TWI742963B - Composite solder and method for manufacturing the same - Google Patents
Composite solder and method for manufacturing the same Download PDFInfo
- Publication number
- TWI742963B TWI742963B TW109144209A TW109144209A TWI742963B TW I742963 B TWI742963 B TW I742963B TW 109144209 A TW109144209 A TW 109144209A TW 109144209 A TW109144209 A TW 109144209A TW I742963 B TWI742963 B TW I742963B
- Authority
- TW
- Taiwan
- Prior art keywords
- solder
- weight
- temperature
- parts
- composite
- Prior art date
Links
Images
Abstract
Description
本發明是有關於一種焊料及其製造方法，且特別是有關於一種複合焊料及其製造方法。The present invention relates to a solder and its manufacturing method, and more particularly to a composite solder and its manufacturing method.
隨著科技的進步，電子元件不斷朝向「輕、薄、短、小」的型態發展，具高密度和高精確度之電子封裝技術也逐漸受到重視。電子封裝技術可依據製程分為五種不同的層級。第零層級是針對積體電路晶片進行連線的製程。第一層級是將數個積體電路晶片黏著於封裝基板上並完成其中的電性連接和密封保護之製程，又可稱為晶片至模組（chip to module）的製程。第二層級是將經第一層級封裝完成的數個元件安裝於電路板上的製程，又可稱為模組至印刷電路板（module to PCB）的製程。第三層級則是將經第二層級封裝完成的數個印刷電路板安裝於主板上的製程，又可稱為印刷電路板至母板（PCB to mother board）的製程。第四層級則是結合數個母板以形成完整的電子產品。With the advancement of technology, electronic components continue to develop toward the "light, thin, short, and small" type, and electronic packaging technology with high density and high precision has gradually attracted attention. Electronic packaging technology can be divided into five different levels according to the manufacturing process. The zeroth level is the process of wiring for integrated circuit chips. The first level is the process of adhering several integrated circuit chips to the package substrate and completing the electrical connection and sealing protection therein. It can also be called the chip to module process. The second level is the process of mounting several components completed by the first level of packaging on a circuit board, which can also be called a module to PCB process. The third level is the process of mounting several printed circuit boards on the motherboard through the second level of packaging, which can also be called the process of PCB to mother board (PCB to mother board). The fourth level is to combine several motherboards to form a complete electronic product.
然而，在各層級中或是不同層級間的封裝製程中，都會經過多道回焊製程，故已結合之元件可能會因為焊接點的重新熔化而導致電子元件掉落或是焊接點位移等問題，如此可能會造成相鄰的兩個焊接點相互接觸而造成短路的現象發生。However, in the packaging process at each level or between different levels, there will be multiple reflow processes. Therefore, the combined components may cause problems such as the drop of the electronic components or the displacement of the solder joints due to the re-melting of the solder joints. , This may cause two adjacent solder joints to contact each other and cause a short circuit.
本發明提供一種複合焊料及其製造方法，將含有Ag和Bi的二元合金與含有Sn、Ag、Cu的三元合金進行混合以形成具有低液化溫度的複合焊料，如此可避免熱應力之累積並確保其他封裝製程中的焊接點的可靠度。The present invention provides a composite solder and a manufacturing method thereof. The binary alloy containing Ag and Bi and the ternary alloy containing Sn, Ag, Cu are mixed to form a composite solder with a low liquefaction temperature, which can avoid the accumulation of thermal stress And to ensure the reliability of solder joints in other packaging processes.
本發明提供一種製造複合焊料的方法，其包括以下步驟。提供第一焊料。第一焊料包含有Ag和Bi的二元合金。相對於100重量份的二元合金，Ag的含量約為2.5重量份，Bi的含量約為97.5重量份。提供第二焊料。第二焊料包含有Sn、Ag和Cu的三元合金。相對於100重量份的三元合金，Sn的含量約為96.5重量份，Ag的含量約為3重量份，Cu的含量約為0.5重量份。在混合溫度下混合第一焊料和第二焊料以形成複合焊料。The present invention provides a method for manufacturing composite solder, which includes the following steps. Provide the first solder. The first solder contains a binary alloy of Ag and Bi. With respect to 100 parts by weight of the binary alloy, the content of Ag is about 2.5 parts by weight, and the content of Bi is about 97.5 parts by weight. Provide a second solder. The second solder contains a ternary alloy of Sn, Ag, and Cu. Relative to 100 parts by weight of the ternary alloy, the content of Sn is about 96.5 parts by weight, the content of Ag is about 3 parts by weight, and the content of Cu is about 0.5 parts by weight. The first solder and the second solder are mixed at the mixing temperature to form a composite solder.
在本發明的一實施例中，第一焊料和第二焊料的重量比為25:75至75:25。In an embodiment of the present invention, the weight ratio of the first solder to the second solder is 25:75 to 75:25.
在本發明的一實施例中，第一焊料的共晶溫度大於第二焊料的共晶溫度之間。In an embodiment of the present invention, the eutectic temperature of the first solder is greater than the eutectic temperature of the second solder.
在本發明的一實施例中，在混合溫度下混合第一焊料和第二焊料的過程中，第二焊料包覆第一焊料並使得第二焊料的Sn擴散而與第一焊料的Bi形成共晶相。In an embodiment of the present invention, in the process of mixing the first solder and the second solder at the mixing temperature, the second solder covers the first solder and causes the Sn of the second solder to diffuse to form a co-existence with the Bi of the first solder. Crystalline phase.
在本發明的一實施例中，複合焊料的液化溫度介於130℃和136℃之間。In an embodiment of the present invention, the liquefaction temperature of the composite solder is between 130°C and 136°C.
在本發明的一實施例中，在混合第一焊料和第二焊料的步驟中包括使用助焊劑。In an embodiment of the present invention, the step of mixing the first solder and the second solder includes using a flux.
在本發明的一實施例中，複合焊料經回焊製程後，其固化之析出物具有以下介金屬相：針狀Ag 3Sn相、Cu 6Sn 5相以及Bi和β-Sn之共晶相。 In an embodiment of the present invention, after the reflow process of the composite solder, the solidified precipitates have the following intermetallic phases: acicular Ag 3 Sn phase, Cu 6 Sn 5 phase, and eutectic phase of Bi and β-Sn .
在本發明的一實施例中，製備第一焊料的步驟包括將Ag金屬和Bi金屬以2.5:97.5之重量比進行混合並於800℃下進行均質化處理。In an embodiment of the present invention, the step of preparing the first solder includes mixing Ag metal and Bi metal in a weight ratio of 2.5:97.5 and performing homogenization treatment at 800°C.
本發明提供一種複合焊料，其是藉由上述製造複合焊料的方法製備。The present invention provides a composite solder, which is prepared by the above-mentioned method for manufacturing composite solder.
基於上述，在本發明的複合焊料及其製造方法中，將含有Ag和Bi的二元合金與含有Sn、Ag、Cu的三元合金進行混合，如此可大幅降低複合焊料的液化溫度，以避免熱應力累積在焊點並確保焊點的可靠度。Based on the above, in the composite solder and its manufacturing method of the present invention, the binary alloy containing Ag and Bi is mixed with the ternary alloy containing Sn, Ag, and Cu. This can greatly reduce the liquefaction temperature of the composite solder to avoid Thermal stress accumulates in the solder joints and ensures the reliability of the solder joints.
參照本實施例之圖式以更全面地闡述本發明。然而，本發明亦可以各種不同的形式體現，而不應限於本文中所述之實施例。圖式中的層與區域的厚度會為了清楚起見而放大。相同或相似之參考號碼表示相同或相似之元件，以下段落將不再一一贅述。The present invention will be explained more fully with reference to the drawings of this embodiment. However, the present invention can also be embodied in various different forms and should not be limited to the embodiments described herein. The thickness of the layers and regions in the drawing will be exaggerated for clarity. The same or similar reference numbers indicate the same or similar elements, and the following paragraphs will not repeat them one by one.
應當理解，當諸如元件被稱為在另一元件「上」或「連接到」另一元件時，其可以直接在另一元件上或與另一元件連接，或者也可存在中間元件。若當元件被稱為「直接在另一元件上」或「直接連接到」另一元件時，則不存在中間元件。如本文所使用的，「連接」可以指物理及/或電性連接，而「電性連接」或「耦合」可為二元件間存在其它元件。It should be understood that when an element is referred to as being "on" or "connected to" another element, it can be directly on or connected to the other element, or intervening elements may also be present. If an element is referred to as being "directly on" or "directly connected to" another element, there are no intermediate elements. As used herein, "connection" can refer to physical and/or electrical connection, and "electrical connection" or "coupling" can mean that there are other elements between two elements.
本文使用的「約」、「近似」或「實質上」包括所提到的值和在所屬技術領域中具有通常知識者能夠確定之特定值的可接受的偏差範圍內的平均值，考慮到所討論的測量和與測量相關的誤差的特定數量（即，測量系統的限制）。例如，「約」可以表示在所述值的一個或多個標準偏差內，或±30％、±20％、±10％、±5％內。再者，本文使用的「約」、「近似」或「實質上」可依光學性質、蝕刻性質或其它性質，來選擇較可接受的偏差範圍或標準偏差，而可不用一個標準偏差適用全部性質。As used herein, "about", "approximately" or "substantially" includes the mentioned value and the average value within the acceptable deviation range of the specific value that can be determined by a person with ordinary knowledge in the technical field. The measurement in question and the specific number of errors associated with the measurement (ie, the limitations of the measurement system). For example, "about" can mean within one or more standard deviations of the stated value, or within ±30%, ±20%, ±10%, ±5%. Furthermore, the "about", "approximate" or "substantially" used herein can select a more acceptable deviation range or standard deviation based on optical properties, etching properties or other properties, and not one standard deviation can be applied to all properties .
使用本文中所使用的用語僅為闡述例示性實施例，而非限制本揭露。在此種情形中，除非在上下文中另有解釋，否則單數形式包括多數形式。The terms used herein are only used to illustrate exemplary embodiments, but not to limit the present disclosure. In this case, unless otherwise explained in the context, the singular form includes the majority form.
圖1為本發明一實施例的複合焊料的製造方法的流程圖。FIG. 1 is a flowchart of a method for manufacturing a composite solder according to an embodiment of the present invention.
請參照圖1，執行步驟S1，提供包含有Ag和Bi的二元合金的第一焊料。相對於100重量份的二元合金，Ag的含量可約為2.5重量份，而Bi的含量可約為97.5重量份。第一焊料（即Ag-Bi合金）的共晶溫度可約為262.5℃。在一些實施例中，第一焊料為無鉛焊料。Ag和Bi之間無介金屬化合物生成，且Ag和Bi以2.5 wt.%和97.5 wt.%的比例形成之Ag-Bi合金，其共晶溫度為其合金之最低溫度且Ag比例佔很少，可有效降低成本。Please refer to FIG. 1 and perform step S1 to provide a first solder containing a binary alloy of Ag and Bi. Relative to 100 parts by weight of the binary alloy, the content of Ag may be about 2.5 parts by weight, and the content of Bi may be about 97.5 parts by weight. The eutectic temperature of the first solder (ie, Ag-Bi alloy) may be about 262.5°C. In some embodiments, the first solder is lead-free solder. There is no intermetallic compound formed between Ag and Bi, and Ag-Bi alloys formed at the ratios of 2.5 wt.% and 97.5 wt.% of Ag and Bi, the eutectic temperature is the lowest temperature of the alloy and the proportion of Ag is very small , Can effectively reduce costs.
在一些實施例中，第一焊料的製造方法可包括以下步驟。首先，使用純度為99.9%的Ag金屬和Bi金屬。接著，以相對於Ag金屬和Bi金屬的總重量，分別秤取2.5 wt.%和97.5 wt.%的Ag金屬和Bi金屬。然後，對經秤取好的Ag和Bi金屬進行清洗製程。而後，將清洗完成之Ag金屬和Bi金屬置於容器（例如石英玻璃管）中並進行密封（避免氧化）。之後，對放置有Ag金屬和Bi金屬的容器進行均質化處理。最後，將經完成均質化處理的容器立即放入冰水中進行淬冷並使溫度達到室溫。In some embodiments, the manufacturing method of the first solder may include the following steps. First, Ag metal and Bi metal with a purity of 99.9% are used. Next, 2.5 wt.% and 97.5 wt.% of Ag metal and Bi metal were weighed with respect to the total weight of Ag metal and Bi metal. Then, the weighed Ag and Bi metals are cleaned. Then, the cleaned Ag metal and Bi metal are placed in a container (such as a quartz glass tube) and sealed (to avoid oxidation). After that, the container in which the Ag metal and Bi metal are placed is homogenized. Finally, immediately put the homogenized container into ice water for quenching and bring the temperature to room temperature.
在一些實施例中，可採用以下步驟進行上述清洗製程。首先，以例如丙酮等的有機溶液去除Ag金屬和Bi金屬的表面油汙。接著，以例如稀鹽酸等的酸性溶液去除Ag金屬和Bi金屬的表面氧化物。然後，以例如酒精等的有機溶液去除Ag金屬和Bi金屬的表面雜質。In some embodiments, the following steps may be used to perform the above-mentioned cleaning process. First, an organic solution such as acetone is used to remove the surface oil stains of Ag metal and Bi metal. Next, the surface oxides of Ag metal and Bi metal are removed with an acidic solution such as dilute hydrochloric acid. Then, the surface impurities of Ag metal and Bi metal are removed with an organic solution such as alcohol.
在一些實施例中，可採用以下參數進行均質化處理。均質化處理的溫度可為800℃。均質化處理的時間可為24小時。均質化處理的壓力可為2.0×10 -3torr。 In some embodiments, the following parameters can be used for homogenization treatment. The temperature of the homogenization treatment may be 800°C. The time for the homogenization treatment can be 24 hours. The pressure of the homogenization treatment may be 2.0×10 -3 torr.
請繼續參照圖1，執行步驟S2，提供包含有Sn、Ag和Cu的三元合金的第二焊料。相對於100重量份的三元合金，Sn的含量可約為96.5重量份，Ag的含量可約為3重量份，Cu的含量可約為0.5重量份。Sn、Ag和Cu原子之間相互反應所生成的相除了有Sn基質相以外，還會生成Ag 3Sn、Cu 6Sn 5和Cu 3Sn共晶相。Ag 3Sn和Cu 6Sn 5共晶相可使Sn基質區域減小且可有助於阻礙晶界的滑動，以改善材料的機械性質並延長材料在高溫中的疲勞壽命。 Please continue to refer to FIG. 1 and perform step S2 to provide a second solder containing a ternary alloy of Sn, Ag, and Cu. Relative to 100 parts by weight of the ternary alloy, the content of Sn may be about 96.5 parts by weight, the content of Ag may be about 3 parts by weight, and the content of Cu may be about 0.5 parts by weight. In addition to the Sn matrix phase, the phases formed by the mutual reaction of Sn, Ag and Cu atoms will also generate Ag 3 Sn, Cu 6 Sn 5 and Cu 3 Sn eutectic phases. The Ag 3 Sn and Cu 6 Sn 5 eutectic phases can reduce the Sn matrix area and can help hinder the sliding of grain boundaries, so as to improve the mechanical properties of the material and prolong the fatigue life of the material at high temperatures.
第二焊料的共晶溫度可小於第一焊料的共晶溫度。第二焊料（即Sn-Ag-Cu合金，又可稱為SAC合金）的共晶溫度可約為217℃。在一些實施例中，第二焊料為無鉛焊料。The eutectic temperature of the second solder may be lower than the eutectic temperature of the first solder. The eutectic temperature of the second solder (ie Sn-Ag-Cu alloy, also known as SAC alloy) may be about 217°C. In some embodiments, the second solder is lead-free solder.
請繼續參照圖1，執行步驟S3，在混合溫度下混合第一焊料和第二焊料以形成複合焊料。複合焊料的液化溫度可介於130℃和136℃之間。在一些實施例中，在混合第一焊料和所述第二焊料的步驟中可包括使用例如松香中性活化類助焊劑（rosin mildly activated，RMA）等的助焊劑。助焊劑為松香類的有機物，添加微酸性的有機酸，具有高揮發性。添加助焊劑目的是在焊接過程中，助焊劑會清潔金屬表面，增加焊料間的濕潤性，並在焊接過程結束後揮發，不會殘留在在焊料間。一般的添加量約在0.03mL左右。在一些實施例中，第一焊料和第二焊料的重量比可為25:75至75:25。在一些實施例中，混合溫度介於第一焊料的共晶溫度和第二焊料的共晶溫度之間。在一些實施例中，混合溫度可為230℃。Please continue to refer to FIG. 1 and perform step S3 to mix the first solder and the second solder at the mixing temperature to form a composite solder. The liquefaction temperature of the composite solder can be between 130°C and 136°C. In some embodiments, the step of mixing the first solder and the second solder may include using a flux such as rosin mildly activated (RMA) flux. The flux is organic rosin, with slightly acidic organic acid added, which has high volatility. The purpose of adding flux is that during the soldering process, the flux will clean the metal surface, increase the wettability between the solders, and volatilize after the soldering process is completed, and will not remain in the soldering room. The general addition amount is about 0.03mL. In some embodiments, the weight ratio of the first solder to the second solder may be 25:75 to 75:25. In some embodiments, the mixing temperature is between the eutectic temperature of the first solder and the eutectic temperature of the second solder. In some embodiments, the mixing temperature may be 230°C.
在一些實施例中，可採用以下步驟混合第一焊料和第二焊料以形成複合焊料。首先，將第一焊料和第二焊料以預設的重量比放置於容器（例如石英玻璃管）中。接著，於容器中加入助焊劑。然後，將容器放置在230℃的熔解爐中待其完全溶解並恆溫5分鐘，以形成複合焊料。最後，將複合焊料取出並於空氣中進行冷卻。In some embodiments, the following steps may be used to mix the first solder and the second solder to form a composite solder. First, the first solder and the second solder are placed in a container (for example, a quartz glass tube) in a predetermined weight ratio. Next, add flux to the container. Then, the container was placed in a melting furnace at 230° C. to be completely dissolved and kept at a constant temperature for 5 minutes to form a composite solder. Finally, the composite solder is taken out and cooled in the air.
在一些實施例中，由於第一焊料的共晶溫度大於第二焊料的共晶溫度，且混合溫度介於第一焊料的共晶溫度和第二焊料的共晶溫度之間，因此，在該混合溫度下混合第一焊料和第二焊料的過程中，第二焊料會先熔化而包覆第一焊料並使得第二焊料的Sn擴散而與第一焊料的Bi形成共晶相。如此一來，即便混合溫度低於第一焊料的共晶溫度，但隨著Sn的擴散而與Bi形成較穩定之共晶相組成，使得第一焊料的液化溫度逐漸降低而可在混合溫度下完全熔解。In some embodiments, since the eutectic temperature of the first solder is greater than the eutectic temperature of the second solder, and the mixing temperature is between the eutectic temperature of the first solder and the eutectic temperature of the second solder, the In the process of mixing the first solder and the second solder at the mixing temperature, the second solder will first melt to cover the first solder and cause the Sn of the second solder to diffuse to form a eutectic phase with the Bi of the first solder. In this way, even if the mixing temperature is lower than the eutectic temperature of the first solder, with the diffusion of Sn, a relatively stable eutectic phase composition is formed with Bi, so that the liquefaction temperature of the first solder is gradually lowered and can be at the mixing temperature. Completely melted.
基於上述，在實施例的複合焊料及其製造方法中，將含有Ag和Bi的二元合金與含有Sn、Ag、Cu的三元合金進行混合，如此可大幅降低複合焊料的液化溫度，以避免熱應力累積在焊點並確保焊點的可靠度。Based on the foregoing, in the composite solder and the manufacturing method of the embodiment, the binary alloy containing Ag and Bi is mixed with the ternary alloy containing Sn, Ag, and Cu, which can greatly reduce the liquefaction temperature of the composite solder to avoid Thermal stress accumulates in the solder joints and ensures the reliability of the solder joints.
下文將參照實施例1-3和比較例1來更具體地描述本發明的特徵。雖然描述了以下實施例，但是在不逾越本發明範疇之情況下，可適當地改變所用材料、其量及比率、處理細節以及處理流程等等。因此，不應由下文所述之實施例對本發明作出限制性地解釋。 第一焊料 Hereinafter, the features of the present invention will be described more specifically with reference to Examples 1-3 and Comparative Example 1. Although the following embodiments are described, the materials used, their amounts and ratios, processing details, processing procedures, etc. can be appropriately changed without going beyond the scope of the present invention. Therefore, the embodiments described below should not restrictively interpret the present invention. First solder
首先，使用純度為99.9%的Ag金屬和Bi金屬（自友和貿易股份有限公司購得）。接著，以相對於Ag金屬和Bi金屬的總重量，分別秤取2.5 wt.%和97.5 wt.%的Ag金屬和Bi金屬。然後，依序以丙酮、稀鹽酸和酒精來清洗Ag金屬和Bi金屬。而後，將清洗完成之Ag金屬和Bi金屬置於石英玻璃管中並進行封管。之後，將裝有Ag金屬和Bi金屬的石英玻璃管放入高溫爐中，進行溫度為800℃、時間為24小時的均質化處理。然後，待均質化處理完成之後，取出石英玻璃管並立即放入冰水中進行淬冷以使溫度達到室溫。最後，敲碎石英玻璃管以取出Ag-Bi合金棒。 第二焊料 First, Ag metal and Bi metal (purchased from Youhe Trading Co., Ltd.) with a purity of 99.9% are used. Next, 2.5 wt.% and 97.5 wt.% of Ag metal and Bi metal were weighed with respect to the total weight of Ag metal and Bi metal. Then, the Ag metal and Bi metal are washed sequentially with acetone, dilute hydrochloric acid and alcohol. Then, the cleaned Ag metal and Bi metal are placed in the quartz glass tube and sealed. After that, the quartz glass tube containing Ag metal and Bi metal was placed in a high-temperature furnace, and a homogenization treatment was performed at a temperature of 800° C. and a time of 24 hours. Then, after the homogenization process is completed, the quartz glass tube is taken out and immediately placed in ice water for quenching to bring the temperature to room temperature. Finally, break the quartz glass tube to take out the Ag-Bi alloy rod. Second solder
自岱輝電子取得SAC合金，其中SAC合金含有3 wt.%的Ag、0.5 wt.%的Cu和96.5 wt.%的Sn。 實施例 1-3 Obtained SAC alloy from Daihui Electronics. The SAC alloy contains 3 wt.% Ag, 0.5 wt.% Cu and 96.5 wt.% Sn. Example 1-3
以下表1所示出的比例將第一焊料和第二焊料置於石英玻璃管中。接著，將約0.03mL之松香中性活化類助焊劑（RMA）加入至石英玻璃管中。然後，放入230℃的熔解爐中待其完全熔解並恆溫5分鐘以形成複合焊料。之後，取出來後於空氣中進行冷卻。
[表1]
自岱輝電子取得SAC合金，其中SAC合金含有3 wt.%的Ag、0.5 wt.%的Cu和96.5 wt.%的Sn。
實驗 1 Obtained SAC alloy from Daihui Electronics. The SAC alloy contains 3 wt.% Ag, 0.5 wt.% Cu and 96.5 wt.% Sn.
使用Pandat軟體計算實施例1-3的固化曲線以得到實施例1-3的薛爾固化路徑，實驗結果分別顯示於圖2A、圖3A和圖4A。圖2A為實施例1的複合焊料的薛爾固化曲線圖。圖3A為實施例2的複合焊料的薛爾固化曲線圖。圖4A為實施例3的複合焊料的薛爾固化曲線圖。Pandat software was used to calculate the curing curves of Examples 1-3 to obtain the Scherr curing path of Examples 1-3. The experimental results are shown in FIG. 2A, FIG. 3A, and FIG. 4A, respectively. FIG. 2A is a graph showing the Sheer curing curve of the composite solder of Example 1. FIG. FIG. 3A is a Sheer curing curve diagram of the composite solder of Example 2. FIG. FIG. 4A is a Sheer curing curve diagram of the composite solder of Example 3. FIG.
從圖2A、3A和4A所示出的結果可知，實施例1-3一開始皆會析出Ag
3Sn，但隨著溫度下降，實施例1和實施例2會析出Ag
3Sn+Cu
6Sn
5相（見圖2A和圖3A），而實施例3（見圖4A）則會析出Ag
3Sn+Bi相。接著，隨著溫度繼續下降，實施例1和實施例2會析出Ag
3Sn+Cu
6Sn
5+Sn相（見圖2A和圖3A），而實施例3（見圖4A）仍不會有介金屬Cu
6Sn
5相生成。最後固化溫度降低142.6℃後，實施例1、2析出共晶之Bi+β-Sn相，而不會有較脆之純Bi相，但實施例3除了析出共晶之Bi+β-Sn相之外，還析出了較脆之純Bi相。
實驗 2 From the results shown in Figures 2A, 3A and 4A, it can be seen that in Examples 1-3, Ag 3 Sn is precipitated at the beginning, but as the temperature drops, Ag 3 Sn+Cu 6 Sn is precipitated in Examples 1 and 2 5 phases (see Figure 2A and Figure 3A), and Example 3 (see Figure 4A) will precipitate Ag 3 Sn+Bi phase. Then, as the temperature continues to drop, the Ag 3 Sn+Cu 6 Sn 5 +Sn phase will be precipitated in Example 1 and Example 2 (see Figure 2A and Figure 3A), while Example 3 (see Figure 4A) will still not have The intermetallic Cu 6 Sn 5 phase is formed. After the final solidification temperature was reduced by 142.6℃, the eutectic Bi+β-Sn phase was precipitated in Examples 1 and 2 without the brittle pure Bi phase. However, in Example 3, except for the precipitation of the eutectic Bi+β-Sn phase In addition, a relatively brittle pure Bi phase was also precipitated.
以SEM分析實施例1-3在230℃下進行回焊1次後的合金微結構，實驗結果分別顯示於圖2B、圖3B和圖4B。圖2B為實施例1的複合焊料經回焊一次後的SEM圖像。圖3B為實施例2的複合焊料經回焊1次後的SEM圖像。圖4B為實施例3的複合焊料經回焊1次後的SEM圖像。圖5為實施例1-3的複合焊料經回焊一次後的SEM圖像，其中圖5的(a)、(d)、(g)為實施例1於不同放大倍率下的SEM圖；圖5的(b)、(e)、(h)為實施例2於不同放大倍率下的SEM圖；圖5的(c)、(f)、(i)為實施例3於不同放大倍率下的SEM圖。The alloy microstructures of Examples 1-3 after being reflowed once at 230° C. were analyzed by SEM. The experimental results are shown in Fig. 2B, Fig. 3B and Fig. 4B, respectively. 2B is an SEM image of the composite solder of Example 1 after being reflowed once. Fig. 3B is an SEM image of the composite solder of Example 2 after being reflowed once. FIG. 4B is an SEM image of the composite solder of Example 3 after being reflowed once. Figure 5 is an SEM image of the composite solder of Example 1-3 after reflowing once, wherein (a), (d), (g) of Figure 5 are SEM images of Example 1 at different magnifications; 5 (b), (e), (h) are the SEM images of Example 2 at different magnifications; Figure 5 (c), (f), (i) are Example 3 at different magnifications SEM image.
請參照圖2B和圖5，可從圖2B觀察到針狀的Ag 3Sn相和較小點狀之Cu 6Sn 5相，符合圖2A所示出的薛爾固化路徑。由此可知，實施例1具有可增加機械強度之Ag 3Sn相，且並未生成較脆之Bi相。另外，從圖5可觀察到共晶之Bi+β-Sn相，符合圖2A所示出的薛爾固化路徑。 2B and FIG. 5, it can be observed from FIG. 2B that the needle-shaped Ag 3 Sn phase and the smaller dot-shaped Cu 6 Sn 5 phase conform to the Scherr curing path shown in FIG. 2A. From this, it can be seen that Example 1 has an Ag 3 Sn phase that can increase mechanical strength, and does not generate a brittle Bi phase. In addition, it can be observed from FIG. 5 that the Bi+β-Sn phase of the eutectic is in accordance with the Scherr solidification path shown in FIG. 2A.
請參照圖3B和圖5，可從圖3B觀察到針狀的Ag 3Sn相和較小點狀之Cu 6Sn 5相，符合圖3A所示出的薛爾固化路徑。由此可知，實施例2具有可增加機械強度之Ag 3Sn相，且並未生成較脆之Bi相。比較圖2B和圖3B所示出的結果，由於實施例1的Sn含量較高，故在185.5℃即析出Ag 3Sn+Cu 6Sn 5+Sn相，而實施例2則是在147.5℃（接近共晶溫度）才析出Ag 3Sn+Cu 6Sn 5+Sn相。另外，從圖5可觀察到共晶之Bi+β-Sn相，符合圖3A所示出的薛爾固化路徑。 Please refer to FIG. 3B and FIG. 5, it can be seen from FIG. 3B that the needle-shaped Ag 3 Sn phase and the smaller dot-shaped Cu 6 Sn 5 phase conform to the Scherr curing path shown in FIG. 3A. From this, it can be seen that Example 2 has an Ag 3 Sn phase that can increase mechanical strength, and does not generate a brittle Bi phase. Comparing the results shown in Figure 2B and Figure 3B, due to the higher Sn content in Example 1, Ag 3 Sn+Cu 6 Sn 5 +Sn phase was precipitated at 185.5°C, while that in Example 2 was at 147.5°C ( It is close to the eutectic temperature) that Ag 3 Sn+Cu 6 Sn 5 +Sn phase is precipitated. In addition, it can be observed from FIG. 5 that the Bi+β-Sn phase of the eutectic is in accordance with the Scherr solidification path shown in FIG. 3A.
請參照圖4B和圖5，可從圖4B觀察到Ag 3Sn相和塊狀的純Bi相（Bi phase），且未觀察到Cu 6Sn 5相，符合圖4A所示出的薛爾固化路徑。由此可知，實施例3具有可增加機械強度之Ag 3Sn相，但生成塊狀之較脆的Bi相。另外，從圖5可觀察到共晶之Bi+β-Sn相，符合圖3A所示出的薛爾固化路徑。 實驗 3 Please refer to Figure 4B and Figure 5, you can observe from Figure 4B Ag 3 Sn phase and bulk pure Bi phase (Bi phase), and no Cu 6 Sn 5 phase is observed, in line with the Sher solidification shown in Figure 4A path. It can be seen from this that Example 3 has an Ag 3 Sn phase that can increase the mechanical strength, but a bulky and brittle Bi phase is formed. In addition, it can be observed from FIG. 5 that the Bi+β-Sn phase of the eutectic is in accordance with the Scherr solidification path shown in FIG. 3A. Experiment 3
以DSC對在不同回焊次數後的實施例1-3和比較例1進行熱分析。在DSC分析中，以升溫速率為5℃/min，從室溫升溫至250℃，恆溫3分鐘後，再以降溫速率為5℃/min至室溫。實驗結果分別顯示於圖6A至圖6D和圖7A至圖7D。Thermal analysis was performed on Examples 1-3 and Comparative Example 1 after different reflow times by DSC. In the DSC analysis, the temperature is increased from room temperature to 250°C at a heating rate of 5°C/min, and after a constant temperature for 3 minutes, the temperature is reduced at a rate of 5°C/min to room temperature. The experimental results are shown in Figs. 6A to 6D and Figs. 7A to 7D, respectively.
圖6A至圖6D分別為實施例1-3和比較例1的複合焊料在不同回焊次數後以升溫速率為5℃/min的DSC曲線圖。圖7A至圖7D分別為實施例1-3和比較例1的複合焊料在不同回焊次數後以降溫速率為5℃/min的DSC曲線圖。在圖6A-6D以及圖7A-7D中，比較例1以及實施例1-3前面的數值表示回焊的次數。舉例而言，圖6A和7A中所示出的1-比較例1表示比較例1經回焊1次的DSC曲線；圖6B和圖7B中所示出的2-實施例1表示實施例1經回焊2次的DSC曲線。6A to 6D are respectively the DSC curve diagrams of the composite solders of Examples 1-3 and Comparative Example 1 at a heating rate of 5° C./min after different reflow times. 7A to 7D are respectively the DSC curve diagrams of the composite solders of Examples 1-3 and Comparative Example 1 at a cooling rate of 5° C./min after different reflow times. In FIGS. 6A-6D and FIGS. 7A-7D, the numerical values in front of Comparative Example 1 and Examples 1-3 indicate the number of reflow soldering. For example, 1-Comparative Example 1 shown in FIGS. 6A and 7A represents the DSC curve of Comparative Example 1 after reflowing once; 2-Example 1 shown in FIGS. 6B and 7B represents Example 1 DSC curve after reflowing twice.
從圖6A至圖6D所示出的結果可知，比較例1在回焊1-5次後的初始液化溫度（T onset）均為215.5℃。而實施例1-3在回焊1-5次後的初始液化溫度在130至136℃的範圍內。另外，從圖6B可看出在溫度180℃附近會有一個較小的峰值，由於實施例1的Sn含量較多，故該峰值應為β-Sn相熔化因素所致，此符合圖2A所示出的薛爾固化路徑，β-Sn相在約185℃開始析出。 From the results shown in FIGS. 6A to 6D, it can be seen that the initial liquefaction temperature (T onset ) of Comparative Example 1 after 1-5 times of reflow is 215.5°C. The initial liquefaction temperature of Examples 1-3 after 1-5 times of reflow was in the range of 130 to 136°C. In addition, it can be seen from Fig. 6B that there will be a small peak near the temperature of 180°C. Since the Sn content in Example 1 is relatively large, the peak should be caused by the melting factor of the β-Sn phase, which is consistent with that shown in Fig. 2A. In the Scherr curing path shown, the β-Sn phase begins to precipitate at about 185°C.
從圖6A至圖6D所示出的結果可計算出實施例1-3和比較例1的糊狀區域（pasty range，∆T）。糊狀區域是藉由在DSC的升溫曲線中結束液化之溫度減去初始液化之溫度（T
end-T
onset）。糊狀區域若過高則表示焊料在固化過程中，以部分液態存在的時間較長，故無法形成可靠的焊點。將圖6A至圖6D所示出之初始液化溫度（T
onset）和糊狀區域（∆T）的結果整理於表2中。
[表2]
從圖7A所示出的結果可知，比較例1在固化過程僅出現一個峰值，主要是因為比較例1的組成接近共晶點，因此，固化過程直接由共晶點析出固化相。比較圖7B至圖7D所示出的結果可知，實施例2在固化過程中僅出現一個峰值，根據圖3A所示出之固化路徑的結果可解釋，實施例2在固化過程中，一開始即析出Ag
3Sn+Cu
6Sn
5，僅歷經一個折點隨即在接近最低共晶溫度142.6℃析出最後之共晶相。不同於實施例1和實施例3，根據圖2A和圖4A所示出之固化路徑的結果可解釋，實施例1和實施例3在固化過程中，歷經兩個折點（Ag
3Sn+Cu
6Sn
5和Ag
3Sn+Cu
6Sn
5+Sn）後才析出最後之共晶相。將圖7A至圖7D所示出之第一峰值和第二峰值的數據整理於表3中。
[表3]
從圖6A至圖6D和圖7A至圖7D所示出的結果來計算實施例1-3和比較例1的過冷度。過冷度定義為升溫過程之初始液化溫度（表中以T
onset( 升溫 )表示）減去降溫過程之初始液化溫度（表中以T
onset( 降溫 )表示），結果整理於表4。
[表4]
從表4可看出，相較於實施例1和實施例2，實施例3具有較低之過冷度，其是因為實施例3所析出的Bi可有效降低過冷度，因其可抑制β-Sn的生長速度和細化微結構，也可減緩金屬相的生長。此外，Bi顆粒析出可提供異質成核之位置，促進固化過程而使過冷度下降。 實驗 4 It can be seen from Table 4 that, compared with Example 1 and Example 2, Example 3 has a lower degree of supercooling. This is because the Bi precipitated in Example 3 can effectively reduce the degree of supercooling, because it can suppress The growth rate and refined microstructure of β-Sn can also slow down the growth of the metal phase. In addition, the precipitation of Bi particles can provide sites for heterogeneous nucleation, promote the solidification process and reduce the degree of subcooling. Experiment 4
藉由潤濕天平（solder checker, SAT-5100, Rhesca Co. Ltd., Japan）來測量實施例1-3和比較例1的潤濕性質（wettability），實施例1-3和比較例1的最大潤濕力（F
max）及2/3最大潤濕力（2/3F
max）整理於表5中，而實施例1-3和比較例1的平均潤濕時間整理於表6中。
[表5]
從表5和表6可知，實施例1-3的潤濕性質與比較例1皆符合業界的標準，即潤濕時間在2秒內就達到潤濕效果。此外，實施例1的最大潤濕力（F max）及2/3最大潤濕力（2/3F max）與比較例1相差不多，故可證明實施例1不僅具有低的液化溫度且其在潤濕性質的表現上與比較例1相似。 It can be seen from Table 5 and Table 6 that the wetting properties of Examples 1-3 and Comparative Example 1 all meet the industry standard, that is, the wetting time is within 2 seconds to achieve the wetting effect. In addition, the maximum wetting force (F max ) and 2/3 maximum wetting force (2/3F max ) of Example 1 are similar to those of Comparative Example 1, so it can be proved that Example 1 not only has a low liquefaction temperature but also The performance of the wetting properties is similar to that of Comparative Example 1.
綜上所述，在本上述複合焊料及其製造方法中，將含有Ag和Bi的二元合金與含有Sn、Ag、Cu的三元合金進行混合，如此可大幅降低複合焊料的液化溫度，以避免熱應力累積在焊點並確保焊點的可靠度。In summary, in the above-mentioned composite solder and its manufacturing method, the binary alloy containing Ag and Bi is mixed with the ternary alloy containing Sn, Ag, and Cu. This can greatly reduce the liquefaction temperature of the composite solder and Avoid the accumulation of thermal stress on the solder joints and ensure the reliability of the solder joints.
雖然本發明已以實施例揭露如上，然其並非用以限定本發明，任何所屬技術領域中具有通常知識者，在不脫離本發明的精神和範圍內，當可作些許的更動與潤飾，故本發明的保護範圍當視後附的申請專利範圍所界定者為準。Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention. Anyone with ordinary knowledge in the relevant technical field can make some changes and modifications without departing from the spirit and scope of the present invention. The protection scope of the present invention shall be subject to those defined by the attached patent application scope.
S1、S2、S3:步驟S1, S2, S3: steps
圖1為本發明一實施例的複合焊料的製造方法的流程圖。 圖2A為實施例1的複合焊料的薛爾（Scheil）固化曲線圖。 圖2B為實施例1的複合焊料經回焊一次後的掃描電子顯微鏡（scanning electron microscope，SEM）圖像。 圖3A為實施例2的複合焊料的薛爾固化曲線圖。 圖3B為實施例2的複合焊料經回焊1次後的SEM圖像。 圖4A為實施例3的複合焊料的薛爾固化曲線圖。 圖4B為實施例3的複合焊料經回焊1次後的SEM圖像。 圖5為實施例1-3的複合焊料經回焊一次後的SEM圖像。 圖6A至圖6D分別為實施例1-3和比較例1的複合焊料在不同回焊次數後以升溫速率為5℃/min的差示掃描熱量測定（differential scanning calorimetry，DSC）曲線圖。 圖7A至圖7D分別為實施例1-3和比較例1的複合焊料在不同回焊次數後以降溫速率為5℃/min的DSC曲線圖。 FIG. 1 is a flowchart of a method for manufacturing a composite solder according to an embodiment of the present invention. FIG. 2A is a Scheil curing curve diagram of the composite solder of Example 1. FIG. 2B is a scanning electron microscope (SEM) image of the composite solder of Example 1 after reflowing once. FIG. 3A is a Sheer curing curve diagram of the composite solder of Example 2. FIG. Fig. 3B is an SEM image of the composite solder of Example 2 after being reflowed once. FIG. 4A is a Sheer curing curve diagram of the composite solder of Example 3. FIG. FIG. 4B is an SEM image of the composite solder of Example 3 after being reflowed once. Fig. 5 is an SEM image of the composite solder of Examples 1-3 after reflowing once. 6A to 6D are the differential scanning calorimetry (DSC) curves of the composite solders of Examples 1-3 and Comparative Example 1 at a heating rate of 5° C./min after different reflow times. 7A to 7D are respectively the DSC curve diagrams of the composite solders of Examples 1-3 and Comparative Example 1 at a cooling rate of 5° C./min after different reflow times.
S1、S2、S3:步驟 S1, S2, S3: steps
Claims (9)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW109144209A TWI742963B (en) | 2020-12-15 | 2020-12-15 | Composite solder and method for manufacturing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW109144209A TWI742963B (en) | 2020-12-15 | 2020-12-15 | Composite solder and method for manufacturing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TWI742963B true TWI742963B (en) | 2021-10-11 |
| TW202225420A TW202225420A (en) | 2022-07-01 |
Family
ID=80782575
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW109144209A TWI742963B (en) | 2020-12-15 | 2020-12-15 | Composite solder and method for manufacturing the same |
Country Status (1)
| Country | Link |
|---|---|
| TW (1) | TWI742963B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200303245A (en) * | 2002-02-15 | 2003-09-01 | Ibm | Lead-free tin-silver-copper alloy solder composition |
| CN102216478A (en) * | 2008-10-15 | 2011-10-12 | 奥典私人有限公司 | Solder alloy |
| WO2015083661A1 (en) * | 2013-12-03 | 2015-06-11 | 国立大学法人広島大学 | Solder material and joining structure |
| CN111906469A (en) * | 2019-05-09 | 2020-11-10 | 铟泰公司 | Low-temperature melting point and medium-temperature melting point lead-free soldering paste with mixed soldering tin alloy powder |
-
2020
- 2020-12-15 TW TW109144209A patent/TWI742963B/en active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200303245A (en) * | 2002-02-15 | 2003-09-01 | Ibm | Lead-free tin-silver-copper alloy solder composition |
| CN102216478A (en) * | 2008-10-15 | 2011-10-12 | 奥典私人有限公司 | Solder alloy |
| WO2015083661A1 (en) * | 2013-12-03 | 2015-06-11 | 国立大学法人広島大学 | Solder material and joining structure |
| CN111906469A (en) * | 2019-05-09 | 2020-11-10 | 铟泰公司 | Low-temperature melting point and medium-temperature melting point lead-free soldering paste with mixed soldering tin alloy powder |
Also Published As
| Publication number | Publication date |
|---|---|
| TW202225420A (en) | 2022-07-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2883649B1 (en) | High-temperature lead-free solder alloy | |
| JP6477965B1 (en) | Solder alloy, solder paste, solder ball, flux cored solder and solder joint | |
| JP5724411B2 (en) | Solder, soldering method and semiconductor device | |
| TW201938809A (en) | Solder alloy, solder paste, solder ball, resin cored solder, and solder joint | |
| CN114245765A (en) | Lead-free and antimony-free solder alloy, solder ball, ball grid array and solder joint | |
| WO2019069788A1 (en) | Solder alloy, solder junction material, and electronic circuit substrate | |
| WO2008056676A1 (en) | Lead-free solder paste, electronic circuit board using lead-free solder paste, and method for manufacturing electronic circuit board | |
| AU2012359292A1 (en) | High-temperature lead-free solder alloy | |
| KR102543580B1 (en) | Lead-free and antimony-free solder alloys, solder balls and solder joints | |
| TWI771903B (en) | Lead-free and antimony-free solder alloys, solder balls, and solder joints | |
| JP2018047500A (en) | Bi-BASED SOLDER ALLOY AND METHOD FOR PRODUCING THE SAME, AND ELECTRONIC COMPONENT AND ELECTRONIC COMPONENT-MOUNTED SUBSTRATE COMPRISING THE SOLDER ALLOY | |
| TWI742963B (en) | Composite solder and method for manufacturing the same | |
| JP6708942B1 (en) | Solder alloy, solder paste, preform solder, solder ball, wire solder, grease solder, solder joint, electronic circuit board and multilayer electronic circuit board | |
| JP2004034134A (en) | Line-solder and process of producing electronic equipment | |
| JP2007313548A (en) | Cream solder | |
| JP2008221330A (en) | Solder alloy | |
| JP6038187B2 (en) | Solder alloy for die bonding | |
| JP2018047499A (en) | Bi-BASED SOLDER ALLOY AND METHOD FOR PRODUCING THE SAME, AND ELECTRONIC COMPONENT AND ELECTRONIC COMPONENT-MOUNTED SUBSTRATE COMPRISING THE SOLDER ALLOY | |
| JP7068370B2 (en) | Solder alloys, solder balls and solder fittings | |
| JP2005177842A (en) | Brazing material, manufacturing method of semiconductor device using the same and semiconductor device | |
| JP2018047497A (en) | Bi-BASED SOLDER ALLOY AND METHOD FOR PRODUCING THE SAME, AND ELECTRONIC COMPONENT AND ELECTRONIC COMPONENT-MOUNTED SUBSTRATE COMPRISING THE SOLDER ALLOY | |
| JP2003205388A (en) | Method of producing lead-free solder for package | |
| JP2014146713A (en) | Solder material and soldering method | |
| JP2019063865A (en) | Solder alloy, solder junction material, and electronic circuit substrate | |
| JP2006159265A (en) | High temperature solder and cream solder |