TW200928006A - Sn-B plating solution and plating method using it - Google Patents

Abstract

The object of the present invention is to prevent generation of whisker in a Pb-free plating layer. Provided is a Pb-free Sn-B plating solution containing tin sulfate, which is a source of Sn ions, and dimethyl amine borane or trimethyl amine borane, which is a source of B ions.

Description

200928006 九、發明說明： 【發明所屬之技術領域】 本發明是關於一種不具有錯之Sn-B電錢液（衣下文 中稱作不含Pb之Sn-B電鍍液），以及一種使用該電鍍液 之電鍍方法，且更特定言之是關於一種可防止電二廣中產 生鬚晶（whisker)之不含Pb之Sn-B電鍍液，以種使 用該電鍍液之電鍍方法。200928006 IX. Description of the Invention: [Technical Field] The present invention relates to a Sn-B electro-money liquid (hereinafter referred to as a Sn-B plating solution containing no Pb) which has no error, and a use of the electroplating The liquid plating method, and more specifically, a plating method for preventing the use of a Pb-free Sn-B plating solution for generating a whisker in the electric power to use the plating solution.

【先前技術】 半導體引線框（semiconductor lead frame )為製造具有 半導體晶片之半導體封裝裝置之最重要元件中的一f ^半 導體引線框充當連接半導體晶片與外部電路之弓丨線，且充 當支撐半導體晶片之框架。視半導體晶片之高密度化或整 合或將半導體晶片安裝於基板上之方法而定，半導艘引線 框具有各種形狀。 基本上’半導體引線框由以下部分形成：概塾（pad)， 晶片安裝於其上且其保持其上晶片（亦即半導體記憶體裝 置）之靜態（static state );内部引線’其藉由導線結合（wire bonding)與晶片連接；以及外部引線，其將半導體引線框 與外部電路連接。通常使用衝壓法（stamping meth〇(i)或 钱刻法（etchingmethod)來製造具有此結構之半導體引線 框。 經由裝配製程（assembling process)用晶片封裝半導 體引線框，所述裝配製程包括晶片附著製程（chip attaching process)、導線結合製程（wire bonding process)、模製製 5 200928006 程（molding process )、標記製程（marking process )、分離 製程（separatingprocess)等。 在裝配製程期間，將襯墊以及内部引線之末端電鍍金 屬材料（諸如銀（Ag))，以保持連接晶片與内部引線之導 線（leadwire)之結合性（bondability)以及襯墊之出色特 性。此外’將外部引線之預定區域電鍍焊接材料（亦即錫_ 錯（Sn-Pb))，以改良在模製樹脂保護膜後安裝之基板之焊 接效能。然而，難以實施此電鍍方法，且半導體晶片通常 因電鍍液在半導體引線框與環氧樹脂模製之表面之間渗透 而發生故障。此外，需要另一製程以消除電鍍層之不均勻 性。 因此’建議預鍍框架（pre-platedframe ; PPF)法，藉 此在裝配製程之前將具有良好引線可濕性（lead wettability)之材料預鍍於半導體引線框之頂面上。在 法中，商業上使用2層結構，其中鎳（Ν〇層作為中間層 而形成於引線框之金屬基底材料（諸如銅（Cu》上，且 具有良好引線可濕性之鈀（Pd)層完全或部分形成於中間 層上；3層結構’其中Ni層、pd層以及作為頂層之金（aJ 質快閃層（flash layer)分別形成於基底材料上；以及 結構，其中Ni打底層（血此iayer)、pd_Ni合金層、n. 層以及Pd層分別形成於基底材料上。然而，當从1 為Cu或合金（諸如不包括Cu組份之合金们（“I ·二 時，半導體引線框嚴重腐蝕。此外，兇之價格不穩〜，）） 當Pd之價格增加時，半導體封裝之製造成本亦增^疋。，且 6 200928006 近來，已使用雙調（two-tone)預锻框架法，藉此金 屬基底材料中對應於内部引線之區域以及對應於外部引線 之區域獨立地電鍍不同金屬。舉例而言，對應於内部引線 之區域可電鑛Ag’且對應於外部引線之區域可電鍍Sn_pb。[Prior Art] A semiconductor lead frame is one of the most important components for manufacturing a semiconductor package having a semiconductor wafer. The semiconductor lead frame serves as a bow line connecting the semiconductor wafer and the external circuit, and serves as a supporting semiconductor wafer. The framework. Depending on the method of densifying or integrating the semiconductor wafer or mounting the semiconductor wafer on the substrate, the semi-conductor lead frame has various shapes. Basically, the 'semiconductor lead frame is formed by a pad on which the wafer is mounted and which holds the static state of the wafer (ie, the semiconductor memory device); the inner leads 'by the wires Wire bonding to the wafer; and external leads that connect the semiconductor leadframe to an external circuit. A semiconductor lead frame having such a structure is typically fabricated using a stamping method (i) or an etching method. The semiconductor lead frame is packaged with a wafer via an assembly process, the assembly process including a wafer attach process (chip attaching process), wire bonding process, molding system 5 200928006 molding process, marking process, separation process, etc. During the assembly process, the liner and the interior A metal material such as silver (Ag) is plated at the end of the lead to maintain the bondability of the bond wafer to the lead wire of the inner lead and the excellent characteristics of the pad. Further, the predetermined area of the outer lead is plated with the solder material. (ie, tin-Pb) to improve the soldering efficiency of the substrate mounted after molding the resin protective film. However, it is difficult to implement this plating method, and the semiconductor wafer is usually in the semiconductor lead frame and ring due to the plating solution. The surface of the oxy resin molding penetrates and fails. In addition, another process is required. Eliminate the unevenness of the plating layer. Therefore, a pre-plated frame (PPF) method is recommended, whereby a material with good lead wettability is pre-plated on top of the semiconductor lead frame before the assembly process. In the method, a two-layer structure is commercially used in which nickel (the tantalum layer is used as an intermediate layer to form a metal base material of a lead frame such as copper (Cu), and palladium having good lead wettability ( The Pd) layer is formed entirely or partially on the intermediate layer; the 3-layer structure 'where the Ni layer, the pd layer, and the gold as the top layer (aJ flash layer are respectively formed on the base material; and the structure, wherein Ni plays The bottom layer (blood iayer), the pd_Ni alloy layer, the n. layer, and the Pd layer are respectively formed on the base material. However, when from 1 to Cu or an alloy (such as alloys not including the Cu component ("I · II, The semiconductor lead frame is seriously corroded. In addition, the price of the fissure is unstable~,))) When the price of Pd increases, the manufacturing cost of the semiconductor package also increases., and 6 200928006 Recently, the two-tone pre-use has been used. Forging frame method, The base material of this metal in the region corresponding to the inner lead of the well region corresponding to the outer lead independent plated different metals. For example, the region corresponding to the inner lead of electrically ore Ag 'and corresponds to the area of the external lead of platable Sn_pb.

由於鉛所導致的環境污染，PPF法以及雙調預鍍框架 法中所用之電鍍方法具有若干問題。遍及世界，正實施各 種法規以控制電子產品中鉛之使用。此外，正對可替代使 用錯以及Sn-Pb電鍍材料之焊膏（solder paste)之材料持 續進行研究。 、 純Sn電鍍可為Sn-Pd電鍍之最佳替代者。然而，在純 Sri電鍍中，由於過量產生鬚晶可能會形成短路。 、 鬚晶指在兩種不同材料彼此結合且因而相互擴散 (inter-diffuse)後於電鍵層表面上產生之突出晶體。鬚晶易 受熱以及濕度的脚。晶形成於半導則線框之電鑛 層之表面上時，半導體電性短路（dectricaiiy让⑽ circuit)，且因而電路發生故障。 為防止產生鬚晶，考慮在Sn電鑛後進行熱製程、见 電鑛、調節Sn粒度（particle size)以及％與異種金屬 (dissimOar metal)之合金。Sn_Bi (鉍）合 用 與異種金狀合金。 Ml 然而’ Sn-Bi合金不可充分抑制鬚晶之產生，且％盥 牆η帅，具錢著差異， =而共析困難。此外’當溶液中則漢度較 局時，说《尤積於陰極表面上’且可能會在谭接後脫落。此 7 200928006 外，當電鍍層中Bi含量較高時，在電鍍層彎曲時電鍍層中 可能會形成裂縫。 【發明内容】 ' 本發明提供一種不含Pb之Sn-B電鍍液’其可防止電 鍍層中產生鬚晶；以及一種使用該電鍍液之電鍍方法。 根據本發明之一態樣，提供一種不含Pb之Sn-B電鍍 液’其含有作為Sn離子源之硫酸錫（tin sulfate)，以及作 ❹為B離子源之二甲胺硼烧（dimethyl amine borane，DMAB) 或二曱胺獨院（trimethyl amine borane，TMAB )。The plating method used in the PPF method and the double-tune pre-plating frame method has several problems due to environmental pollution caused by lead. Throughout the world, various regulations are being implemented to control the use of lead in electronic products. In addition, research is continuing on materials that can replace the use of solder pastes of Sn-Pb plating materials. Pure Sn plating is the best alternative to Sn-Pd plating. However, in pure Sri plating, a short circuit may be formed due to excessive generation of whiskers. A whisker refers to a protruding crystal that is produced on the surface of an electric bond layer after two different materials are bonded to each other and thus inter-diffuse. Whisker is easy to heat and humidity the feet. When the crystal is formed on the surface of the electric ore layer of the semi-conductor wire frame, the semiconductor is electrically short-circuited (dectricaiiy (10) circuit), and thus the circuit malfunctions. In order to prevent the generation of whiskers, it is considered to carry out the thermal process after the Sn ore, see the electric ore, adjust the particle size of Sn, and alloy the % with dissimOar metal. Sn_Bi (铋) is used in combination with a heterogeneous gold alloy. Ml However, the Sn-Bi alloy cannot sufficiently suppress the generation of whiskers, and the %盥 wall is handsome, with a difference in money, and it is difficult to analyze. In addition, when the Hant is in the solution, it is said to be "on the surface of the cathode" and may fall off after the tan. In addition to the higher content of Bi in the plating layer, cracks may form in the plating layer when the plating layer is bent. SUMMARY OF THE INVENTION The present invention provides a Sn-B plating solution containing no Pb, which prevents the generation of whiskers in the plating layer, and an electroplating method using the plating solution. According to an aspect of the present invention, there is provided a Pb-free Sn-B plating solution which contains tin sulfate as a source of Sn ions and dimethyl amine as a source of B ions. Borane, DMAB) or trimethyl amine borane (TMAB).

Sn離+源之量可為15 g/L至5〇 g/L。 B離子源之量可為o.i g/L至3.0g/L。 不含Pb之Sn-B電鍍液可進一步含有30 ml/L至70 ml/L之硫酸（sulfuric acid)。不含Pb之Sn-B電鍍液可進 步含有 10 g/L 至 40 g/L 之甲紛續酸（cresolsulfonic acid) 或苯盼確酸（phenolsulfonic acid)。不含Pb之Sn-B電鑛 液可進一步含有0.1 g/L至0.5 g/L之卜萘紛（p_Naphth〇l)。 ❹ 不含之Sn~B電鍍液可進一步含有〇·ι g/L至3 g/L之明 膠（gelatin ) 〇 根據本發明之另一態樣’提供一種使用不含Pb之Sn-B 電錄液之電錢方法，所述電鑛液含有作為Sn離子源之硫 ， 酸錫，以及作為B離子源之二曱胺硼烷或三曱胺硼烷。 . 電鍍方法可包含在0.5 A/dm2至5 A/dm2之電流密度下 電鏡不含Pb之Sn-B電鍵液。 電鑛方法可在室溫下實施。 8 200928006 【實施方式】 下文中，將參照隨附圖式更完全地描述本發明，其中 展示本發明之例示性實施例。 * 如上所述，在習知Sn型電鍍層中，電鍍層表面上之 鬚晶為一個難題。然而，尚未清楚瞭解產生鬚晶之原因。 已注意到當由Sn型電鍍液形成之電鍍層形成於由Cu 形成之引線框上時，在Sn與Cu之結合界面處Cu之擴散 速度高於Sn之擴散速度。 © 換言之，因為在Sn與Cu之結合界面處Cu之擴散速 度咼於Sn之擴散速度’所以引線框之Cu組份向電鑛層尤 Sn之晶粒邊界擴散。隨後’在電鍍層上形成金屬間化合 物’其具有Cu6Sn5之組成。 在本申請案中，認為金屬間化合物在電鍍層之Sn内 部提供壓縮應力，且藉由在電鍍層表面上在Sn中產生鬚 晶（其為鬚晶形式之單晶）來解決壓縮應力。 因此，藉由向Sn之晶體結構之間隙位置中***具有 ❹ 小原子尺寸之金屬來抑制金屬之間的擴散，且因而Sn内 部之壓縮應力降低。因此，鬚晶之產生得以防止。具有小 原子尺寸之金屬可為硼（B)。 然而，根據本發明之實施例之電鍍液不包括鉛離子 (lead ion)’且含有作為Sn離子源之硫酸錫以及作為b離 子源之二甲胺硼烷。 作為Sn離子源之硫酸錫（SnS〇4)之量可為15至 50 g/L ’且作為β離子源之二甲胺硼烷（DMAB)之量可 9 200928006 為0.1 g/L至3.0 g/L。三甲胺硼烷（TMAB)可用作B離 子源。 當B離子源之量大於〇1 g/L時，與當B離子源之量 小於0.1 g/L時之情況相比，***電鍍層之Sn間隙位置中 的B之量足夠。因此如上所述，抑制Sn與基底材料之金 屬間化合物之生長的作用顯著，且因此不會產生鬚晶。同 時，當B離子源之量超過3.〇 g/L時，***Sn間隙位置中 〇 之B的量飽和，且因而在B上花費不必要之費用，其為浪 費的。此外，由於B過量，電鍍層之表面變得不均勻，且 電鍍液自身可能會不穩定。 向電鍵液中添加30 ml/L至70 ml/L之硫酸（H2S04 ) 以控制電解質之傳導率以及離子（諸如Sn2+)之遷移率。 當硫酸之量小於30 ml/L時，電鍍液之傳導率降低，亦即 電鍍液之電阻增加，且因而電鍍速度降低。因此，生產率 降低，且電鍍可能會不均勻。當硫酸之量超過70 ml/L時， 在陽極中產生顯著量之黏液（slime)，且因而電鑛液變得 〇 不穩定’且電鍍層可能會有缺陷。 此外，可將10 g/L至40 g/L的甲酚磺酸或苯酚磺酸添 加至電鍍液中以延遲Sn之氧化。當甲酚磺酸或苯酚磺酸 之量小於10 g/L時，Sn易於氧化，且當甲酚磺酸或苯酚磺 酸之量超過40 g/L時，電鍍液可能會不穩定。 . 可將0.1 g/L至0.5 g/L的β-萘盼添加至電鍵液中以控 制電鍍層表面之粗糙度。當β-萘酚之量小於〇.1 g/L時， 200928006 可能產生粗劣的晶體粒子，且當β-萘酚之量超過〇.5 g/L 時，電鍍層表面可能會極粗糙。 另外，可將0.1 g/L至3 g/L的明膠添加至電錄液中。 當明膠之量小於0.1 g/L時，晶體粒子過於粗劣，且當明膠 之量超過3 g/L時，可能產生許多針狀物或突出物。 ❹The amount of Sn from the source can be from 15 g/L to 5 〇 g/L. The amount of B ion source can range from o.i g/L to 3.0 g/L. The Sn-B plating solution containing no Pb may further contain 30 ml/L to 70 ml/L of sulfuric acid. The Pb-free Sn-B plating solution may further contain 10 g/L to 40 g/L of cresolsulfonic acid or phenolsulfonic acid. The Sn-B electrowinning solution containing no Pb may further contain 0.1 g/L to 0.5 g/L of p-Naphth〇l. S The Sn~B plating solution not contained may further contain gelatin of ι·ι g/L to 3 g/L. According to another aspect of the present invention, a Sn-B recording using Pb-free is provided. In the liquid electricity method, the electro-mineral liquid contains sulfur as a source of Sn ions, tin acid, and diamine or borane borane as a source of B ions. The electroplating method may include an electron microscope having a Pb-free Sn-B key solution at a current density of 0.5 A/dm2 to 5 A/dm2. The electrominening process can be carried out at room temperature. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described more fully hereinafter with reference to the accompanying drawings. * As described above, in the conventional Sn-type plating layer, whiskers on the surface of the plating layer are a problem. However, the reason for the generation of whiskers has not been clearly understood. It has been noted that when a plating layer formed of a Sn-type plating solution is formed on a lead frame formed of Cu, the diffusion speed of Cu at the bonding interface of Sn and Cu is higher than the diffusion speed of Sn. © In other words, since the diffusion speed of Cu at the bonding interface between Sn and Cu is higher than the diffusion speed of Sn', the Cu component of the lead frame diffuses to the grain boundary of the electric ore layer. Subsequently, an intermetallic compound is formed on the plating layer, which has a composition of Cu6Sn5. In the present application, it is considered that the intermetallic compound provides a compressive stress inside the Sn of the plating layer, and the compressive stress is solved by generating a whisker (which is a single crystal in the form of whiskers) in Sn on the surface of the plating layer. Therefore, diffusion between the metals is suppressed by inserting a metal having a small atomic size into the gap position of the crystal structure of Sn, and thus the compressive stress inside the Sn is lowered. Therefore, the generation of whiskers is prevented. The metal having a small atomic size may be boron (B). However, the plating solution according to an embodiment of the present invention does not include lead ions and contains tin sulfate as a source of Sn ions and dimethylamine borane as a source of b ions. The amount of tin sulfate (SnS〇4) as a source of Sn ions may be 15 to 50 g/L 'and the amount of dimethylamine borane (DMAB) as a source of β ions may be 0.1 g/L to 3.0 g for 200928006 /L. Trimethylamine borane (TMAB) can be used as a B ion source. When the amount of the B ion source is larger than 〇1 g/L, the amount of B inserted into the Sn gap position of the plating layer is sufficient as compared with the case where the amount of the B ion source is less than 0.1 g/L. Therefore, as described above, the effect of suppressing the growth of the intermetallic compound of Sn and the base material is remarkable, and thus whiskers are not produced. At the same time, when the amount of the B ion source exceeds 3. 〇 g / L, the amount of B inserted into the Sn gap position is saturated, and thus an unnecessary cost is incurred on B, which is wasteful. Further, since the B is excessive, the surface of the plating layer becomes uneven, and the plating solution itself may be unstable. Add 30 ml/L to 70 ml/L of sulfuric acid (H2S04) to the key solution to control the conductivity of the electrolyte and the mobility of ions such as Sn2+. When the amount of sulfuric acid is less than 30 ml/L, the conductivity of the plating solution is lowered, that is, the resistance of the plating solution is increased, and thus the plating speed is lowered. Therefore, productivity is lowered and plating may be uneven. When the amount of sulfuric acid exceeds 70 ml/L, a significant amount of slime is generated in the anode, and thus the electromineral becomes unstable, and the plating layer may be defective. Further, 10 g/L to 40 g/L of cresolsulfonic acid or phenolsulfonic acid may be added to the plating solution to delay the oxidation of Sn. When the amount of cresolsulfonic acid or phenolsulfonic acid is less than 10 g/L, Sn is easily oxidized, and when the amount of cresolsulfonic acid or phenolsulfonic acid exceeds 40 g/L, the plating solution may be unstable. 0.1 g/L to 0.5 g/L of β-naphthene can be added to the electrode fluid to control the roughness of the surface of the plating layer. When the amount of β-naphthol is less than 〇.1 g/L, 200928006 may produce coarse crystal particles, and when the amount of β-naphthol exceeds 〇.5 g/L, the surface of the plating layer may be extremely rough. In addition, 0.1 g/L to 3 g/L of gelatin can be added to the electrocaloric solution. When the amount of gelatin is less than 0.1 g/L, the crystal particles are too coarse, and when the amount of gelatin exceeds 3 g/L, many needles or protrusions may be generated. ❹

將電鍍液電鍍於Cu板上，所述Cu板可為引線框之主 要材料。Cu板用作陰極且可溶性Sn用作陽極。電鍍期間 的電流密度可為0.5 A/dm2至5 A/dm2，且較佳為i A/d 2 至3 A/dm2 °在以下實施财，電餘度為丨A/W。當電 流密度超過5 A/dm2時，魏表面極粗糙，晶體生長不均 勻’且電鑛不穩定。因此，魏膜之可靠性降低。當電流 密度小於0.5 A/dm2時，電鍵時間過長，進而不利影響生產 率〇 、”：鍍f度為室溫(25〇C±3。。)。當電鍍液之 二雪合Ϊ )听吹時，添加劑可能會分解，且 /•πτίΓ會異常進行。因此，可能會產生鬚晶。 將參照以下實例更完全地描述本發明。 &lt;實施例1&gt; 裝備含有15 g/L的琉酸錫、3〇 ml/L的邮〇4、1〇 ^ 的甲盼％酸、0.1 g/L的卜萘紛以及0.1 g/L的明膠之電 液0 在實驗1中，向 DMAB，在實驗2中， 電鍍液中進一步添加0.1 g/L的 向電鍍液中進一步添加0.5 g/L的 200928006 且在實驗3 t，向電鍵液中進—步添加3 g/L的 陰極在件下進行電鍍。換言之，Q板用作 溫度為常溫。作陽極，電流密度為lA/W，且電鑛 將實驗！至實驗3之電 隨後測定在電制表面上是否產生鬚/儲存12個月，且 ❹ ❹ 圖1 U)至® 1 (e)為分別說明 驗1至實驗3中電錢層 =存试驗後實 — —icr〇s &lt;實施例2&gt; /豕The plating solution is electroplated on a Cu plate, which may be the main material of the lead frame. A Cu plate was used as the cathode and soluble Sn was used as the anode. The current density during electroplating may range from 0.5 A/dm2 to 5 A/dm2, and preferably i A/d 2 to 3 A/dm 2 ° is implemented below, and the electrical margin is 丨A/W. When the current density exceeds 5 A/dm2, the surface of the Wei is extremely rough, the crystal growth is uneven, and the electric ore is unstable. Therefore, the reliability of the Wei film is lowered. When the current density is less than 0.5 A/dm2, the time of the key is too long, which adversely affects the productivity 〇,": the plating degree is room temperature (25 〇C±3.). When the plating solution is chilled) At the time, the additive may decompose and /•πτίΓ may proceed abnormally. Therefore, whiskers may be generated. The present invention will be more fully described with reference to the following examples. <Example 1> Equipment containing 15 g/L of tin citrate 3 〇 ml / L of postal 〇 4, 1 〇 ^ of the 盼 % % acid, 0.1 g / L of the naphthene and 0.1 g / L of gelatin of the electro-hydraulic 0 in the experiment 1, to DMAB, in the experiment 2 Further, 0.1 g/L of 0.1 g/L was added to the plating solution to further add 0.5 g/L of 200928006. In the experiment 3 t, a 3 g/L cathode was further added to the electrophoresis solution to perform electroplating under the member. In other words, the Q plate is used as the temperature at normal temperature. As the anode, the current density is 1A/W, and the electric ore will be tested! The electricity to the experiment 3 is then determined whether the whisker is generated/stored on the electromade surface for 12 months, and ❹ ❹ Fig. 1 U) to ® 1 (e) are respectively illustrating the electric money layer in the test 1 to the experiment 3 = the actual test -icr〇s &lt;example 2&gt; /豕

製備含有30 g/L的硫酸錫、5〇 ml/L =_、°.一一。.5心== 在實驗4中，向電鍍液中進一步添加 DMAB，在實驗5中，向電鑛液中進一步添加ο1弋的 DMAB，且在實驗6 t ’向電链液中進—步. DMAB。 J g’L 的 在實例i之相同電鍍條件下進行魏。將 驗6之^層在室溫下儲存12则，且隨後測定在電= 表面上是否產生鬚晶。 观層 圖2 (a)至圖2 (c)為分別說明在室溫儲存 驗4至實驗6中電鍍層之表面狀態之SEM照相景 〈實施例3&gt; ^冢。 12 200928006 製備含有50 g/L的硫酸錫、7〇 ‘的邮〇4、4〇叭 波盼績酸、0.5 g/L的卜萘紛以及工〇 g/L的明膠 液0 又 在實驗7中’向電鑛液中進-步添加0.1 g/L的 DMAB ’在實驗8中’向電鍵液中進-步添加0.5 g/L的 且在實驗9中’向電贿中進-步添加3 g/L的 ❹ ❹ 在丄：相同電鍍條件下進行電鍍。將實驗7至實 = 儲存12個月，且隨後測定在電鍵層 驗7 = =2=:=存試驗後實 〈實施例4&gt; 之表祿紅漏_影像。 製備含有50 g/L的硫酸錫、7〇遗的H :曱峨、。·5—蔡盼以及¥的明膠之‘ 在實驗10巾，向電鍵液中進一步添加〇 DMAB’在實驗U中，向電鑛液中進—步添加g = DMAB，且在實驗12中，向電難中進一步添 = DMAB。 s丄的 在實例1之相㈣鱗件下騎電鍍。將實驗ι〇至 驗12之電鑛層在室溫下儲存12個月，且隨後 j 層表面上是否產生鬚晶。 锻 13 200928006 圖4 (a)至圖4 (c)為分別說明在室溫儲存試驗後實 驗10至實驗12中電鍍層之表面狀態之SEM照相影像。 ' &lt;實施例5&gt; 製備含有30 g/L的硫酸錫、50 ml/L的H2S04、20 g/L 的甲酚磺酸、0.5 g/L的β-萘酚以及3.0 g/L的明膠之電鍍 液。 在實驗13中，向電鑛液中進一步添加0.1 g/L的 DMAB，在實驗14中，向電鐘液中進一步添加0.5 g/L的 ® DMAB，且在實驗15中，向電鍍液中進一步添加3 g/L的 DMAB 〇 在實例1之相同電鍍條件下進行電鍍。將實驗13至實 驗15之電鍍層在室溫下儲存12個月，且隨後測定在電鍍 層表面上是否產生鬚晶。 圖5 (a)至圖5 (c)為分別說明在室溫儲存試驗後實 驗13至實驗15中電鍍層之表面狀態之SEM照相影像。 〈實施例6&gt;Preparation of 30 g / L of tin sulfate, 5 〇 ml / L = _, °. .5 Heart == In Experiment 4, DMAB was further added to the plating solution. In Experiment 5, DMAB of ο1弋 was further added to the electro-mineral solution, and the experiment was carried out in the experiment 6 t 'to the electric chain liquid. DMAB. J g'L was carried out under the same plating conditions as in Example i. The layer 6 was stored at room temperature for 12 hours, and then it was determined whether or not whiskers were generated on the electric surface. Fig. 2 (a) to Fig. 2 (c) are SEM photographs illustrating the surface state of the plating layer in the test 4 to the experiment 6 at room temperature, respectively. [Example 3 &gt; 12 200928006 Preparation of gelatin solution containing 50 g/L of tin sulphate, 7 〇 ' 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 Add '0.1 g/L DMAB' to the electric ore solution. In Experiment 8, 'Add 0.5 g/L to the key solution and add it to the electric bribe in Experiment 9. 3 g/L ❹ 电镀 Plating at the same plating conditions. Experiment 7 to real = stored for 12 months, and then measured in the electrophoretic layer test 7 = = 2 =: = test after the test <Example 4> Table Lu Hong leak_image. Preparation of 50 g/L of tin sulfate, 7 〇 of H: 曱峨,. ·5—Cai Pan and ¥ gelatin' In the experiment 10 towel, further add 〇DMAB to the electric button solution. In experiment U, add g = DMAB to the electric ore solution, and in experiment 12, Add further DMAB to the electric disaster. s丄 The electroplating was carried out under the phase (4) scale of Example 1. The electroplated layer of the test ι to test 12 was stored at room temperature for 12 months, and then whiskers were formed on the surface of the j layer. Forging 13 200928006 Figures 4(a) to 4(c) are SEM photographs showing the surface states of the plating layers in Experiments 10 to 12, respectively, after the storage test at room temperature. '&lt;Example 5&gt; Preparation of 30 g/L of tin sulfate, 50 ml/L of H2S04, 20 g/L of cresytone, 0.5 g/L of β-naphthol, and 3.0 g/L of gelatin The plating solution. In Experiment 13, 0.1 g/L of DMAB was further added to the electro-mineral solution, and in Experiment 14, 0.5 g/L of ® DMAB was further added to the electric clock solution, and in Experiment 15, further to the electroplating solution Electroplating was carried out under the same plating conditions as in Example 1 by adding 3 g/L of DMAB. The electroplated layers of Experiment 13 to Experiment 15 were stored at room temperature for 12 months, and then it was determined whether or not whiskers were generated on the surface of the plating layer. Fig. 5 (a) to Fig. 5 (c) are SEM photographs showing the surface states of the plating layers in Experiments 13 to 15 after the storage test at room temperature, respectively. <Example 6>

❹ 製備含有50 g/L的硫酸錫、70 ml/L的H2S04、40 g/L 的甲酚磺酸、0.5 g/L的β-萘酚以及1.0 g/L的明膠之電鍍 液。 在實驗16中，向電鍍液中進一步添加30 ppm的 DMAB，且在實驗17中，向電鍍液中進一步添加4 g/L的 DMAB。 200928006 在實例1之相同電鍍條件下進行電鍍。將實驗16以及 實驗17之電鑛層在室溫下儲存以個月，且隨後測定在電 鍍層表面上是否產生鬚晶。 圖6 (a)為在實驗16中在電鍍電鍍層之表面後電鍍 層之SEM照相影像’圖6 (b)為在室溫儲存試驗後實驗 16之電锻層之SEM照相影像，且圖6 (c)為說明在室溫制备 A plating bath containing 50 g/L of tin sulfate, 70 ml/L of H2S04, 40 g/L of cresol sulfonic acid, 0.5 g/L of β-naphthol, and 1.0 g/L of gelatin was prepared. In Experiment 16, 30 ppm of DMAB was further added to the plating solution, and in Experiment 17, 4 g/L of DMAB was further added to the plating solution. 200928006 Electroplating was carried out under the same plating conditions as in Example 1. The electric ore layers of Experiments 16 and 17 were stored at room temperature for several months, and then it was determined whether or not whiskers were generated on the surface of the plating layer. Figure 6 (a) is an SEM photographic image of the electroplated layer after the surface of the electroplated plating layer in Experiment 16 ' Figure 6 (b) is an SEM photograph of the electro-forged layer of Experiment 16 after storage test at room temperature, and Figure 6 (c) for illustration at room temperature

儲存試驗後實驗π中魏層之表面狀態之SEM照相影 像。 如圖1 (a)至圖15 (c)中所說明，在根據實施例1 至實施例5之電鍍層表面上，甚至在長時期後，未產生鬚 晶。 此外，如圖6(a)以及圖66(b)中所說明，當DMAB =量極低時，在製造電鍵層後不久未產生鬚晶，但 間過去後產生鬚晶❶ ^ 如圖6 (c)中所說明，當DMAB之量較大時，不產 生鬚晶，但電鍍層之表面不均勻且粗糙。 &lt;比較性實例&gt; 在比較性實施例1至比較性實施例5中，分別自 例1至實施例5中排除DMAB。 在與實施例1相同之電鍍條件下進行電鑛，且將 性實施例1至比較性實補5之紐層在室 個月且隨後檢查鬚晶。 于 15 ❹ 〇 200928006 較性溫儲存試驗後比 相影像。 Τ1：縣之表面狀ϋ之SEM照 如圖7 (a)至圖7 (e)中所說明， 鬚晶=:本發明提供一種不含pb之電鑛層，其可抑制 錢層根據本發明，可提供—種不產生鬚晶之Μ合金電 與Sn原子械’ b原子相龍小，且_ B原子可 ㈣叙％之間_置中。因此’當含有 n，= B之電紐在由Cu形成之引線框上形成電鑛層 鸾曰w防止Cu擴散人Snt，且因而防止在電鍵層上產生 =°因此，具有含有Sn以及B之電鑛區域（包括Μ ▲電錢層）之半導體引線框之電性短路得以防止，且使 =半導體引線框之電子裝置（eleetrieal deviee)之耐久性 得以改良。The SEM photographic image of the surface state of the Wei layer in the experiment π after the test was stored. As illustrated in Fig. 1 (a) to Fig. 15 (c), on the surface of the plating layer according to Example 1 to Example 5, no whiskers were produced even after a long period of time. Further, as illustrated in Fig. 6(a) and Fig. 66(b), when the amount of DMAB = is extremely low, whiskers are not generated shortly after the production of the electric bond layer, but after the past, whiskers are generated ^ as shown in Fig. 6 ( As explained in c), when the amount of DMAB is large, whiskers are not generated, but the surface of the plating layer is uneven and rough. &lt;Comparative Example&gt; In Comparative Example 1 to Comparative Example 5, DMAB was excluded from Example 1 to Example 5, respectively. The electric ore was subjected to the same plating conditions as in Example 1, and the layers of Comparative Example 1 to Comparative Substituting 5 were subjected to room temperature and then examined for whiskers. On 15 ❹ 〇 200928006 Comparative phase storage image after the test. Τ1: The SEM of the surface enamel of the county is as shown in Fig. 7 (a) to Fig. 7 (e), whisker =: The present invention provides a pb-free electric ore layer which can suppress the money layer according to the present invention. , can provide - the kind of alloy that does not produce whisker and the Sn atomic machinery 'b atom phase dragon small, and _ B atom can be (four) between the % _ center. Therefore, when the electric button containing n, = B forms an electric ore layer on the lead frame formed of Cu, it prevents Cu from diffusing the human Snt, and thus prevents generation of = on the electroconductive layer, thus having Sn and B. The electrical short circuit of the semiconductor lead frame of the electro-mineral area (including the 电 电 电 层 layer) is prevented, and the durability of the electronic device (eleetrieal deviee) of the semiconductor lead frame is improved.

Sn以及B之電鍍液可產生平滑電鍍表面。在外部衝擊 = &gt;兄下，平滑電鍍表面之延性（ductmty)優於相對粗糖 冤鍍表面。此外，平滑電鍍表面可在不具有任何損壞之情The plating solutions of Sn and B produce a smooth plated surface. Under external impact = &gt; brother, the smoothness of the plated surface is better than that of the relatively coarse sugar plated surface. In addition, smooth plating surfaces can be used without any damage

況下變形，且因而適於提供可保護外部引線框之外表面I 電鑛層。 16 200928006 對環魏液不絲（叫，且_對人想無害且 t制本㈣之電繼，可在常溫下在㈣低電流 需另外加熱電鍍液。因此，生產率 ❹ Ο 一儘管已參照本發明之例示性實施例對本發明進行詳盡 =示以及描述，但一般技術者將瞭解到可在不悖離如以下 在神以及_情況下 【圖式簡單說明】 驗Λ1，至圖1 (c)為分別說明在常溫儲存試驗後實 (随=相驗^:電㈣之表錄態之掃描電子顯微鏡 驗存:後實 驗 7 = ; 室二=Γ 實 驗π&gt;至實=圖中說明在室溫儲存試驗後實 τι：銀層之表面狀態之SEM照相影像。 驗13至實2 = 分別說明在室溫儲存試驗後實 m f：c 電鍍層之表面狀態之SEM照相影像。 圖6 (b) ^在實驗16 1&quot;電齡面後之SEM照相影像， 圖6⑻為在室溫_試驗後實驗16之龍照相影像， 17 200928006 且圖6 (c)為說明在室溫儲存試驗後實驗17中電鍍層之 表面狀態之SEM照相影像。 圖7 (a)至圖7 (e)為分別說明在室溫儲存試驗後比 較性實驗1至比較性實驗5中電鍍層之表面狀態之S EM照 相影像。 【主要元件符號說明】 無It is deformed and thus is suitable for providing a surface I electro-mineral layer that protects the outer lead frame. 16 200928006 The ring Wei fluid is not silky (called, and _ is not harmless to people and the electricity of t (this) can be heated at room temperature at (4) low current needs to be heated separately. Therefore, productivity ❹ Ο DETAILED DESCRIPTION OF THE INVENTION The present invention will be described and illustrated in detail, but will be understood by those of ordinary skill in the art, and in the case of God and in the case of the following, [1], to Figure 1 (c) To illustrate the scanning electron microscopy of the recorded state after the normal temperature storage test (with the = phase test ^: electricity (four): post experiment 7 = ; room two = Γ experiment π &gt; to the real = figure shows at room temperature SEM photographic images of the surface state of the silver layer after storage test. Test 13 to real 2 = SEM image of the surface state of the real mf:c plating layer after storage test at room temperature. Figure 6 (b) ^ SEM photographic images after the experiment 16 1 &quot;Electric age, Figure 6 (8) is the photographic image of the experiment 16 at room temperature _ test, 17 200928006 and Figure 6 (c) shows the plating in the experiment 17 after the storage test at room temperature SEM image of the surface state of the layer. Figure 7 (a) to Figure 7 (e) are points DESCRIPTION than S EM photographic image of the surface state of the plated layer compared to Comparative Experiment 1 Experiment 5 storage test at room temperature. The main element SIGNS LIST None

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Claims (1)

200928006 十、申請專利範圍： 1.一種不含Pb之Sn-B電鍍液，含有作為Sn離子源之 ' 硫酸錫，以及作為B離子源之二甲胺硼烷或三甲胺硼烷。 • 2.如申請專利範圍第1項所述之不含Pb之Sn-B電鍍 液，其中所述Sn離子源之量為15g/L至50g/L。 3. 如申請專利範圍第1項所述之不含Pb之Sn-B電鍍 液，其中所述B離子源之量為0.1g/L至3.0g/L。 4. 如申請專利範圍第1項所述之不含Pb之Sn-B電鍍 ® 液，進一步含有30 ml/L至70 ml/L的硫酸。 5. 如申請專利範圍第1項所述之不含Pb之Sn-B電鍍 液，進一步含有10 g/L至40 g/L的曱紛續酸或苯紛確酸。 6. 如申請專利範圍第1項所述之不含Pb之Sn-B電鍍 液，進一步含有0.1 g/L至0.5 g/L的β-萘紛。 7. 如申請專利範圍第1項所述之不含Pb之Sn-B電鍍 液，進一步含有0.1g/L至3g/L的明膠。 8. —種電鍍方法，使用不含Pb之Sn-B電鍍液，所述 ❹ 不含Pb之Sn-B電鍍液含有作為Sn離子源之硫酸錫，以 及作為B離子源之二甲胺硼烷或三甲胺硼烷。 9. 如申請專利範圍第8項所述之電鍍方法，包含在0.5 A/dm2至5 A/dm2之電流密度下電鑛所述不含Pb之Sn-B • 電鍍液。 - 10.如申請專利範圍第8項或第9項所述之電鍍方法， 其中所述Sn離子源之量為15 g/L至50 g/L，且所述B離 子源之量為0.1 g/L至3.0 g/L，且所述不含Pb之Sn-B電 19 200928006 鍍液進一步含有30ml/L至70ml/L的硫酸、10g/L至40g/L 的甲酚磺酸或苯酚磺酸、0.1 g/L至0.5 g/L的β-萘酚以及 0.1 g/L至3 g/L的明膠。 ❹200928006 X. Patent application scope: 1. A Sn-B plating solution containing no Pb, containing tin sulfate as a source of Sn ions, and dimethylamine borane or trimethylamine borane as a source of B ions. 2. The Sn-B plating solution containing no Pb as described in claim 1, wherein the amount of the Sn ion source is from 15 g/L to 50 g/L. 3. The Pb-free Sn-B plating solution according to claim 1, wherein the amount of the B ion source is from 0.1 g/L to 3.0 g/L. 4. For the Pb-free Sn-B plating solution described in item 1 of the patent application, further containing 30 ml/L to 70 ml/L of sulfuric acid. 5. The Pb-free Sn-B plating solution described in the first paragraph of the patent application further contains 10 g/L to 40 g/L of strontium or benzoic acid. 6. The Pb-free Sn-B plating solution described in claim 1 further contains 0.1 g/L to 0.5 g/L of β-naphthalene. 7. The Pb-free Sn-B plating solution described in claim 1 further contains 0.1 g/L to 3 g/L of gelatin. 8. An electroplating method using a Sn-B plating solution containing no Pb, the Sn-B plating solution containing no Pb containing tin sulfate as a source of Sn ions, and dimethylamine borane as a source of B ions Or trimethylamine borane. 9. The electroplating method according to claim 8, comprising the electroplating of the Pb-free Sn-B plating solution at a current density of 0.5 A/dm2 to 5 A/dm2. 10. The electroplating method according to claim 8 or 9, wherein the amount of the Sn ion source is from 15 g/L to 50 g/L, and the amount of the B ion source is 0.1 g. /L to 3.0 g / L, and the Pb-free Sn-B electricity 19 200928006 plating solution further contains 30ml / L to 70ml / L of sulfuric acid, 10g / L to 40g / L of cresysulfonic acid or phenolsulfonate Acid, 0.1 g/L to 0.5 g/L β-naphthol and 0.1 g/L to 3 g/L gelatin. ❹ 2020