TW200425363A - Tin whisker generation-preventing agent and method of producing a whiskerless tin-plated product by using the same - Google Patents
Tin whisker generation-preventing agent and method of producing a whiskerless tin-plated product by using the same Download PDFInfo
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- TW200425363A TW200425363A TW093105750A TW93105750A TW200425363A TW 200425363 A TW200425363 A TW 200425363A TW 093105750 A TW093105750 A TW 093105750A TW 93105750 A TW93105750 A TW 93105750A TW 200425363 A TW200425363 A TW 200425363A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/38—Fibrous materials; Whiskers
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/76841—Barrier, adhesion or liner layers
- H01L21/76871—Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers
- H01L21/76874—Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers for electroless plating
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Abstract
Description
200425363 ⑴ 玖、發明說明 【發明所屬之技術領域】 本發明係有關爲防止鍍錫物相關之鬚晶之防止錫鬚晶 產生劑及使用其製造防鬚晶性鍍錫物的方法。 【先前技術】200425363 ⑴ 玖, Description of the invention [Technical field to which the invention belongs] The present invention relates to a tin whisker generation preventing agent for preventing whiskers related to tin plating and a method for manufacturing the whisker-resistant tin plating using the tin whisker generation agent. [Prior art]
由於鍍錫係錫焊性及耐蝕性良好，適用於電氣•電子 零件（例如，電氣零件之端子或印刷配線基板等）之電鍍 ，廣泛的被利用。 但是，鍍錫物，已知鍍錫後鍍錫表面產生所謂鬚晶之 鬚狀錫結晶。此錫鬚晶，特別是，爲引起有關電氣•電子 零件之短路，相關之鍍錫物希望防止錫鬚晶之產生。Due to its excellent solderability and corrosion resistance, tin-plating is suitable for electroplating of electrical and electronic parts (for example, terminals of electrical parts or printed wiring boards), and is widely used. However, tin plating is known to produce so-called whisker-like tin crystals on the tin plating surface after tin plating. This tin whisker, in particular, is intended to prevent the occurrence of tin whiskers in order to cause a short circuit in electrical and electronic parts.
錫鬚晶之產生被認爲被鍍錫物表面凹凸的起因，被鍍 錫物表面嘗試平滑化，專利文獻1提案以含酸、氧化物、 及硫酸基或磷酸基由親水基之直鏈或環狀烴基以疏水基之 有機高分子化合物之處理液平滑化處理被鍍錫物表面。 〔專利文獻1〕 日本特開平5_ 1 4 8 6 5 8號公報（專利申請範圍等） 【發明內容】 〔發明所欲解決之課題〕 但是，專利文獻1記載之處理液，爲了平滑化被鍍錫 物表面，被鍍錫物表面須蝕刻2 // m或以上之厚度。因此 ，使用如此之處理液對年年高積體化進展之電子零件有關 -4- (2) 200425363 之線幅之微細線路銅等之被鍍錫物時，被鍍錫自身之形狀 安定性有難保之問題。 因此本發明之目的爲提供僅以少許之蝕刻量亦可充分 平滑化被鍍錫物表面可防止產生錫鬚晶之防止錫鬚晶產生 劑。The generation of tin whiskers is considered to be the cause of the unevenness on the surface of the tin-plated object, and the surface of the tin-plated object is attempted to be smoothed. Patent Document 1 proposes to include an acid, oxide, and sulfate or phosphate group from a The cyclic hydrocarbon group smoothes the surface of the object to be tinned with a treating solution of a hydrophobic organic polymer compound. [Patent Document 1] Japanese Patent Laid-Open No. 5_ 1 4 8 6 5 8 (Scope of Patent Application, etc.) [Summary] [Problems to be Solved by the Invention] However, the treatment liquid described in Patent Document 1 is plated for smoothing. The surface of tin objects and the surface of tin objects must be etched to a thickness of 2 // m or more. Therefore, the use of such a treatment solution is relevant to electronic components that have been accumulating high-volume accumulations every year. -4- (2) 200425363 Tin-plated objects such as fine-line copper with wire width, the shape of tin-plated itself is stable Insurable issue. It is therefore an object of the present invention to provide a tin whisker preventing agent that can sufficiently smooth the surface of a tin-plated object and prevent tin whisker generation with only a small amount of etching.
又’本發明之另一目的爲提供微細之被鍍錫物僅施以 少許之蝕刻量亦可充分保持被鍍錫物之形狀安定性之防止 錫鬚晶性鍍錫之製造方法。 〔課題解決手段〕 本發明者爲解決上述課題經深入硏究結果完成本發明 即本發明係ρ Η 5以下含鐵化合物系氧化劑、非離子 性界面活性劑、及銅離子之水溶液爲特徵之防止錫鬚晶產 生劑。Another object of the present invention is to provide a method for preventing tin whisker crystalline tin plating, which can maintain the shape stability of the tin-plated object sufficiently even by applying a small amount of etching to a fine tin-plated object. [Problem Solving Means] The present inventors have completed intensive research in order to solve the above-mentioned problems, and completed the present invention, that is, the present invention is a ρ Η 5 or lower iron-containing compound-based oxidant, a nonionic surfactant, and an aqueous solution of copper ions. Tin whisker generator.
有關本發明之防止錫鬚晶產生劑之非離子性界面活性 劑爲以下一般式（1 )及/或一般式（2 ) A[ ( C3H6〇 ) n ( C2H40 ) mH]k ( 1 ) A ( C2H40 ) m[ ( C3H60 ) nH]k ( 2 ) 所示之化合物者爲理想（式中，A爲k價之含有活性 氫化合物之殘基、k爲1〜4之數，η爲3〜35之數，m爲 1〜70之數）。又鐵化合物系氧化劑爲至少一種以上由氯 化鐵、硫酸鐵及硝酸鐵所成群所選者爲理想。 又，本發明係被鍍錫物表面以防止錫鬚晶產生劑處理 -5- (3) 200425363 後，施以鍍錫之鬚晶性鍍錫物之製造方法。 本發明相關之製造方法，理想爲被鍍錫物爲電子裝置 之配線銅者。 〔發明之實施型態〕 以下具體的說明本發明之實施型態。The non-ionic surfactant of the tin whisker generation preventing agent of the present invention is the following general formula (1) and / or general formula (2) A [(C3H6〇) n (C2H40) mH] k (1) A ( C2H40) m [(C3H60) nH] k (2) is ideal (wherein A is a k-valent residue containing an active hydrogen compound, k is a number from 1 to 4, and η is 3 to 35 Number, m is a number from 1 to 70). The iron compound-based oxidant is preferably at least one selected from the group consisting of iron chloride, iron sulfate, and iron nitrate. In addition, the present invention is a method for manufacturing tin whisker-like tin plating material after tin surface is prevented from being treated with a tin whisker generating agent (3) 200425363. The manufacturing method related to the present invention is preferably one in which the object to be plated is wiring copper for electronic devices. [Embodiment of Invention] The embodiment of the present invention will be specifically described below.
本發明之防止錫鬚晶產生劑，爲pH 5以下，理想爲 pH 4以下之酸性水溶液。水溶液之PH超過5時被鍍錫 物，特別是銅之蝕刻性惡化，又容易產生污泥。一方面， pH無特別下限，工業化適當之範圍以較低者爲理想。 水溶液調整爲上述之pH之方法無任何限制，依周知 之方法即可，例如可由含有酸而達成。酸爲有機酸或無機 酸均可，例如可單獨或混合使用鹽酸、硫酸、硝酸、磷酸 、蟻酸、醋酸等，由粘性等之作業觀點以鹽酸、磷酸或犠 酸爲理想。The tin whisker generation preventing agent of the present invention is an acidic aqueous solution having a pH of 5 or less, and preferably a pH of 4 or less. When the pH of the aqueous solution exceeds 5, the etchability of tinned materials, especially copper deteriorates, and sludge is easily generated. On the one hand, there is no particular lower limit for pH, and a lower range is suitable for industrialization. The method for adjusting the aqueous solution to the above-mentioned pH is not limited in any way, and it may be performed by a well-known method, for example, it can be achieved by containing an acid. The acid may be either an organic acid or an inorganic acid. For example, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, formic acid, acetic acid, or the like may be used alone or in combination. Hydrochloric acid, phosphoric acid, or osmic acid is preferred from the viewpoint of work such as viscosity.
本發明之防止錫鬚晶產生劑爲含鐵化合物系氧化劑。 由鐵化合物系氧化劑對被鍍錫物表面，特別是銅之表面不 作激烈之蝕刻，僅少許之蝕刻，且均勻的蝕刻觀點，而使 用於本發明。 由此觀點可使用之鐵化合物系氧化物無特別限制，氧 化劑爲公知之鐵化合物者任何物質都可使用，例如可舉例 如氯化鐵、硫酸鐵及硝酸鐵等。 本發明使用之鐵化合物系氧化劑之使用量無特別的限 制’被鑛錫物之表面’特別是銅之表面以1 · 〇 // m /分〜 -6- (4) (4)200425363 5·0 // m/分程度蝕刻者，約爲ο]〜ι〇重量％，理想爲 〜5重量％程度者即可適用。 又’本發明之防止錫鬚晶產生劑爲含非離子界面活性 劑者。可使用任何之非離子性界面活性劑，依可得到本發 明效果良好觀點，以下一般式（1 )及/或一般式（2 )， A[ ( C3H60 ) n ( C2H40 ) mH]k ⑴ A ( C2H40 ) m[ ( C3H60 ) nH]k ( 2 ) 所不之化合物爲理想（式中，A爲k價之含有活性氫 化合物之殘基、k爲1〜4之數，η爲3〜35之數，⑺爲1 〜70之數）。 上述一般式中，對應Α之含活性氫化合物，可列舉 如碳數3〜1 8之醇類，具碳數3〜1 8之烷基之烷基苯酚 ，乙二醇、丙二醇、丁二醇等之甘醇類，三羥甲基丙烷、 甘油、季戊四醇、山梨糖醇等之多價醇類爲代表之含烴基 化合物，或乙二胺、二乙三胺等之烷基胺等，特別以乙二 胺等之烷基胺爲理想。 又，上述一般式中，多氧乙撐基鏈、多氧丙撐基鏈， 可由如上述含活性氫化合物以環氧乙烷或環氧丙烷依常法 加成而得。有關其加成莫耳數（上述一般式之η及m)， 爲達成本發明之期待之目的，η爲3〜3 5，理想爲6〜1 5 ，m爲1〜7 0，更理想爲2〜2 0之數。又，此係以平均値 表不。 本發明使用之非離子性界面活性劑之使用量無特別之 限制，約0. 1〜7重量％，理想爲0 · 5〜3重量％程度者可 (5) 200425363 適用。 又，本發明之防止錫鬚晶產生劑爲含銅離子者 子由氯化銅、硫酸銅、硝酸銅等之銅鹽溶解亦可， 劑存在於系中之階段溶解亦可。又，溶解銅鹽時， 以與上述鐵化合物或酸等同樣離子之鹽理想。此銅 想之適用銅ί辰度爲0.05〜10 g/L，更理想爲0 · 5〜 ，最理想爲1 . 5〜5 g / L。 本發明之防止錫鬚晶產生劑，上述之配合物以 不妨礙本發明之目的範圍內可配合添加其他希望之 劑或濕潤性提昇劑等。 其A ’ δ兌明本發明鑛錫物之製造方法。本發明 錫鬚晶產生劑之製造方法係於被鍍錫物表面以本發 止錫鬚ΒΗ產生劑處理後’施以鑛錫者。 被鍍錫物爲金屬即可，無特別限制，被鍍錫物 銅或銅合金者本發可得到顯著的效果爲理想。又被 爲微細之電子裝置之銅配線等時亦可得到本發明理 之效果。 本發明之防止錫鬚晶產生劑之被鍍錫物表面之 段，無特別限制，例如由浸漬法或噴霧法等公知之 於被鍍錫物表面與本發明之防止錫鬚晶產生劑接觸 又，處理條件亦無特別限制，由少許之蝕刻量 分平滑化被鍍錫物表面之本發明顯著效果觀點，使 明防止錫鬚晶產生劑之被鍍錫物表面之触刻量爲0 μ m，理想爲 0 · 3〜1 // m之程度，於 1 〇〜4 0 °c 。銅離 或氧化 作業上 離子理 5 g/ L 外，在 可溶化 之防止 明之防 特別是 鑛錫物 想顯著 處理手 方法， 即可。 即可充 用本發 • 1 〜1 .5 0 〜1 2 0 (6) 200425363 秒，理想爲20〜60秒程度處理之。 【實施方式】 以下以實施例說明本發明，本發明不限於實施例。 [實施例1]The tin whisker preventing agent of the present invention is an iron-containing compound-based oxidant. The surface of the object to be plated, especially the surface of copper, is not etched violently, and only a little is etched by an iron compound-based oxidizing agent, and a uniform etching viewpoint is used for the present invention. The iron compound-based oxide that can be used from this viewpoint is not particularly limited, and any substance may be used as long as the oxidizing agent is a known iron compound, and examples thereof include iron chloride, iron sulfate, and iron nitrate. The use amount of the iron compound-based oxidant used in the present invention is not particularly limited. The surface of the ore to be mined, especially the surface of copper is 1 · 〇 // m / min ~ -6- (4) (4) 200425363 5 · Etching at a level of 0 // m / min is about ο] to ι0% by weight, and ideally, it is about 5% by weight. Further, the tin whisker preventing agent of the present invention is a nonionic surfactant-containing agent. Any nonionic surfactant can be used, and according to the viewpoint that the effect of the present invention is good, the following general formula (1) and / or general formula (2), A [(C3H60) n (C2H40) mH] k ⑴ A ( C2H40) m [(C3H60) nH] k (2) is not the ideal compound (where A is a k-valent active hydrogen-containing compound residue, k is a number from 1 to 4, and η is from 3 to 35 Number, ⑺ is a number from 1 to 70). In the above general formula, the active hydrogen-containing compound corresponding to A includes alcohols having 3 to 18 carbons, alkylphenols having alkyls having 3 to 18 carbons, ethylene glycol, propylene glycol, and butanediol. Glycols such as trimethylolpropane, glycerol, pentaerythritol, sorbitol and other polyvalent alcohols are typical hydrocarbon-containing compounds, or alkylamines such as ethylenediamine and diethylenetriamine. Alkylamines such as ethylenediamine are preferred. In the above general formula, a polyoxyethylene chain and a polyoxypropylene chain can be obtained by the addition of an active hydrogen-containing compound as described above with ethylene oxide or propylene oxide in a conventional manner. Regarding the addition mol number (η and m of the above general formula), in order to achieve the expected purpose of the invention, η is 3 to 35, ideally 6 to 1 5 and m is 1 to 70, and more preferably, 2 to 2 0. In addition, this is expressed by average 値. The amount of the non-ionic surfactant used in the present invention is not particularly limited, about 0.1 to 7% by weight, preferably about 0.5 to 3% by weight (5) 200425363 is applicable. The tin whisker generating agent of the present invention can be dissolved by a copper salt such as copper chloride, copper sulfate, copper nitrate, or the like when the agent containing copper ions is dissolved. Moreover, when dissolving a copper salt, the same ion salt as the said iron compound, an acid, etc. is preferable. This copper is suitable for copper with a temperature of 0.05 ~ 10 g / L, more preferably 0 · 5 ~, and most preferably 1.5 ~ 5 g / L. In the tin whisker generation preventing agent of the present invention, the above-mentioned complex may be blended with other desired agents or wettability enhancers, etc., within the range not hindering the object of the present invention. The A 'δ clarifies the method for producing the ore and tin according to the present invention. The manufacturing method of the tin whisker generating agent of the present invention is a method in which the tin whisker BΗ generating agent is treated on the surface of the object to be tinned, and the tin is applied. The object to be plated may be a metal, and there is no particular limitation. It is desirable that the object to be plated with copper or a copper alloy can obtain a significant effect. When it is used as a copper wiring of a fine electronic device, the effect of the present invention can be obtained. The section of the surface of the tin-plated object of the whisker generation preventing agent of the present invention is not particularly limited. For example, it is known that the surface of the tin-plated object is in contact with the tin-whisker generation preventive of the present invention by a known method such as dipping or spraying. The processing conditions are also not particularly limited. The significant effect of the present invention that smoothes the surface of the tin-plated object by a small amount of etching makes the contact amount of the surface of the tin-plated object to prevent tin whisker generation agent 0 μ m. Ideally, it should be in the range of 0 · 3 to 1 // m, and in the range of 0 to 40 ° c. For copper ionization or oxidation operation, in addition to 5 g / L of ionization, prevent dissolution, prevent it, and prevent it, especially for tin and minerals. If you want a significant treatment method, you can. This hair can be used as a full charge. • 1 to 1.5 0 to 1 2 0 (6) 200425363 seconds, ideally 20 to 60 seconds. [Embodiment] The present invention will be described below with examples, but the present invention is not limited to the examples. [Example 1]
混合40重量％氯化鐵82.1重量份，20重量％鹽酸 117.4重量份’76重量％蟻酸10.5重量份，85重量％磷 酸1 0 · 8重量份，作爲濕潤性提昇劑之二丙二醇單甲基醚 1〇·7重量份，一般式（1)A爲乙二胺之殘基，η爲11.6 ，m爲10.5，k=4之化合物11.0重量份，一般式（1) A 爲乙一胺之殘基，η爲11.6，m爲4，k=4之化合物1.1 重量份，純水8 5 6.4重量份，以上溶解3.8重量份銅片， 得到本發明之防止錫鬚晶產生劑（1 )。82.1 parts by weight of 40% by weight of ferric chloride, 117.4 parts by weight of 20% by weight of hydrochloric acid, 10.5 parts by weight of 76% by weight formic acid, and 10 · 8 parts by weight of 85% by weight phosphoric acid as dipropylene glycol monomethyl ether as a wettability enhancer 10.7 parts by weight, general formula (1) A is the residue of ethylenediamine, η is 11.6, m is 10.5, k = 4 is 11.0 parts by weight of the compound, general formula (1) A is the residue of ethylene monoamine 1.1 parts by weight of the compound with η being 11.6, m being 4, and k = 4, 8 5 6.4 parts by weight of pure water, and 3.8 parts by weight of copper flakes were dissolved to obtain the tin whisker preventing agent (1) of the present invention.
所得之防止錫鬚晶產生劑（1 )爲pH 0 . 1 2，氯化鐵含 量3.0重量％，合計非離子性界面活性劑含量丨.1重量％ ，銅濃度3.0 g/ L。 一方面，以l〇cm xlOcm厚170//m之聚醯胺薄膜 爲絕緣基材，於其上以半添加法形線幅25 // m，線間隔 2 5 // m，線厚8 // m之銅配線回路，得到試驗用片。 其次，此試驗用片以2 5 °C上述防止錫鬚晶產生劑（1 )中浸漬3 0秒，水洗乾燥。其次，進行無電解電鍍，於 銅配線回路上設置〇. 5 // m之鍍錫皮膜。 經處理之試驗用片於大氣中放置，以顯微觀察經6 0 -9- (7) (7)200425363 曰後及經90日後鬚晶產生狀況，任一者均無鬚晶產生， 銅配線回路之形狀亦保持良好。又，以防止錫鬚晶產生劑 (1 )處理之該試驗用片之銅配線回路之線厚減少爲7 # m [實施例2] 混合40重量％氯化鐵82.1重量份，20重量％鹽酸 117.4重量份，76重量％蟻酸10.5重量份，85重量％磷 酸1 〇 . 8重量份，作爲濕潤性提昇劑之二丙二醇單甲基醚 10.7重量份，一般式（2)A爲乙二胺之殘基，η爲11·6 ，111爲10.5，k=4之化合物11.0重量份，一般式（2) A 爲乙二胺之殘基，η爲11.6，m爲4，k=4之化合物1·1 重量份，純水8 5 6.4重量份，以上溶解3.8重量份銅片， 得到本發明之防止錫鬚晶產生劑（2 )。 所得之防止錫鬚晶產生劑（2 )爲pH 0.1 2，氯化鐵含 量3.0重量％，合計非離子性界面活性劑含量1 . 1重量％ ’銅濃度3.0 g / L。 使用與實施例1同樣之試驗用片，以實施例1同樣作 試驗，觀察經60日後及經90日後鬚晶產生狀況，任一者 均無鬚晶產生，銅配線回路之形狀亦保持良好。 又，以防止錫鬚晶產生劑（2 )處理之該試驗用片之 銅配線回路之線厚減少爲7 // m。 [實施例3] -10- (8) (8)200425363 混合40重量％氯化鐵82.1重量份，20重量％鹽酸 117.4重量份’76重量％蟻酸10.5重量份，85重量％磷 酸1 0 · 8重量份，作爲濕潤性提昇劑之二丙二醇單甲基醚 10.7重量份，一般式（i)a爲乙二胺之殘基，η爲11.6 ，❿爲1〇.5，k=4之化合物11.0重量份，一般式（2) A 爲乙二胺之殘基，η爲11.6，m爲4，k=4之化合物i.i 重量份，純水8 5 6 · 4重量份，以上溶解3 · 8重量份銅片， 得到本發明之防止錫鬚晶產生劑（3 )。 所得之防止錫鬚晶產生劑（3 )爲pH 0 · 1 2，氯化鐵含 量3 · 0重量％，合計非離子性界面活性劑含量1 . 1重量％ ’銅濃度3.0 g / L。 使用與實施例1同樣之試驗用片，以實施例1同樣作 試驗，觀察經60日後及經90日後鬚晶產生狀況，任一者 均無鬚晶產生，銅配線回路之形狀亦保持良好。 又，以防止錫鬚晶產生劑（3 )處理之該試驗用片之 銅配線回路之線厚減少爲7 // m。 〔發明的功效〕 如以上之說明，依本發明之以防止錫鬚晶產生劑，僅 以少許之蝕刻量亦可充分平滑化被鍍錫物表面可有效的防 止產生錫鬚晶。又，依本發明之防止錫鬚晶性鍍錫之製造 方法，微細之被鍍錫物僅施以少許之鈾刻量亦可充分保持 被鍍錫物之形狀安定性下施以鍍錫。 -11 -The obtained whisker generation preventing agent (1) had a pH of 0.12, a ferric chloride content of 3.0% by weight, a total nonionic surfactant content of 丨 1% by weight, and a copper concentration of 3.0 g / L. On the one hand, a polyamide film with a thickness of 10 cm x 10 cm and a thickness of 170 // m is used as an insulating substrate, and a normal line width of 25 // m is added on the half, the line interval is 2 5 // m, and the line thickness is 8 / / m copper wiring circuit to obtain test pieces. Next, the test sheet was immersed in the above-mentioned tin whisker preventing agent (1) at 25 ° C for 30 seconds, washed with water and dried. Second, electroless plating was performed, and a tin plating film of 0.5 // m was provided on the copper wiring circuit. The treated test pieces were placed in the atmosphere, and microscopic observations were made of the whisker generation after 60 0 -9- (7) (7) 200425363, and after 90 days, no whisker generation occurred. Copper wiring circuit The shape also remains good. In addition, the wire thickness of the copper wiring circuit of the test piece treated with a tin whisker generator (1) was reduced to 7 # m. [Example 2] 402.1% by weight of 82.1 parts by weight of ferric chloride and 20% by weight of hydrochloric acid were mixed. 117.4 parts by weight, 76% by weight formic acid 10.5 parts by weight, 85% by weight phosphoric acid 10.8 parts by weight, dipropylene glycol monomethyl ether as a wettability enhancer 10.7 parts by weight, and general formula (2) A is ethylenediamine Residue, 11.0 parts by weight of compound with η of 11.6, 111 of 10.5, k = 4, general formula (2) A is the residue of ethylenediamine, η is 11.6, m is 4, compound of k = 4 · 1 part by weight, 8 5 6.4 parts by weight of pure water, and 3.8 parts by weight of copper flakes are dissolved above to obtain the tin whisker generation preventing agent (2) of the present invention. The obtained whisker generation preventing agent (2) had a pH of 0.1 2, a ferric chloride content of 3.0% by weight, and a total nonionic surfactant content of 1.1% by weight, and a copper concentration of 3.0 g / L. The same test piece as in Example 1 was used, and the same test was performed as in Example 1. Observation of whisker generation after 60 days and 90 days, no whisker generation was observed, and the shape of the copper wiring circuit was also good. In addition, the wire thickness of the copper wiring circuit of the test piece treated with a whisker preventing agent (2) was reduced to 7 // m. [Example 3] -10- (8) (8) 200425363 mixed 402.1% by weight 82.1 parts by weight of ferric chloride, 117.4 parts by weight of 20% by weight hydrochloric acid '76% by weight 10.5 parts by weight formic acid, 85% by weight phosphoric acid 10 8 Parts by weight, 10.7 parts by weight of dipropylene glycol monomethyl ether as a wetting enhancer, the general formula (i) a is a residue of ethylene diamine, η is 11.6, hydrazone is 10.5, and k = 4 is a compound 11.0 Parts by weight, general formula (2) A is the residue of ethylenediamine, η is 11.6, m is 4, and k = 4 is compound ii by weight, pure water is 8 5 6 · 4 parts by weight, and the above is dissolved by 3 · 8 parts by weight Parts of copper flakes to obtain the tin whisker preventing agent (3) of the present invention. The obtained whisker generation preventing agent (3) had a pH of 0.12, a ferric chloride content of 3.0% by weight, and a total non-ionic surfactant content of 1.1% by weight, with a copper concentration of 3.0 g / L. The same test piece as in Example 1 was used, and the same test was performed as in Example 1. Observation of whisker generation after 60 days and 90 days, no whisker generation was observed, and the shape of the copper wiring circuit was also good. In addition, the wire thickness of the copper wiring circuit of the test piece treated with a whisker preventing agent (3) was reduced to 7 // m. [Effect of the Invention] As described above, according to the present invention, the tin whisker generation preventing agent can sufficiently smooth the surface of the object to be tinned with only a small amount of etching, which can effectively prevent the generation of tin whisker. In addition, according to the method for preventing tin whisker-like tin plating of the present invention, only a small amount of uranium engraving can be applied to a fine tin-plated object, and tin plating can be performed while maintaining the shape stability of the tin-plated object. -11-
Claims (1)
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003079529A JP4162217B2 (en) | 2003-03-24 | 2003-03-24 | Tin whisker inhibitor and method for producing whisker preventive tin plating using the same |
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| TW200425363A true TW200425363A (en) | 2004-11-16 |
| TWI319605B TWI319605B (en) | 2010-01-11 |
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| TW093105750A TWI319605B (en) | 2003-03-24 | 2004-03-04 | Tin whisker generation-preventing agent and method of producing a whiskerless tin-plated product by using the same |
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| JP (1) | JP4162217B2 (en) |
| KR (1) | KR101059487B1 (en) |
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| JP4822714B2 (en) * | 2005-02-01 | 2011-11-24 | 荏原ユージライト株式会社 | Whisker inhibitor for tin or tin alloy plating and whisker prevention method using the same |
| JP6469895B2 (en) * | 2015-06-16 | 2019-02-13 | スリーエム イノベイティブ プロパティズ カンパニー | Plating polymer article comprising a tin / copper bond / seed layer |
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| JP4186029B2 (en) * | 1998-10-05 | 2008-11-26 | 石原薬品株式会社 | Abnormal crystal precipitation inhibitor in tin or tin alloy plating film on copper foil substrate and method for preventing the same |
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- 2003-03-24 JP JP2003079529A patent/JP4162217B2/en not_active Expired - Lifetime
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- 2004-03-04 TW TW093105750A patent/TWI319605B/en not_active IP Right Cessation
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| TWI319605B (en) | 2010-01-11 |
| JP4162217B2 (en) | 2008-10-08 |
| KR20040084653A (en) | 2004-10-06 |
| JP2004285417A (en) | 2004-10-14 |
| KR101059487B1 (en) | 2011-08-25 |
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