銀濃度為〇1 里百刀比，可知到電化學腐姓能增加的效應 上述之此例。 藉由外加銀’辞_銀化合物相形成於接合表面當焊 妾；銅上因此當作一障礙層以抑制銅與辞作用“士果， 易被氧化__銅化合物層的形成可被中止，以致抑難合 1〇表面的氧化，因此防止接合力降低。 實例6 母一焊料含’以重量百分比， =:其餘為錫。焊财高歸化溫度的溫度贼溶化至 平板狀，且製備好一延展性的樣本。 15 此樣本為爪4樣本。延展性測試進行於延展速5 /秒0 如第6圖所證，當㈣量百分比 或更多的延展程度。 其結果描述於第6圖。 在〇到4%範圍時，可有3〇% 實例7 20 早父往地 ” 口、_助熔唞形成之無 利用於焊線及_。在此，該焊料 ㈣材科被 t、；击& 金从錫-辞-銦·銀系統 為基底，以重量百分比表示·· 3.0%〈辞 <5·〇% ; 〇·1% S銦 $4.0% ; 15 1301854 〇·1% $ 銀‘0.4% ;及 其餘為錫。 又，說到助焊劑，可能使用一已知助焊劑。 實例8 5 實例8中，一焊料接合力可被描述藉由利用一焊料合 金，其具有至少一選自於由鎳，鈦，鎂，銘及始所構成群 組的元素，該合金並以錫-鋅-銦-銀系統為基底，具有（以 重量百分比表示）： 3.0% <鋅<5.0% ; ίο 0.1% S 銦‘4.0% ;及 0.1% $ 銀‘0.4%。 在此，該至少一元素的總濃度係在約0·001%至約〇〇5 % (重量百分比）範圍内，且該焊料合金之其餘部分為錫。 高溫高濕測試進行如下列實例。第7圖顯示不同的接合 15力。接合力測量方法同實例1。使用焊料合金焊料製備樣 本，該焊料合金含有一上述元素並在一銅薄膜上進行回流 焊接。 第7圖中，F表示本發明中一標準無鉛焊料。又，α，β， C，D及Ε具有與F—樣的組成份除了錫外，並依序包含〇· 〇〇4 20 %鈦，〇·〇1 %鎳，〇· 〇1 %鎂，0· 05 %鋁及〇· 〇5 %鈷，以 重量百分比。又，其餘的部分為錫。在暴露於高溫高濕環 境1000小時之後比較接合力，發現樣本A，Β，C及Ε較標準F 好。又，可注意到樣本D保持至少相同或更多的接合力。 第8圖顯不在高溫高濕下三焊料接頭不同的接合力，三 16 1301854 焊料接頭的組成分：錫-8辞，錫-4鋅-3銦-0.3銀，及錫 -4鋅-3銦-0.3銀-0.003鈦。又，焊料接頭的形成方法如同實 例1。由第8圖可看出，外加鈦已確實證明為有效的在1500 小時之後。 又，比較於錫-8鋅-3鉍，接合力變成低於1公斤力在250 小時後。其他元素如鎳，鎂，鋁及鈷提供與鈦相同的效應。 實例9 10 15 20 實例9中一焊料合金與助焊劑形成之無鉛焊料材料被 利用為焊線與焊糊。在此，該焊料合金具有至少一選自於 由鎳，鈦，鎂，鋁及鈷所構成群組的元素，該合金並以錫· 辞•銦-銀系統為基底，以重量百分比表示： 3·〇%〈鋅 <5.0% ； 〇·1% S銦 $4.0% ;及 0·1% $銀€0.4%。 在此，該挑選出之至少一元素的總濃度在重量百分比 0.00U至0.05%範圍内，其餘為錫。 又，說到助焊劑，可能使用一已知助焊劑。 ^如上述，依據本發明，辞濃度在約重量百分比3%到5 1辄圍内，因此焊料接頭的可靠性可改善，在高溫高濕環 兄下又私明的焊料合金為一條狀焊料（溶解之焊料）， ^無料料合金作擴散結合之用。仍又，本發明包含電 一又備和電子攻備中使用本發明之焊料合金的焊料接頭。 據本《明巾使用焊料合金的無船焊料具有的炼點每 貝上相同於傳統锡娜料。因此，現用之錫·錯焊接法以及 17 1301854 現用零件與生產設備皆可使用此法。又，可提供無鉛焊料 材料具有焊料特性中極佳的零件接合力。 又，因為其固化溫度與液化溫度間的差距很小，可抑 制零件的浮動，即使組裝進程進行非常多次。仍又，當接 5 頭暴露在高溫高濕環境下，可避免降低接合力。 雖本發明已顯示並描述於較佳具體實例的觀點，仍可 藉由熟習技藝者理解之，該技藝可能在不離本發明申請專 利範圍精神下做不同改變與修飾。 I：圖式簡單說明3 10 由上述的較佳具體實例連同圖例可顯見本發明中上述 及其他的目標與特徵，圖例中： 第1圖顯示一個焊料接頭之剝落力呈暴露時間函數圖 表，上述的焊料與本發明中實例1 一致； 第2A圖至第2E圖顯示DSC測量焊料合金之結果呈溫度 15 函數，其中，本發明中實例1的錫-3銦-0.3銀外加入辞，改 變鋅濃度從2%至6%重量百分比； 第3A圖到第3C圖描繪出結構的典型圖，其中，本發明 中實例2的錫-4辞-3銦外加小量銀； 第4圖圖解顯示電化學腐蝕電位呈時間函數圖表，其 20 中，本發明中實例3的錫-4鋅-3銦外加小量銀； 第5A圖至第5E圖解釋不同熔解溫度呈銀濃度函數，其 中，本發明中實例1的錫-4鋅-3銦外加小量銀； 第6圖提供一個顯示了焊料合金各樣機械性能呈銦濃 度函數圖表，其中，本發明中實例6的錫-4鋅-0.3銀外加範 18 1301854 圍從0%到10%重量百分比的銦； 第7圖陳述一個顯示了與本發明中實例8—致的焊料合 金各樣機械性能呈暴露時間函數的圖表； 第8圖呈現一個顯示了本發明中實例8的另一焊料合金 5 各樣機械性能呈暴露時間； 第9圖描述一傳統錫-6鋅-6銦-1銀合的金DSC之測量 值。 【主要元件符號說明】 19: The temperature in this I Ming is wet, meaning an 85. (: and 85% RH (relative humidity) environment. 10 Example Example 1 夕^中中重重 percentage 3°/. Indium and 0_6% words (the rest is under the 剥 ήΓ ήΓ 洛 洛 洛 , , , Different bonding forces in high temperature and high pressure environment. 15 ^ " $ The solder alloy is kept at 230 ° C, the solder 2 has been mixed to the predetermined composition. Then the agent will be the fox of the fox & mm Material level) / piece and discuss a nail material to the glass attached to the copper = ^ ° 11 samples have used flux, then, the sample 2 (four) open material connection. Make the wave cleaning machine called _ cleaning welded so that the aid agent The residue was removed. The welded and cleaned PCB samples were placed in a man-shirt temperature (four) (shirts _ _ sub), kept at % 〇 C and 85% RH, and then, prepared, four (four) 250 hours to measure the wrong joint force Peeling force. Brother 1 shows a different wrong bonding force, in which QFP parts are soldered with solder, the solder contains 3% by weight of indium, and the rest is tin. 20 1301854 Here, 0-6% zinc The concentration of zinc is in the range from 〇 to 6%. Again, it can be exposed to high temperature and high humidity. The concentration of the rhythm increases, and the joint strength drops significantly. Further, when the concentration is 6% by weight, the joint force becomes 1 kg or less at the exposure time of 500 hours. 5 That is, in a high temperature and high humidity environment. When the concentration of zinc in the solder increases, the bonding force of the part tends to decrease. In a high-temperature and high-humidity environment, the zinc phase in the solder spreads to the bonding surface and acts on the copper-based substance, thereby forming a copper-zinc compound layer. During the progress of the process, the zinc is oxidized due to high humidity, so that the bonding force of the copper-zinc compound layer of the bonding surface and the solder is significantly reduced. As can be seen from Fig. 1, the zinc concentration is less than 5% by weight. At the same time, Figures 2A to 2E depict the results of measuring solder by DSC. The solder contains 3% by weight of indium, 2-6% zinc, 〇·3% silver, and the rest is tin. If the zinc concentration is less than 3% by weight, the melting point 15 of the metal will exceed 21 〇c. Therefore, it is preferred that the zinc concentration is higher than 3% by weight. Also, if the zinc concentration is more than 5% by weight, the temperature is high. Bonding in wet environment It will gradually decrease. Therefore, a zinc concentration of less than 5% by weight is preferred. Example 2 20 Example 2 shows the observation of the structure in which a small amount of silver is added to the tin-4 zinc indium. Each solder is about 0.6 gram. The weight percentage is 4% zinc, 3% indium, 〇·1-0.5% silver, and the balance is tin. The solder dissolves on the ceramic plate to form a spherical shape, and in this condition is cooled in the air. The cut surface of each solder particle is polished and bright. The results are observed by scanning electron microscopy. The results are depicted in Figures 3A to 3C. 12 1301854 It is known that from the 3A to 3C, the needles such as the zinc phase are reduced as the concentration of silver is increased. Also, the spherical shape can be noted. The zinc-silver phase is increased in Figures 3B and 3C. The fine structure of the solder has been confirmed. The zinc phase is delicately dispersed, so that the zinc-phase connection disappears. In this case, the oxidation of zinc which causes a decrease in the bonding force is not spread to the inside of the solder under high temperature and high humidity, and the bonding force is not lowered. The silver concentration in this example is 1·1% by weight, and many needles such as the zinc phase are observed and are shown in Figure 3. However, it was confirmed that a spherical zinc-silver layer was confirmed. 10 Example 3 Example 3 explains the different electrochemical corrosion energies. For example, a small amount of silver is added to the tin-4. Each solder has a weight percentage of 4% zinc, 3% indium, 〇_〇·5% silver, and the rest is tin, and is arranged in a strip shape of 5 mm χ 5 mm. The 15 sides of the strip sample were polished with 1200 holes of water-repellent polishing paper and then buffered with an alumina suspension. Subsequently, the sample was immersed in a 3.5% by weight aqueous solution of sodium carbonate at 25 °C. Further, by using a standard electrode using a silver electrode, a vaporized silver electrode, and a saturated aqueous solution of potassium chloride, the electromotive force difference of silver generated between the standard electrode and the solder 2 sample can be measured. The measurement results are shown in Figure 4. Further, the electrochemical corrosion energy of zinc indium containing no zinc is described as a reference sample. It is known from the fourth figure that when the electromotive force is close to the electromotive force of the indium. 3 indium tantalum, it is difficult to oxidize the solder. That is, the addition of a weight percentage of 〇1% silver or more gives an effect of avoiding oxidation in the process. Example 4 13 1301854 The observation of the bonding surface of the soldered tin-zinc-3 indium-niobium-3 silver to a copper disk in Example 4 can be explained. 〇·3 gram of tin _4 zinc _3 indium _ 〇 3 silver solder is placed on a copper disk and provides flux. Next, the plate was heated to 23 ° C & After the sample was injected into a resin, polished, and evaporated, the cut surface of the joint surface was observed by SEM and X-ray microanalysis (XMA). From the observations of SEM and XMA, it was observed that a layer of a layer and a layer of silver were produced on the joint surface between the solder and the copper disk. That is, it can be known that the silver phase is formed between the solder and the copper plate. If the copper compound phase is formed on the bonding surface, the interface between the solder and the zinc-copper compound is oxidized, so that the bonding force is lowered. That is, by avoiding the formation of the copper compound layer, it is possible to avoid a decrease in the bonding force. Example 5 In Example 5, different refining points were explained, in which a small amount of silver was externally added to tin-4Zn-3 indium. Fig. 5A to the first measurement show the measurement of the solder melting point measured by Dsc, wherein the solder is 4% by weight of zinc, 3% of indium, 15% of silver, and the balance is tin. As can be seen from Fig. 5A to Fig. 5E, it can be noted that as the silver concentration increases, the apex of the heat absorption is displayed in the vicinity of 2G5t: to 21 (four) and becomes larger and the amount of solder melting increases in this range. If the silver concentration becomes a percentage of the weight of the sputum, the reading lion grows from 2 to (10) (10) to the same condition at 190. As a result, in the case where solder is used, it is very difficult to dissolve. In other words, the solder will first melt at a lower temperature (about 193 dies), Ί high temperature, and then melt. Further, the wettability or fineness of the solder is improved by the aforementioned measurement results, and the weight percentage G i% silver electrochemical noise is improved. On the other hand, the material is added in excess of the weight percentage of silver 〇.5%, measured by DSC, and the higher temperature apex is raised. Accordingly, the roasting of 20 1301854 is difficult to melt. (4) The wettability or fluidity is thus deteriorated. d. Further, in the solder containing zinc added to the outside of the silver, the name such as the zinc phase is reduced and the spherical zinc-silver phase is increased. As a result, the fine structure of the solder can be observed by the structure of the junction: the needle is observed as a zinc phase, and the silver concentration of the towel is 〇1 百百比比, and the effect of the electrochemical rot can be increased. example. By adding silver 'words' - silver compound phase formed on the bonding surface as a solder joint; copper as a barrier layer to inhibit copper and rhyme "success, easy to be oxidized __ copper compound layer formation can be suspended, Therefore, the oxidation of the surface is inhibited, so that the bonding force is prevented from decreasing. Example 6 The mother-solder contains '% by weight, =: the rest is tin. The temperature of the high-densification temperature of the weld is melted to a flat shape, and is prepared. A malleable sample. 15 This sample is a claw 4 sample. The ductility test is performed at an extension speed of 5 / sec. 0 As shown in Figure 6, when (4) the percentage of the volume or more is extended. The results are described in Figure 6. In the range of 4%, there may be 3〇%. Example 7 20 The early father goes to the ground, and the formation of the fused flux is not used in the welding line and _. Here, the solder (four) material is t,; hit & gold from the tin-word-indium-silver system as the base, expressed in weight percent · 3.0% <word <5·〇%; 〇·1% S Indium $4.0%; 15 1301854 〇·1% $ Silver '0.4%; and the rest is tin. Again, when it comes to flux, it is possible to use a known flux. Example 8 5 In Example 8, a solder bonding force can be described by using a solder alloy having at least one element selected from the group consisting of nickel, titanium, magnesium, and the beginning, which is tin-plated. - Zinc-indium-silver system as substrate, with (in weight percent): 3.0% <zinc<5.0%; ίο 0.1% S Indium '4.0%; and 0.1% $silver '0.4%. Here, the total concentration of the at least one element is in the range of about 0.001% to about 5% by weight, and the remainder of the solder alloy is tin. The high temperature and high humidity test was carried out as in the following examples. Figure 7 shows the different joint forces. The joint force measurement method is the same as in Example 1. A sample was prepared using a solder alloy solder containing one of the above elements and reflow soldering on a copper film. In Fig. 7, F denotes a standard lead-free solder in the present invention. Further, α, β, C, D and Ε have a F-like composition in addition to tin, and sequentially include 〇·〇〇4 20% titanium, 〇·〇1% nickel, 〇·〇1% magnesium, 0· 05 % aluminum and 〇· 〇 5 % cobalt, by weight. Also, the rest is tin. The joint strength was compared after exposure to a high temperature and high humidity environment for 1000 hours, and it was found that the samples A, Β, C and Ε were better than the standard F. Again, it can be noted that sample D maintains at least the same or more bonding forces. Figure 8 shows the different bonding forces of the three solder joints under high temperature and high humidity. The composition of the three 16 1301854 solder joints: tin-8, tin-4zinc-3 indium-0.3 silver, and tin-4zinc-3 indium -0.3 silver - 0.003 titanium. Further, the solder joint is formed in the same manner as in Example 1. As can be seen from Figure 8, the addition of titanium has indeed proven to be effective after 1500 hours. Also, compared to tin-8 zinc-3铋, the bonding force becomes less than 1 kg force after 250 hours. Other elements such as nickel, magnesium, aluminum and cobalt provide the same effect as titanium. Example 9 10 15 20 A lead-free solder material formed of a solder alloy and a flux in Example 9 was utilized as a bonding wire and a solder paste. Here, the solder alloy has at least one element selected from the group consisting of nickel, titanium, magnesium, aluminum, and cobalt, and the alloy is based on a tin·indium-silver system, expressed as a percentage by weight: 3 ·〇%<zinc<5.0%; 〇·1% S indium $4.0%; and 0·1% $silver €0.4%. Here, the total concentration of the selected at least one element is in the range of 0.00U to 0.05% by weight, and the balance is tin. Again, when it comes to flux, it is possible to use a known flux. ^ As described above, according to the present invention, the concentration of the word is in the range of about 3% to about 5% by weight, so that the reliability of the solder joint can be improved, and the solder alloy under the high temperature and high humidity ring is a strip solder ( Dissolved solder), ^No material alloy for diffusion bonding. Still further, the present invention encompasses solder joints using the solder alloy of the present invention in electrical and electronic attack. According to this "Woodless solder using a solder alloy, the refining point has the same refining point per berth as the conventional tin material. Therefore, the current tin-wrong welding method and the current parts and production equipment of 17 1301854 can be used. In addition, a lead-free solder material can be provided which has excellent part bonding strength in solder characteristics. Also, since the difference between the curing temperature and the liquefaction temperature is small, the floating of the parts can be suppressed even if the assembly process is performed many times. Still, when the head is exposed to high temperature and high humidity, the joint force can be avoided. While the invention has been shown and described with respect to the preferred embodiments of the embodiments of the present invention, it is understood that the invention may be variously modified and modified without departing from the scope of the invention. I: BRIEF DESCRIPTION OF THE DRAWINGS 3 10 The above and other objects and features of the present invention are apparent from the above-described preferred embodiments, together with the drawings. In the drawings: FIG. 1 is a graph showing the peeling force of a solder joint as a function of exposure time, The solder is consistent with Example 1 of the present invention; FIGS. 2A to 2E show that the result of DSC measurement of the solder alloy is a function of temperature 15, wherein the tin-3 indium-0.3 silver of Example 1 of the present invention is added to change the zinc. The concentration is from 2% to 6% by weight; Figures 3A to 3C depict a typical diagram of the structure, wherein the tin-4 of the example 2 of the present invention is in addition to a small amount of silver; Figure 4 is a diagram showing the electrification The corrosion potential is a time function graph, in which the tin-4 zinc-3 indium of Example 3 of the present invention is applied with a small amount of silver; FIGS. 5A to 5E illustrate different melting temperatures as a function of silver concentration, wherein the present invention Tin-4Zn-3 indium of Example 1 plus a small amount of silver; Figure 6 provides a graph showing the mechanical properties of the solder alloy as a function of indium concentration, wherein the tin-4 zinc-0.3 silver of Example 6 of the present invention Plus Van 18 1301854 from 0% to 10% by weight Indium; Figure 7 illustrates a graph showing the various mechanical properties of the solder alloy as shown in Example 8 of the present invention as a function of exposure time; Figure 8 shows another solder alloy 5 showing Example 8 of the present invention. The mechanical properties are shown as exposure times; Figure 9 depicts the measurement of a conventional tin-6 zinc-6 indium-1 silver gold DSC. [Main component symbol description] 19