200536955 (1) 九、發明說明 【發明所屬之技術領域】 本發明爲關於以羥基鏈烷磺酸作爲主成分之鍍浴用添 加劑，以及使用此添加劑之鍍浴。 【先前技術】 以往羥基鏈烷磺酸多被作爲各種鍍浴之成分使用，例 如於專利文獻一中，即有其可作爲提升焊錫焊接性用被膜 或抗鈾刻用被膜之用於錫鉛合金電鍍用之的鍍浴成份。 又於專利文獻二中，其被使用於對電子零件電鍍或作 爲形成半導體晶圓表面之Pb-Sn合金突起電極的鍍浴成 分。 又，於專利文獻三中，其被使用爲銀或銀合金電鍍的 鍍浴成分。 又於專利文獻四中，其被使用爲無電解錫一鉍合金鍍 浴的鍍浴成分。 但是，以往所供應之一般的羥基鏈烷磺酸，例如爲羥 乙磺酸時，因環氧乙烷與亞硫酸氫鈉作用會產生鈉鹽（參 照非專利文獻一），故必須經由離子交換去除鹼金屬成分 後之酸方可使用。 另一方面，於含有羥基鏈烷磺酸之鍍浴電鍍半導體設 備等電子構件時，會有產生電子構件之電路間的絕緣不良 等問題。 〔專利文獻一〕特開昭5 3 - 1 4 1 3 1號公報 〔專利文獻二〕特開平1 1 一 1 792號公報 (2) 200536955 〔專利文獻三〕特開平1 1 — 2 7 9 7 8 7號公報 〔專利文獻四〕特開2000 — 87252號公報 〔非專利文獻一〕化學大辭典（第1卷5 8 1 出版股份有限公司刊） 【發明內容】 因此，本發明爲提供一種即使使用含有羥基 之鍍浴對如半導體設備等電子構件電鍍時，也不 成電路間絕緣不良等問題之起因的鍍浴用添加劑 〇 本發明者們對於上述問題深入硏究的結果， 鍍浴中含有鹼金屬時，則即使於電鍍後對被鍍物 工業上容許之經濟範圍下之洗淨後，仍會殘留鹼 果將會使電子構件之電路間發生絕緣不良，基於 而達成本發明。 即，本發明爲一種鍍浴用添加劑，其爲以羥 酸作爲主成分之鍍浴用添加劑，其特徵爲，相對 磺酸而言，鹼金屬成分的含量爲未達〇.〇5質量％ 又’本發明之上述鍍浴用添加劑，其中羥基 爲羥乙磺酸。 又本發明之上述鍍浴用添加劑，其中羥基鏈 將羥烷基硫醇以過氧化氫氧化的方法製成。 又本發明爲一種添加有上述鍍浴用添加劑爲 浴。 本發明，爲提供一種即使使用含有羥基鏈烷 頁、共立 鏈烷磺酸 會成爲造 以及鍍浴 得知若於 表面施以 金屬，結 前述理解 基鏈烷磺 羥基鏈烷 〇 鏈烷磺酸 烷磺酸爲 特徵之鍍 磺酸之鍍 -6- (3) (3)200536955 浴對如半導體設備等電子零件電鍍時，也不會成爲造成電 路間絕緣不良等問題之起因的鍍浴用添加劑以及鍍浴。。 本發明之鍍浴用添加劑爲，於以羥基鏈烷磺酸作爲主 成分時’相對於羥基鏈烷磺酸而言，鹼金屬成分的含量爲 未達0.05質量％。 羥基鏈烷磺酸並無特別指定，較佳爲一般式HO - R -S03H(其中，R爲碳原子數1〜12之烴基，且羥基可於R 的任意位置）所示之化合物，具體而言，例如2 -羥基乙 院一 1 一磺酸（經乙磺酸）、2 -羥基丙院—1 一磺酸、1 一 經基丙院一 2 -磺酸、3-經基丙院一 1 一磺酸、2—經基丁 烷一 1—磺酸、4 —羥基丁烷—1 一磺酸、2-羥基戊烷一 1 一磺酸、2-羥基己烷一 1 一磺酸、2-羥基癸烷一 1 一磺酸 等，其中又以2 -羥基乙烷- 1 一磺酸（羥乙磺酸）作爲鍍 浴用添加劑爲最佳。 取得羥基鏈烷磺酸之方法並無特別指定，若以羥乙磺 酸作爲例說明，其以一般製造方法，即使環氧乙烷與亞硫 酸氫鈉作用以製得鈉鹽，再以離子交換將鹼金屬成分除去 以製得羥乙磺酸時，需重複進行離子交換處理步驟使直到 鹼金屬成分至0.05質量％以下，直到鹼金屬成分對羥基 鏈烷磺酸爲低於0.05質量％即可。 又，如特開平1〇— 204052號公報所記載般，將羥基 烷基硫醇以過氧化氫氧化之方法，因不使用鹼金屬，故可 更有效率地取得鹼金屬成分低於〇. 〇 5質量％之羥基鏈烷 磺酸，故爲較佳。 本發明之鍍浴用添加劑爲，一種適合添加至鍍浴中的 (4) (4)200536955 羥基鏈烷磺酸成分，且鍍浴用添加劑中之羥基鏈烷磺酸含 量可爲任意量。本發明之鍍浴，除羥基鏈烷磺酸以外，也 可配合其他欲添加至鍍浴中的成分，但必須維持對羥基鏈 烷磺酸的鹼金屬成分不超過0.05質量％以上。 添加至鍍浴中的其他成分爲任意成分，舉例說明時， 例如氧化防止劑（例如鄰苯二酚、氫醌、抗壞血酸等）、 光澤劑或光澤助劑（例如苯醛、甲醛水、乙二醛等）、錯 化劑（EDTA、伸乙基二胺、檸檬酸等）、作爲均化劑的 非離子性介面活性劑（例如聚乙烯乙二醇、氧代乙烯氧丙 烯嵌段共聚物、烷基酚環氧乙烷附加物、高級醇環氧乙烷 附加物、多元醇脂肪酸酯、脂肪酸烷醇醯胺等）、氧化防 止劑或平滑劑（硫脲、乙烯硫脲、硫代乙醇酸等）等。 以下，本發明的鍍浴爲，添加上述本發明之鍍浴用添 加劑的鍍浴，除羥基鏈烷磺酸以外，以往，已知含有羥基 鏈院擴酸的鍍浴成分於一般使用量的範圍內也可任意的添 加，又，羥基鏈烷磺酸之使用量爲以往公知的範圍即可。 因此，本發明之鍍浴中的羥基鏈烷磺酸成分可依使用 者所需作任意之選擇，而無特別限定，例如，以提供欲電 鍍之金屬離子的化合物（例如銅、錫、銀以及其鹽、氧化 物等的單數或複數）開始，至使用無機酸、有機酸、氧化 劑、還原劑、界面活性劑、pH調整劑、緩衝劑、平滑劑 、應力和緩劑、安定劑、錯化劑（螯合劑）、光澤劑、半 光澤劑、抗氧化劑、分散劑、均化劑、其他可添加於鍍浴 中的添加劑，以及可添加至上述本發明之鍍浴用添加劑的 任意成分皆可使用。 -8- (5) 200536*955 【實施方式】 以下將以本發明的實施例藉以再說明本發明，但本發 '明並非限定於此。 〔實施例一〕 於備有內部冷卻劑、攪拌裝置、附有餾去溶媒所使用 的開關閥之冷卻器以及液體導入裝置之玻璃製反應裝置， ¥ 加入60質量％的過氧化氫357g(6.3mol)後，在攪拌的 同時，將156g(2.0mol)的2 —氫硫基乙醇以0.4ml /分 鐘之速度由液體導入口連續進料。其間，調節注入冷卻器 的冷卻水量使液溫維持於4 5 °C。於2 -氫硫基乙醇添加結 束後，於室溫下持續攪拌1 〇小時。於此反應液中，以樣 品導入管吹入氮氣，而將蒸氣之一部部分排除至系外的同 時，於攪拌、常壓下加熱至1 1 (TC並維持5小時。將此反 應液以由塡充有離子交換樹脂（狄翁萊特A - 56 1 :住友 0 化學製）200mL的35mm 0之塔的塔頂以（下流速度） S V 0 · 5通液並精製，得到5 4 · 0質量％的羥乙磺酸水溶液（ 產量241.6g:產率95.9%)。由此經乙擴酸水溶液中並未 • 驗出驗金屬成分（檢測界限1 0 p p b )。 將此羥乙磺酸水溶液作爲本發明之鍍浴用添加劑（1200536955 (1) IX. Description of the invention [Technical field to which the invention belongs] The present invention relates to a plating bath additive containing hydroxyalkanesulfonic acid as a main component, and a plating bath using the additive. [Prior art] In the past, hydroxyalkane sulfonic acid was mostly used as a component of various plating baths. For example, in Patent Document 1, there is a tin-lead alloy that can be used as a coating for improving solderability or a coating for resisting uranium etching. Plating bath composition for electroplating. In Patent Document 2, it is used as a plating bath component for electroplating electronic parts or as a Pb-Sn alloy bump electrode for forming a surface of a semiconductor wafer. Further, in Patent Document 3, it is used as a plating bath component for silver or silver alloy plating. In Patent Document 4, it is used as a plating bath component of an electroless tin-bismuth alloy plating bath. However, when conventional hydroxyalkanesulfonic acids supplied in the past, such as isethionsulfonic acid, sodium salts are generated by the interaction of ethylene oxide and sodium bisulfite (see Non-Patent Document 1), so they must be ion-exchanged. Use the acid after removing the alkali metal component. On the other hand, when electronic components such as a plating bath containing hydroxyalkanesulfonic acid are plated on semiconductor devices, there are problems such as poor insulation between the circuits of the electronic components. [Patent Document 1] JP-A Sho 5 3-1 4 1 3 1 [Patent Document 2] JP-A Hei 1 1-1 792 (2) 200536955 [Patent Document 3] JP-A 1-2 7 9 7 8 [Patent Document 4] JP 2000-87252 [Non-Patent Document 1] Chemical Dictionary (Vol. 1 5 8 1 Publishing Co., Ltd.) [Summary of the Invention] Therefore, the present invention provides a Additives for plating baths that do not cause problems such as poor inter-circuit insulation when electroplating electronic components such as semiconductor devices using a plating bath containing hydroxyl groups. As a result of intensive investigations by the present inventors, the plating bath contains alkali metals. In this case, even after washing in the economical range permitted by the industry of the plated material after electroplating, alkali residues will remain, which will cause poor insulation between the circuits of electronic components. This is based on the invention. That is, the present invention is an additive for a plating bath, which is an additive for a plating bath having hydroxy acid as a main component, and is characterized in that the content of an alkali metal component is less than 0.05 mass% relative to sulfonic acid. In the above-mentioned additive for a plating bath of the present invention, the hydroxyl group is isethionate. Furthermore, in the above-mentioned additive for a plating bath of the present invention, the hydroxy chain is made of a hydroxyalkyl mercaptan by a method of hydrogen peroxide oxidation. The present invention is a bath to which the above-mentioned additive for a plating bath is added. The present invention is to provide a alkane sulfonate, a co-paraffinic alkane sulfonic acid, and a plating bath. It is understood that if a metal is applied to the surface, the aforementioned alkane sulfo hydroxy alkane is synthesized. Plating with sulfonic acid is characterized by sulphonic acid plating. 6- (3) (3) 200536955 When plating electronic components such as semiconductor equipment, it will not be an additive for plating baths and plating that will cause problems such as poor insulation between circuits. bath. . In the plating bath additive of the present invention, when a hydroxyalkanesulfonic acid is used as a main component, the content of the alkali metal component relative to the hydroxyalkanesulfonic acid is less than 0.05% by mass. The hydroxyalkanesulfonic acid is not particularly specified, and is preferably a compound represented by the general formula HO-R -S03H (where R is a hydrocarbon group having 1 to 12 carbon atoms, and the hydroxyl group may be at any position of R). In other words, for example, 2-Hydroxyethylamine-1 monosulfonic acid (via ethanesulfonic acid), 2-Hydroxypropylamine-1 sulfonic acid, 1 Monosulfonic acid, 2-via-butane-1-sulfonic acid, 4-hydroxybutane-1 monosulfonic acid, 2-hydroxypentane-1 monosulfonic acid, 2-hydroxyhexane-1 monosulfonic acid, 2 -Hydroxydecane-1 monosulfonic acid and the like, in which 2-hydroxyethane-1 monosulfonic acid (isethionic acid) is the best additive for the plating bath. The method for obtaining hydroxyalkanesulfonic acid is not particularly specified. If isethionate is used as an example, it is a general manufacturing method. Even if ethylene oxide reacts with sodium bisulfite to obtain a sodium salt, it is then exchanged with ions. When the alkali metal component is removed to obtain isethionate, it is necessary to repeat the ion exchange treatment step until the alkali metal component is less than 0.05% by mass, and the alkali metal component is less than 0.05% by mass to the hydroxyalkanesulfonic acid. . In addition, as described in Japanese Patent Application Laid-Open No. 10-204052, a method in which hydroxyalkyl mercaptan is subjected to hydrogen peroxide oxidation, because an alkali metal is not used, so that the alkali metal component can be obtained more efficiently. 5 mass% of hydroxyalkanesulfonic acid is preferred. The additive for the plating bath of the present invention is a (4) (4) 200536955 hydroxyalkanesulfonic acid component suitable for being added to the plating bath, and the content of the hydroxyalkanesulfonic acid in the additive for the plating bath may be any amount. In the plating bath of the present invention, in addition to the hydroxyalkanesulfonic acid, other components to be added to the plating bath may be blended. However, the alkali metal component of the hydroxyalkanesulfonic acid must not exceed 0.05% by mass or more. The other ingredients added to the plating bath are arbitrary. For example, for example, oxidation inhibitors (such as catechol, hydroquinone, ascorbic acid, etc.), gloss agents, or gloss additives (such as benzaldehyde, formaldehyde, ethylene glycol, etc.) Aldehydes, etc.), disabling agents (EDTA, ethylene diamine, citric acid, etc.), nonionic surfactants (such as polyethylene glycol, oxyethylene oxypropylene block copolymers) as leveling agents, Alkylphenol ethylene oxide additives, higher alcohol ethylene oxide additives, polyol fatty acid esters, fatty acid alkanolamines, etc.), oxidation inhibitors or smoothing agents (thiourea, ethylene thiourea, thioethanol Acid, etc.) etc. Hereinafter, the plating bath of the present invention is a plating bath to which the above-mentioned additive for a plating bath of the present invention is added. Except for hydroxyalkanesulfonic acid, conventionally, it is known that a plating bath component containing a hydroxyl chain acid expansion is within a range of a general use amount. It may be added arbitrarily, and the amount of the hydroxyalkanesulfonic acid used may be in a conventionally known range. Therefore, the hydroxyalkanesulfonic acid component in the plating bath of the present invention can be arbitrarily selected according to the needs of the user, and is not particularly limited, for example, to provide compounds (such as copper, tin, silver, and (Singular or plural of its salts, oxides, etc.), to the use of inorganic acids, organic acids, oxidants, reducing agents, surfactants, pH adjusters, buffers, smoothing agents, stress and retarders, stabilizers, dissolving agents (Chelating agent), glossing agent, semi-glossing agent, antioxidant, dispersing agent, leveling agent, other additives that can be added to the plating bath, and any components that can be added to the above-mentioned plating bath additive of the present invention can be used. -8- (5) 200536 * 955 [Embodiment] Hereinafter, the present invention will be described with reference to examples of the present invention, but the present invention is not limited thereto. [Example 1] A glass-made reaction device equipped with an internal coolant, a stirring device, an on-off valve used to distill off the solvent, and a liquid introduction device was charged with 357 g of hydrogen peroxide (6.3% by mass, 6.3 g) mol), while stirring, 156 g (2.0 mol) of 2-hydrothiothioethanol was continuously fed from the liquid introduction port at a rate of 0.4 ml / min. Meanwhile, the amount of cooling water injected into the cooler was adjusted so that the liquid temperature was maintained at 4 5 ° C. After the addition of 2-hydrothioethanol was completed, stirring was continued at room temperature for 10 hours. In this reaction solution, nitrogen was blown in through a sample introduction tube, while part of the vapor was excluded from the system, and then heated to 1 1 (TC and maintained for 5 hours under stirring and normal pressure. This reaction solution was maintained for 5 hours. The top of the 35mm 0 tower filled with 200 mL of ion exchange resin (Dion Wright A-56 1: manufactured by Sumitomo Chemical Co., Ltd.) was passed through (reduced velocity) SV 0 · 5 to obtain 5 4 · 0 mass. % Isethionate aqueous solution (yield 241.6g: yield 95.9%). As a result, no metal component (detection limit 10 ppb) was detected in the ethylene glycol acid aqueous solution. This isethionate aqueous solution was used as Additive for plating bath of the present invention (1
43質 調製市售的羥乙磺酸鈉（青木油脂工業製）之 -9 - (6) (6)200536955 量％水溶液，並將此由塡充有離子交換樹脂（摩諾斯菲爾 630C一H:道化學公司製）82mL的3Omm0之塔之塔頂以 (下流速度）SV 1 ·0通液並精製，而得到對羥乙磺酸之鈉 含量爲5質量％之1 〇質量％的羥乙磺酸水溶液。將此羥 乙磺酸濃度濃縮至40質量％之產物作爲本發明之比較鍍 浴用添加劑（1 )。 將離子交換樹脂依常用方法再生後，進行2次與比較 鍍浴用添加劑（1 )相同之精製步驟，而得到對羥乙磺酸 爲0 · 0 3質量％之之鈉含量的7 · 0質量％的羥乙磺酸水溶液 。將此羥乙磺酸濃度濃縮至40質量％之產物作爲本發明 之比較鍍浴用添加劑（2 )。 〔實施例三〕 於實施例一中，除了以2 -氫硫基丙醇替代2 -氫硫 基乙醇以外，其他均依實施例一之相同方法製得4 9.2質 量％之2 -羥基丙烷一 1 一磺酸水溶液。該2 -羥基丙烷一 1 -磺酸水溶液中並未檢測出鹼金屬成分。 將此2 -羥基丙烷- 1 -磺酸水溶液作爲本發明之鍍浴 用添加劑（3 )。 〔實施例四、比較例二〕 將實施例一〜三所得到之本發明的鍍浴用添加劑以及 比較例一所得到之比較鍍浴用添加劑依表一記載組成的水 溶液製得各鍍浴（鍍錫用鍍浴）。 -10- 20053695543 mass prepared commercially available sodium isethionate (manufactured by Aoki Oil Industry Co., Ltd.)-9-(6) (6) 200536955 volume% aqueous solution, and this was filled with ion exchange resin (Monosfil 630C- H: made by Dow Chemical Co., Ltd.) 82 mL of a 30 mm 0 top of the tower was passed through (reflow velocity) SV 1 · 0 and purified to obtain a sodium p- isethionate with a sodium content of 5% by mass and 10% by mass of hydroxy. Aqueous ethanesulfonic acid. The product obtained by concentrating this isethionate to 40% by mass was used as an additive (1) for a comparative plating bath of the present invention. After regenerating the ion exchange resin according to a common method, the same purification step as that of the additive (1) for the plating bath was performed twice, to obtain 7.0% by mass of sodium content of 0.3% by mass with respect to isethionate. Aqueous isethionate. The product obtained by concentrating this isethionate to 40% by mass was used as the additive for a comparative plating bath (2) of the present invention. [Example 3] In Example 1, 4 9.2% by mass of 2-hydroxypropane-1 was obtained in the same manner as in Example 1, except that 2-hydrothiothiopropanol was used instead of 2-hydrothiothioethanol. 1 Aqueous sulfonic acid solution. No alkali metal component was detected in this 2-hydroxypropane- 1-sulfonic acid aqueous solution. This 2-hydroxypropane-1-sulfonic acid aqueous solution was used as the additive (3) for the plating bath of the present invention. [Example 4 and Comparative Example 2] The plating bath additives of the present invention obtained in Examples 1 to 3 and the comparative plating bath additives obtained in Comparative Example 1 were each prepared according to an aqueous solution with the composition described in Table 1. With a plating bath). -10- 200536955
表1 SnO 3〇g/L 硫脲 8g/L 各種鍍浴用添加劑 (以羥基鏈烷磺酸計） 100g/L P -異丙苯基酚乙烯氧化物（1 〇莫耳）加成物 l〇g/L 乙二醛 lg/L 兒茶酚 lg/L 剩餘量 水 又，於矽晶圓上製造鄰接兩系統之銅回路，並將各銅 回路以上述各鍍浴鍍錫後，再測試其回路間之絕緣性的結 果，得知使用本發明之各鍍浴的情形具有良好絕緣性，但 使用比較例二所得到之使用比較鍍浴用添加劑的鍍浴之情 形則顯示出不良絕緣性。Table 1 SnO 30 g / L thiourea 8 g / L Various plating bath additives (based on hydroxyalkanesulfonic acid) 100 g / LP-cumylphenol ethylene oxide (10 mol) adduct 10 g / L Glyoxal lg / L Catechol lg / L The remaining amount of water was used to produce copper circuits adjacent to the two systems on a silicon wafer, and the copper circuits were tinned with the above-mentioned plating baths, and then the circuits were tested. As a result of the insulative properties, it was found that the cases using the respective plating baths of the present invention had good insulation properties, but the cases using the plating baths obtained by using the comparative plating bath additives obtained in Comparative Example 2 showed poor insulation properties.
-11 --11-