TWI557271B - Formaldehyde-free electroless copper plating solution - Google Patents
Formaldehyde-free electroless copper plating solution Download PDFInfo
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- TWI557271B TWI557271B TW101136996A TW101136996A TWI557271B TW I557271 B TWI557271 B TW I557271B TW 101136996 A TW101136996 A TW 101136996A TW 101136996 A TW101136996 A TW 101136996A TW I557271 B TWI557271 B TW I557271B
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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
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
Description
本發明係關於一種無電鍍銅溶液、利用該溶液進行無電鍍銅之方法及該溶液用於電鍍基板之用途。 The present invention relates to an electroless copper plating solution, a method of performing electroless copper plating using the solution, and the use of the solution for plating a substrate.
無電電鍍為在無外部電子供應之幫助下連續金屬膜之控制自催化沈積。可預處理非金屬表面以使其對沈積具有接受性或催化性。表面之全部或所選部分宜經預處理。無電銅浴之主要組分為銅鹽、錯合劑、還原劑及作為視情況選用之成分的鹼，及添加劑，例如穩定劑。錯合劑係用以螯合所沈積之銅且防止銅自溶液中沈澱(亦即呈氫氧化物及其類似物形式)。螯合銅使得銅可由還原劑獲得，該還原劑將銅離子轉化為金屬形式。 Electroless plating is controlled autocatalytic deposition of a continuous metal film without the aid of an external electron supply. The non-metallic surface can be pretreated to make it receptive or catalytic to deposition. All or selected portions of the surface should be pretreated. The main components of the electroless copper bath are copper salts, complexing agents, reducing agents and bases as optional components, and additives such as stabilizers. The binder is used to sequester the deposited copper and prevent copper from precipitating from the solution (i.e., in the form of hydroxides and the like). Chelating copper allows copper to be obtained from a reducing agent that converts copper ions to a metallic form.
常見的無電銅浴使用甲醛作為還原劑。甲醛為常見無電鍍銅方法之最重要且公認的還原劑。1987年，美國環境保護局(U.S.Environmental Protection Agency)將甲醛分類為可能的人類致癌物。2004年6月，國際癌症研究機構(International Agency for Research on Cancer；IARC)將甲醛分類為人類致癌物。因此，已開發出不含甲醛無電銅浴來滿足安全性及職業健康要求。 A common electroless copper bath uses formaldehyde as a reducing agent. Formaldehyde is the most important and recognized reducing agent for common electroless copper plating processes. In 1987, the U.S. Environmental Protection Agency classified formaldehyde as a possible human carcinogen. In June 2004, the International Agency for Research on Cancer (IARC) classified formaldehyde as a human carcinogen. Therefore, formaldehyde-free copper baths have been developed to meet safety and occupational health requirements.
US 4,617,205揭示一種用於無電銅沈積之組合物，其包含銅離子、作為還原劑之乙醛酸鹽，及錯合劑，例如EDTA，其能夠與銅形成強於乙二酸銅錯合物之錯合物。 No. 4,617,205 discloses a composition for electroless copper deposition comprising copper ions, glyoxylate as a reducing agent, and a complexing agent, such as EDTA, which is capable of forming a stronger copper complex than copper oxalate complex. Compound.
US 7,220,296教示一種無電鍍浴，其包含水溶性銅化合 物、乙醛酸及錯合劑(可為EDTA)。 US 7,220,296 teaches an electroless plating bath comprising a water soluble copper compound , glyoxylic acid and a complexing agent (may be EDTA).
US 20020064592揭示一種無電浴，其包含銅離子來源、作為還原劑之乙醛酸或甲醛，及作為錯合劑之EDTA、酒石酸鹽或烷醇胺。 No. 20020064592 discloses an electroless bath comprising a source of copper ions, glyoxylic acid or formaldehyde as a reducing agent, and EDTA, a tartrate or an alkanolamine as a binder.
US 20080223253揭示一種無電鍍銅溶液，其包括銅鹽、可選自由以下組成之群的還原劑：甲醛、多聚甲醛、乙醛酸、NaBH4、KBH4、NaH2PO2、肼、福馬林(formalin)、多醣(諸如葡萄糖)及其混合物，及可選自由以下組成之群的錯合劑：乙二胺四乙酸(EDTA)、羥乙基乙二胺三乙酸(HEDTA)、環己烷二胺四乙酸、二伸乙三胺五乙酸及肆(2-羥丙基)乙二胺(下文亦稱為「Quadrol」，其為BASF公司之商標)。 US 20080223253 discloses an electroless copper plating solution comprising a copper salt, optionally a reducing agent of the following composition: formaldehyde, paraformaldehyde, glyoxylic acid, NaBH 4 , KBH 4 , NaH 2 PO 2 , hydrazine, formalin (formalin), polysaccharides (such as glucose) and mixtures thereof, and optional combinations of the following components: ethylenediaminetetraacetic acid (EDTA), hydroxyethylethylenediaminetriacetic acid (HEDTA), cyclohexane Aminetetraacetic acid, diethylenetriaminepentaacetic acid, and hydrazine (2-hydroxypropyl)ethylenediamine (hereinafter also referred to as "Quadrol", a trademark of BASF Corporation).
EDTA、HEDTA、肆(2-羥丙基)乙二胺及其他相關錯合劑之缺陷在於缺乏生物降解性。 A drawback of EDTA, HEDTA, bismuth (2-hydroxypropyl) ethylenediamine and other related complexing agents is the lack of biodegradability.
鍍銅溶液之效能一般不可預測且主要視其組分(尤其為錯合劑及還原劑)及其組分之莫耳比而定。 The effectiveness of a copper plating solution is generally unpredictable and depends primarily on the molar ratio of its components, especially the binder and reducing agent, and their components.
本發明之一目標為提供不含甲醛的無電鍍銅溶液。 It is an object of the present invention to provide an electroless copper-free solution that is free of formaldehyde.
另一目標在於提供具有改良之效能(例如改良之銅沈積速率)之無電鍍銅溶液。 Another goal is to provide an electroless copper solution with improved performance, such as improved copper deposition rate.
本發明之另一目標在於採用銅之生物可降解錯合劑的無電鍍銅溶液。 Another object of the invention is an electroless copper plating solution using a copper biodegradable complexing agent.
又一目標在於不含甲醛之鍍銅溶液必須實行甲醛無電銅浴之標準。其應適合應用於水平製程與垂直製程，其中最 終產品例如用於高端技術，如HDI(高密度互連)PCB及IC基板(IC=積體電路，PCB=印刷電路板)。該溶液亦應適於製造顯示器。 Another goal is that the copper-free solution containing formaldehyde must be subjected to the standard of formaldehyde-free copper bath. It should be suitable for horizontal and vertical processes, the most The final products are used, for example, for high-end technologies such as HDI (High Density Interconnect) PCBs and IC substrates (IC = integrated circuits, PCB = printed circuit boards). The solution should also be suitable for the manufacture of displays.
本發明提供一種無電鍍銅溶液，其包含- 銅離子來源，- 作為還原劑之乙醛酸來源，及- 至少一種聚胺基二丁二酸或至少一種聚胺基單丁二酸，或至少一種聚胺基二丁二酸與至少一種聚胺基單丁二酸之混合物作為錯合劑，其中錯合劑與銅離子之莫耳比在1.1：1至5：1之範圍內。 The present invention provides an electroless copper plating solution comprising - a source of copper ions, - a source of glyoxylic acid as a reducing agent, and - at least one polyaminodisuccinic acid or at least one polyamine monosuccinic acid, or at least A mixture of polyaminodisuccinic acid and at least one polyamine monosuccinic acid as a crosslinking agent, wherein the molar ratio of the complexing agent to the copper ion is in the range of 1.1:1 to 5:1.
一或多個上述目標係藉由如技術方案1之無電鍍銅溶液(下文縮寫為「溶液」)或藉由如從屬技術方案及說明書中所述之有利實施例來達成。 One or more of the above objects are achieved by an electroless copper solution (hereinafter abbreviated as "solution") as in claim 1 or by an advantageous embodiment as described in the dependent technical solutions and the specification.
如技術方案1之溶液不含甲醛且顯示改良之銅沈積速率。可達成0.15-1.0μm/10min、0.15-1.5μm/10min或甚至0.15-2.0μm/10min之沈積速率。 The solution of claim 1 contains no formaldehyde and exhibits a modified copper deposition rate. A deposition rate of 0.15-1.0 μm/10 min, 0.15-1.5 μm/10 min or even 0.15-2.0 μm/10 min can be achieved.
此新穎不含甲醛銅浴之優勢在於良好浴效能、浴穩定性、良好覆蓋性、高沈積速度及低起泡趨勢。重要浴組分甲醛以無毒還原劑替代。 The advantages of this novel formaldehyde-free copper bath are good bath performance, bath stability, good coverage, high deposition rate and low foaming tendency. The important bath component formaldehyde is replaced by a non-toxic reducing agent.
錯合劑聚胺基二丁二酸或聚胺基單丁二酸與銅離子之莫耳比產生電鍍溶液之有利性質，即氫氧化銅沈澱受抑制、浴穩定性及鍍銅製程中氣泡形成受抑制，如下文及工作實例中進一步解釋。 The molar ratio of the polyamine succinic acid or polyamine succinic acid to the copper ion produces a favorable property of the plating solution, that is, the precipitation of copper hydroxide is suppressed, the bath stability and the bubble formation in the copper plating process are affected. Inhibition, as further explained below and in the working examples.
在本發明之一個實施例中，乙醛酸與錯合劑之莫耳比為 <4.6：1。本發明中顯示，就例如覆蓋性、背光及鈍化而論，此莫耳比對銅沈積於基板上之品質具有有利影響。乙醛酸與錯合劑(特定言之為EDDS)之進一步有利莫耳比為4.5：1、4.2：1、4.0：1、3.8：1、3.6：1。乙醛酸與錯合劑(特定言之為EDDS)之莫耳比的較佳下限為0.45：1或0.7：1、1：1或2：1。因此，乙醛酸與錯合劑(特定言之為EDDS)之莫耳比的較佳範圍為0.45：1至4.5：1、0.45：1至4.2：1、0.45：1至4.0：1、0.45：1至3.8：1或0.45：1至3.6：1。其他較佳範圍為1：1至4.5：1、1：1至4.2：1、1：1至4.0：1、1：1至3.8：1或1：1至3.6：1。乙醛酸與錯合劑(特定言之為EDDS)之莫耳比的其他較佳範圍為2：1至4.5：1、2：1至4.2：1、2：1至4.0：1、2：1至3.8：1或2：1至3.6：1。該比率與錯合劑之莫耳濃度量有關，若使用一種以上錯合劑，則就此而論意謂錯合劑之總莫耳濃度量。乙醛酸之莫耳濃度較佳地至少高達溶液中銅之莫耳濃度，更佳地更高。因此，乙醛酸與Cu之莫耳比較佳1：1、較佳1.5：1、更佳2：1。 In one embodiment of the invention, the molar ratio of glyoxylic acid to the complexing agent is <4.6:1. It has been shown in the present invention that this molar ratio has a beneficial effect on the quality of copper deposition on the substrate, for example in terms of coverage, backlighting and passivation. Further favorable molar ratio of glyoxylic acid and a complexing agent (specifically, EDDS) 4.5:1 4.2:1 4.0:1 3.8:1 3.6:1. A preferred lower limit for the molar ratio of glyoxylic acid to the complexing agent (specifically EDDS) is 0.45:1 or 0.7:1, 1:1 or 2:1. Therefore, the molar ratio of the molar ratio of glyoxylic acid to the complexing agent (specifically, EDDS) is from 0.45:1 to 4.5:1, from 0.45:1 to 4.2:1, from 0.45:1 to 4.0:1, 0.45: 1 to 3.8:1 or 0.45:1 to 3.6:1. Other preferred ranges are from 1:1 to 4.5:1, 1:1 to 4.2:1, 1:1 to 4.0:1, 1:1 to 3.8:1 or 1:1 to 3.6:1. Other preferred ranges for the molar ratio of glyoxylic acid to the complexing agent (specifically EDDS) are from 2:1 to 4.5:1, from 2:1 to 4.2:1, from 2:1 to 4.0:1, from 2:1. To 3.8:1 or 2:1 to 3.6:1. This ratio is related to the amount of molar concentration of the complexing agent. If more than one complexing agent is used, then the total molar concentration of the wronging agent is used herein. The molar concentration of glyoxylic acid is preferably at least as high as the molar concentration of copper in the solution, and more preferably. Therefore, glyoxylic acid is better than Cu 1:1, better 1.5:1 is better 2:1.
聚胺基二丁二酸及聚胺基單丁二酸顯示極好或甚至高生物降解性。本發明之電鍍溶液不含乙二胺四乙酸(EDTA)、N'-(2-羥乙基)-乙二胺-N,N,N'-三乙酸(HEDTA)及肆(2-羥丙基)乙二胺。 Polyaminodisuccinic acid and polyamine monosuccinic acid show excellent or even high biodegradability. The electroplating solution of the present invention does not contain ethylenediaminetetraacetic acid (EDTA), N'-(2-hydroxyethyl)-ethylenediamine-N,N,N'-triacetic acid (HEDTA) and hydrazine (2-hydroxypropane). Ethylenediamine.
本發明之溶液及本發明之製程較佳用於塗佈印刷電路板、晶片載體及半導體晶圓或亦用於塗佈任何其他電路載體及互連裝置。該溶液特定言之用於印刷電路板及晶片載體，以及半導體晶圓，以將表面、溝槽、盲微通道、通孔 通道(通孔)及類似結構鍍銅。 The solutions of the present invention and the process of the present invention are preferably used to coat printed circuit boards, wafer carriers and semiconductor wafers or also to coat any other circuit carrier and interconnect device. The solution is specifically used for printed circuit boards and wafer carriers, as well as semiconductor wafers to surface, trench, blind microchannels, vias Channel (through hole) and similar structures are plated with copper.
特定言之，本發明之溶液或本發明之製程可用於在印刷電路板、晶片、載體、晶圓及各種其他互連裝置之表面上、溝槽、盲微通道、通孔通道及相當結構中沈積銅。如本發明中所用，術語「通孔通道」或「通孔」涵蓋所有種類之通孔通道且包括矽晶圓中之所謂「矽穿孔(through silicon via)」。 In particular, the solution of the present invention or the process of the present invention can be used on the surface of printed circuit boards, wafers, carriers, wafers, and various other interconnected devices, trenches, blind microchannels, via vias, and equivalent structures. Deposit copper. As used in this invention, the term "via" or "via" encompasses all types of via vias and includes so-called "through silicon vias" in germanium wafers.
對溶液設想之另一應用為顯示器應用之金屬化。就此而言，將銅特定言之沈積於玻璃基板上，特定言之於平板玻璃表面上。與至今使用之金屬濺鍍製程相比，玻璃基板上之濕式無電銅沈積為有利的。與濺鍍技術相比，可用濕式無電沈積達成之益處尤其在於內應力減小及玻璃基板彎曲減小、設備維護減少、金屬有效使用、材料廢料減少。此外，用本發明之溶液達成玻璃基板上的高銅沈積速率，尤其在用相對較少金屬晶種預處理之玻璃基板上。 Another application envisioned for solutions is the metallization of display applications. In this regard, copper is specifically deposited on a glass substrate, in particular on the surface of a flat glass. Wet electroless copper deposition on a glass substrate is advantageous compared to the metal sputtering processes used to date. The benefits that can be achieved with wet electroless deposition compared to sputtering techniques are, inter alia, reduced internal stress and reduced bending of the glass substrate, reduced equipment maintenance, efficient use of metals, and reduced material waste. Furthermore, the high copper deposition rate on the glass substrate is achieved with the solution of the invention, especially on glass substrates pretreated with relatively few metal seed crystals.
本發明之溶液為水溶液。術語「水溶液」意謂佔優勢之液體介質(其為溶液中之溶劑)為水。可添加其他可與水混溶的液體，例如醇及其他極性有機液體，其可與水混溶。 The solution of the invention is an aqueous solution. The term "aqueous solution" means that the predominant liquid medium, which is the solvent in solution, is water. Other water-miscible liquids such as alcohols and other polar organic liquids may be added which are miscible with water.
本發明之溶液可藉由將所有組分溶解於水性液體介質中，較佳於水中來製備。 The solution of the present invention can be prepared by dissolving all components in an aqueous liquid medium, preferably in water.
該溶液含有銅離子來源，其可例如為任何水溶性銅鹽。銅可例如且不限於以硫酸銅、氯化銅、硝酸銅、乙酸銅、甲烷磺酸銅((CH3O3S)2Cu)、氫氧化銅；或其水合物形式添加。 The solution contains a source of copper ions which may, for example, be any water soluble copper salt. Copper may be added, for example and without limitation, in the form of copper sulfate, copper chloride, copper nitrate, copper acetate, copper methane sulfonate ((CH 3 O 3 S) 2 Cu), copper hydroxide; or a hydrate thereof.
使用上述還原劑之無電銅浴較佳採用相對較高pH值，通常在11與14或12.5與14之間，較佳在12.5與13.5或12.8與13.3之間。pH值一般藉由氫氧化鉀(KOH)、氫氧化鈉(NaOH)、氫氧化鋰(LiOH)、氫氧化銨或氫氧化四甲銨(TMAH)來調節。因此，溶液可含有氫氧根離子來源，例如且不限於一或多種上文所列化合物。若需要溶液鹼性pH值且若pH值尚未藉由其他組分而處於鹼性範圍內，則例如添加氫氧化物來源。 The electroless copper bath using the above reducing agent preferably employs a relatively high pH, typically between 11 and 14 or between 12.5 and 14, preferably between 12.5 and 13.5 or between 12.8 and 13.3. The pH is generally adjusted by potassium hydroxide (KOH), sodium hydroxide (NaOH), lithium hydroxide (LiOH), ammonium hydroxide or tetramethylammonium hydroxide (TMAH). Thus, the solution may contain a source of hydroxide ions such as, but not limited to, one or more of the compounds listed above. If the alkaline pH of the solution is desired and if the pH is not in the alkaline range by other components, for example, a source of hydroxide is added.
因為乙二酸鉀之溶解性較高，所以尤其較佳為使用氫氧化鉀。藉由氧化用作還原劑之乙醛酸而在溶液中形成乙二酸根陰離子。 Since potassium oxalate has a high solubility, potassium hydroxide is particularly preferably used. An oxalate anion is formed in the solution by oxidizing glyoxylic acid used as a reducing agent.
乙醛酸為用於將銅離子還原為元素銅之還原劑。如本文所用，術語「乙醛酸」包括未解離乙醛酸以及乙醛酸根離子。在溶液中，可存在未解離乙醛酸及乙醛酸根離子。所存在之物質(酸或鹽)之確切性質將視溶液pH值而定。相同考慮適用於其他弱酸及弱鹼。 Glyoxylic acid is a reducing agent for reducing copper ions to elemental copper. As used herein, the term "glyoxylic acid" includes undissociated glyoxylic acid and glyoxylate ions. In solution, undissociated glyoxylic acid and glyoxylate ions may be present. The exact nature of the substance (acid or salt) present will depend on the pH of the solution. The same considerations apply to other weak acids and weak bases.
術語「乙醛酸來源」涵蓋乙醛酸及所有可在水溶液中轉化為乙醛酸之化合物。在水溶液中，含醛之酸係與其水合物平衡。乙醛酸之適合來源為二鹵乙酸，諸如二氯乙酸，其將在水性介質中水解為乙醛酸水合物。乙醛酸之替代性來源為亞硫酸氫鹽加合物，如為可水解酯或其他酸衍生物。亞硫酸氫鹽加合物可添加至組合物中或當場形成。亞硫酸氫鹽加合物可由乙醛酸鹽及亞硫酸氫鹽、亞硫酸鹽或偏亞硫酸氫鹽製得。 The term "glyoxylic acid source" encompasses glyoxylic acid and all compounds which can be converted to glyoxylic acid in aqueous solution. In aqueous solution, the aldehyde-containing acid is in equilibrium with its hydrate. A suitable source of glyoxylic acid is dihaloacetic acid, such as dichloroacetic acid, which will hydrolyze to glyoxylate hydrate in an aqueous medium. An alternative source of glyoxylic acid is a bisulfite adduct such as a hydrolyzable ester or other acid derivative. The bisulfite adduct can be added to the composition or formed on the spot. The bisulfite adduct can be prepared from glyoxylate and bisulfite, sulfite or metabisulfite.
必要時可添加一或多種其他還原劑，例如低磷酸、乙醇酸或甲酸，或上述酸之鹽。然而，本發明之溶液不含甲醛。因此，該溶液不含甲醛。其他還原劑較佳為充當還原劑，但不能作為唯一還原劑使用之試劑(參看US 7,220,296第4欄第20-43行及第54-62行)。在此意義上，另一還原劑亦稱為「增強劑」。 One or more other reducing agents may be added as necessary, such as low phosphoric acid, glycolic acid or formic acid, or salts of the above acids. However, the solution of the invention does not contain formaldehyde. Therefore, the solution does not contain formaldehyde. Other reducing agents are preferably used as reducing agents, but not as the sole reducing agent (see US 7,220,296, column 4, lines 20-43 and lines 54-62). In this sense, another reducing agent is also referred to as a "enhancer."
聚胺基二丁二酸為具有兩個或兩個以上氮原子之化合物，其中2個氮鍵結於丁二酸(或鹽)基團，較佳僅兩個氮原子各自連接有一個丁二酸(或鹽)基團。如本文所用，術語丁二酸包括其鹽。該化合物具有至少2個氮原子，且由於胺之商業可獲得性，較佳具有不超過約10個氮原子，更佳不超過約6個、最佳2個氮原子。未連接有丁二酸部分的氮原子最佳經氫原子取代。丁二酸基團更佳係在末端氮原子上，最佳地，該等氮各自亦具有氫取代基。末端意謂存在於化合物中之第一個或最後一個氮原子，而不論其他取代基為何。末端氮之另一定義為在連接丁二酸部分之前的一級胺氮。在連接丁二酸部分之後，末端氮轉移至二級胺氮。因為一個氮上之兩個丁二酸基團之位阻，所以具有丁二酸基團之各氮較佳僅具有一個此基團。具有丁二酸基團之氮上之其餘鍵較佳由氫或烷基或伸烷基(直鏈、分支鏈或環狀，包括接合一個以上氮原子或單個氮原子之一個以上鍵的環狀結構，較佳為直鏈)或具有醚或硫醚鍵聯之此等基團(均較佳具有1至10個碳原子、更佳1至6個、最佳1至3個碳原子，但最佳為氫)填補。較佳烷基為甲基、乙基 及丙基。氮原子更佳由伸烷基鍵聯，該等伸烷基較佳各自具有2至12個碳原子、更佳2至10個碳原子、甚至更佳2至8個、最佳2至6個碳原子，亦即為伸乙基、伸丙基、伸丁基、伸戊基或伸己基。聚胺基二丁二酸化合物較佳具有至少約10個碳原子且較佳具有至多約50個、更佳至多約40個、最佳至多約30個碳原子。術語「丁二酸」在本文中係用於酸及其鹽；鹽包括金屬陽離子(例如鉀、鈉)及銨或胺鹽。 Polyaminodisuccinic acid is a compound having two or more nitrogen atoms, wherein two nitrogens are bonded to a succinic acid (or salt) group, preferably only two nitrogen atoms are each bonded to a dibutyl group. Acid (or salt) group. The term succinic acid, as used herein, includes salts thereof. The compound has at least 2 nitrogen atoms and preferably has no more than about 10 nitrogen atoms, more preferably no more than about 6, most preferably 2 nitrogen atoms due to the commercial availability of the amine. The nitrogen atom to which the succinic acid moiety is not attached is preferably substituted with a hydrogen atom. More preferably, the succinic acid group is attached to the terminal nitrogen atom. Most preferably, each of the nitrogens also has a hydrogen substituent. The end means the first or last nitrogen atom present in the compound, regardless of the other substituents. Another definition of terminal nitrogen is the primary amine nitrogen prior to attachment of the succinic acid moiety. After the attachment of the succinic acid moiety, the terminal nitrogen is transferred to the secondary amine nitrogen. Because of the steric hindrance of the two succinic acid groups on a nitrogen, each nitrogen having a succinic acid group preferably has only one such group. The remaining bonds on the nitrogen having a succinic acid group are preferably hydrogen or an alkyl group or an alkyl group (linear, branched or cyclic, including a ring in which one or more nitrogen atoms or one or more bonds of a single nitrogen atom are bonded). a structure, preferably a straight chain) or such a group having an ether or a thioether linkage (all preferably having from 1 to 10 carbon atoms, more preferably from 1 to 6, most preferably from 1 to 3 carbon atoms, but The best for hydrogen) is filled. Preferred alkyl groups are methyl or ethyl And propyl. More preferably, the nitrogen atom is bonded to an alkyl group, and each of the alkyl groups preferably has 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, even more preferably 2 to 8, most preferably 2 to 6 carbons. Atom, that is, an ethyl group, a propyl group, a butyl group, a pentyl group or a hexyl group. The polyaminodisuccinic acid compound preferably has at least about 10 carbon atoms and preferably has up to about 50, more preferably up to about 40, and most preferably up to about 30 carbon atoms. The term "succinic acid" is used herein for acids and their salts; salts include metal cations (eg, potassium, sodium) and ammonium or amine salts.
適用於實踐本發明之聚胺基二丁二酸為未經取代(較佳地)或經惰性取代，亦即經不會不良地干擾所選應用中聚胺基二丁二酸之活性的基團取代。此等惰性取代基包括烷基(較佳具有1至6個碳原子)；芳基，包括芳基烷基及烷基芳基(較佳具有6至12個碳原子)，其中烷基為較佳且烷基中甲基及乙基為較佳。 The polyaminodisuccinic acid suitable for use in the practice of the invention is unsubstituted (preferably) or inertly substituted, i.e., a group which does not adversely interfere with the activity of the polyaminodisuccinic acid in the selected application. Replaced by the regiment. Such inert substituents include alkyl groups (preferably having from 1 to 6 carbon atoms); aryl groups, including arylalkyl groups and alkylaryl groups (preferably having from 6 to 12 carbon atoms), wherein the alkyl group is Preferably, the methyl group and the ethyl group in the alkyl group are preferred.
惰性取代基宜在分子之任何部分上，較佳在碳原子上，更佳在伸烷基(例如在氮原子之間或在羧酸基團之間的伸烷基)上，最佳在氮基團之間的伸烷基上。 The inert substituent is preferably on any part of the molecule, preferably on a carbon atom, more preferably on an alkyl group (for example, an alkyl group between nitrogen atoms or between carboxylic acid groups), most preferably nitrogen. The alkyl group is between the groups.
較佳之聚胺基二丁二酸包括乙二胺-N,N'-二丁二酸(EDDS)、二伸乙基三胺-N,N"-二丁二酸、三伸乙基四胺-N,N"'-二丁二酸、1,6己二胺N,N'-二丁二酸、四伸乙基五胺-N,N""-二丁二酸、2-羥基伸丙基-1,3-二胺-N,N'-二丁二酸、1,2丙二胺-N,N'-二丁二酸、1,3-丙二胺-N,N"-二丁二酸、順式環己烷二胺-N,N'-二丁二酸、反式環己烷二胺-N,N'-二丁二酸及伸乙基雙(氧基伸乙基氮基)-N,N'-二丁二 酸。較佳之聚胺基二丁二酸為乙二胺-N,N'-二丁二酸。 Preferred polyaminodisuccinic acids include ethylenediamine-N,N'-disuccinic acid (EDDS), di-ethyltriamine-N,N"-disuccinic acid, tri-ethylidene tetramine -N,N"'-disuccinic acid, 1,6-hexanediamine N,N'-disuccinic acid, tetra-extension ethylpentamine-N,N""-disuccinic acid, 2-hydroxyl extension Propyl-1,3-diamine-N,N'-disuccinic acid, 1,2 propanediamine-N,N'-disuccinic acid, 1,3-propanediamine-N,N"- Succinic acid, cis-cyclohexanediamine-N,N'-disuccinic acid, trans-cyclohexanediamine-N,N'-disuccinic acid and ethyl bis(oxyethyl) Nitro)-N,N'-dibutyl acid. A preferred polyaminodisuccinic acid is ethylenediamine-N,N'-disuccinic acid.
此等聚胺基二丁二酸可例如藉由Kezerian等人於U.S.專利3,158,635(以全文引用的方式併入本文中)中揭示之製程製備。Kezerian等人揭示使順丁烯二酸酐(或酯或鹽)與對應於所需聚胺基二丁二酸之多元胺在鹼性條件下反應。該反應得到許多光學異構體，例如因為乙二胺二丁二酸中存在兩個不對稱碳原子，所以乙二胺與順丁烯二酸酐之反應得到三種光學異構體[R,R]、[S,S]及[S,R]乙二胺二丁二酸(EDDS)之混合物。此等混合物係以混合物形式使用，或者藉由目前先進技術內的手段分離以獲得所需異構體。或者，[S,S]異構體係藉由諸如L-天冬胺酸之酸與諸如1,2-二溴乙烷之化合物反應來製備，如Neal及Rose,「Stereospecific Ligands and Their Complexes of Ethylenediaminedisuccinic Acid」,Inorganic Chemistry，第7卷，(1968)，第2405-2412頁所述。 Such polyamine succinic acid can be prepared, for example, by the process disclosed in U.S. Patent No. 3,158,635, the entire disclosure of which is incorporated herein by reference. Kezerian et al. disclose the reaction of maleic anhydride (or ester or salt) with a polyamine corresponding to the desired polyaminodisuccinic acid under basic conditions. The reaction yields a plurality of optical isomers, for example, because of the presence of two asymmetric carbon atoms in ethylenediamine disuccinic acid, the reaction of ethylenediamine with maleic anhydride yields three optical isomers [R, R] , a mixture of [S, S] and [S, R] ethylenediamine disuccinic acid (EDDS). These mixtures are used in the form of a mixture or separated by means within the current state of the art to obtain the desired isomer. Alternatively, the [S,S] isomerized system is prepared by reacting an acid such as L-aspartic acid with a compound such as 1,2-dibromoethane, such as Neal and Rose, "Stereospecific Ligands and Their Complexes of Ethylenediaminedisuccinic Acid, Inorganic Chemistry, Vol. 7, (1968), pp. 2405-2412.
聚胺基單丁二酸為具有至少兩個氮原子且丁二酸(或鹽)部分連接於一個氮原子之化合物。該化合物較佳具有至少2個氮原子且由於胺之商業可獲得性，較佳具有不超過約10個氮原子、更佳不超過約6個，最佳2個氮原子。其餘氮原子(即未連接有丁二酸部分之氮原子)較佳經氫原子取代。儘管丁二酸部分可連接於任何胺，但丁二酸基團較佳連接於末端氮原子。末端意謂化合物中存在之第一個或最後一個胺，而不論其他取代基如何。末端氮之另一定義為一級胺氮，隨後連接丁二酸部分。在連接丁二酸部分之 後，末端氮轉移至二級胺氮。具有丁二酸基團之氮上之其餘鍵較佳由氫或烷基或伸烷基(直鏈、分支鏈或環狀，包括接合一個以上氮原子或單個氮原子之一個以上鍵的環狀結構，較佳為直鏈)或具有醚或硫醚鍵聯之此等基團(均較佳具有1至10個碳原子、更佳1至6個、最佳1至3個碳原子，但最佳為氫)填充。較佳烷基為甲基、乙基及丙基。氮原子一般由伸烷基鍵聯，該等伸烷基各自具有2至12個碳原子、較佳2至10個碳原子、更佳2至8個且最佳2至6個碳原子，亦即為伸乙基、伸丙基、伸丁基、伸戊基或伸己基。聚胺基單丁二酸化合物較佳具有至少約6個碳原子且較佳具有至多約50個、更佳至多約40個且最佳至多約30個碳原子。適用於實踐本發明之聚胺基單丁二酸為未經取代(較佳地)或如上文關於聚胺基二丁二酸化合物所述經惰性取代。 Polyaminomonosuccinic acid is a compound having at least two nitrogen atoms and a succinic acid (or salt) moiety attached to a nitrogen atom. Preferably, the compound has at least 2 nitrogen atoms and preferably has no more than about 10 nitrogen atoms, more preferably no more than about 6, and most preferably 2 nitrogen atoms due to the commercial availability of the amine. The remaining nitrogen atom (i.e., the nitrogen atom to which the succinic acid moiety is not attached) is preferably substituted with a hydrogen atom. Although the succinic acid moiety can be attached to any amine, the succinic acid group is preferably attached to the terminal nitrogen atom. The terminus means the first or last amine present in the compound, regardless of the other substituents. Another definition of terminal nitrogen is the primary amine nitrogen followed by the attachment of the succinic acid moiety. In the connection of the succinic acid moiety After that, the terminal nitrogen is transferred to the secondary amine nitrogen. The remaining bonds on the nitrogen having a succinic acid group are preferably hydrogen or an alkyl group or an alkyl group (linear, branched or cyclic, including a ring in which one or more nitrogen atoms or one or more bonds of a single nitrogen atom are bonded). a structure, preferably a straight chain) or such a group having an ether or a thioether linkage (all preferably having from 1 to 10 carbon atoms, more preferably from 1 to 6, most preferably from 1 to 3 carbon atoms, but Best for hydrogen) filling. Preferred alkyl groups are methyl, ethyl and propyl. The nitrogen atom is generally bonded by an alkylene group each having 2 to 12 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 2 to 8 and most preferably 2 to 6 carbon atoms, that is, It is an ethyl group, a propyl group, a butyl group, a pentyl group or a hexyl group. The polyamine monosuccinic acid compound preferably has at least about 6 carbon atoms and preferably has up to about 50, more preferably up to about 40 and most preferably up to about 30 carbon atoms. The polyamine-based monosuccinic acid suitable for use in the practice of the invention is unsubstituted (preferably) or inertly substituted as described above for the polyaminobisduccinic acid compound.
較佳之聚胺基單丁二酸包括乙二胺單丁二酸、二伸乙基三胺單丁二酸、三伸乙基四胺單丁二酸、1,6-己二胺單丁二酸、四伸乙基五胺單丁二酸、2羥基伸丙基-1,3-二胺單丁二酸、1,2-丙二胺單丁二酸、1,3-丙二胺單丁二酸、順式環己烷二胺單丁二酸、反式環己烷二胺單丁二酸及伸乙基雙(氧基伸乙基氮基)單丁二酸。較佳之聚胺基單丁二酸為乙二胺單丁二酸。 Preferred polyamine-based mono-succinic acid includes ethylenediamine monosuccinic acid, di-extension ethyltriamine monosuccinic acid, tri-extension ethyltetraamine monosuccinic acid, 1,6-hexanediamine monobutane Acid, tetra-extension ethyl pentamine mono-succinic acid, 2-hydroxy-propyl-1,3-diamine monosuccinic acid, 1,2-propylenediamine monosuccinic acid, 1,3-propanediamine Succinic acid, cis-cyclohexanediamine monosuccinic acid, trans-cyclohexanediamine monosuccinic acid, and ethyl bis(oxyethylidene)-succinic acid. A preferred polyamine monosuccinic acid is ethylenediamine monobutyric acid.
此等聚胺基單丁二酸可例如藉由Bersworth等人於U.S.專利2,761,874(其揭示內容以引用的方式併入本文中)中及如Jpn.Kokai Tokkyo Koho JP 57,116,031中揭示之製程來製 備。一般而言，Bersworth等人揭示使在溫和條件下之伸烷基二胺及二伸烷基三胺與在溫和條件下(於醇)中之順丁烯二酸酯反應，得到N-烷基取代之天冬胺酸的胺基衍生物。該反應得到R異構體與S異構體之混合物。 Such polyamine-based succinic acid can be prepared, for example, by the process disclosed in Bersworth et al., U.S. Patent No. 2,761,874, the disclosure of which is incorporated herein by reference in Ready. In general, Bersworth et al. disclose the reaction of alkylenediamines and dialkyltriamines under mild conditions with maleic acid esters under mild conditions (in alcohols) to give N-alkyl groups. Substituted amino derivative of aspartic acid. This reaction gives a mixture of the R isomer and the S isomer.
在一個實施例中，當溶液含有聚胺基二丁二酸與聚胺基單丁二酸之混合物時，聚胺基二丁二酸與聚胺基單丁二酸之聚胺基取代基較佳相同。因此舉例而言，若聚胺基二丁二酸為乙二胺-N,N'-二丁二酸，則多元胺單丁二酸為乙二胺單丁二酸。 In one embodiment, when the solution contains a mixture of polyaminodisuccinic acid and polyamine monosuccinic acid, the polyamino substituent of polyaminodisuccinic acid and polyamine monosuccinic acid is more The same is true. Thus, for example, if the polyaminodisuccinic acid is ethylenediamine-N,N'-disuccinic acid, the polyamine monosuccinic acid is ethylenediamine monobutyric acid.
在一較佳實施例中，將乙二胺-N,N'-二丁二酸(EDDS)用作錯合劑。EDDS因為其高生物降解性而為較佳錯合劑。含生物可降解錯合劑(如酒石酸鹽)之其他無電銅浴通常使用毒性共金屬鎳。已發現可在本發明中避免毒性共金屬。因此，本發明之溶液不含毒性共金屬。本發明之溶液較佳無鎳。 In a preferred embodiment, ethylenediamine-N,N'-disuccinic acid (EDDS) is used as a blocking agent. EDDS is a preferred binder because of its high biodegradability. Other electroless copper baths containing biodegradable complexing agents such as tartrate typically use toxic co-metal nickel. It has been found that toxic co-metals can be avoided in the present invention. Thus, the solution of the invention is free of toxic co-metals. The solution of the invention is preferably nickel free.
本發明之發明者已發現在包含乙醛酸及EDDS之本發明溶液中獲得顯著改良之銅沈積速率。因為在採用甲醛之比較實例中，當將甲醛-EDDS組合與甲醛-EDTA相比時，銅沈積未改良或僅稍有改良，所以此為出乎意料的結果。 The inventors of the present invention have found that a significantly improved copper deposition rate is obtained in the inventive solution comprising glyoxylic acid and EDDS. This is an unexpected result because in the comparative example using formaldehyde, the copper deposition was not improved or only slightly improved when the formaldehyde-EDDS combination was compared with formaldehyde-EDTA.
術語「EDDS」包括外消旋EDDS或其所有光學活性異構體，諸如(S,S)-EDDS，及其鹽及衍生物。該術語較佳意謂(S,S)-EDDS或其鹽。EDDS可藉由PCT/GB94/02397之製程來製備。在溶液中，視溶液pH值而定，可存在乙二胺二丁二酸及乙二胺二丁二酸根離子。 The term "EDDS" includes racemic EDDS or all optically active isomers thereof, such as (S,S)-EDDS, and salts and derivatives thereof. The term preferably means (S,S)-EDDS or a salt thereof. EDDS can be prepared by the process of PCT/GB94/02397. In solution, depending on the pH of the solution, ethylenediamine disuccinic acid and ethylenediamine disuccinate ions may be present.
在一個實施例中，本發明之溶液含有以下濃度之銅離子、錯合劑(較佳為EDDS)及乙醛酸： In one embodiment, the solution of the invention contains copper ions, a complexing agent (preferably EDDS) and glyoxylic acid in the following concentrations:
Cu離子：1-5 g/l 對應於 0.016-0.079 mol/l Cu ion: 1-5 g/l corresponds to 0.016-0.079 mol/l
錯合劑：5-50 g/l 對應於 0.034-0.171 mol/l Mixing agent: 5-50 g/l corresponds to 0.034-0.171 mol/l
乙醛酸：2-20 g/l 對應於 0.027-0.270 mol/l Glyoxylic acid: 2-20 g/l corresponds to 0.027-0.270 mol/l
本發明之溶液更佳含有以下濃度之銅離子、錯合劑(較佳為EDDS)及乙醛酸： The solution of the present invention more preferably contains copper ions, a complexing agent (preferably EDDS) and glyoxylic acid in the following concentrations:
Cu離子：2-3 g/l 對應於 0.031-0.047 mol/l Cu ion: 2-3 g/l corresponds to 0.031-0.047 mol/l
錯合劑：20-40 g/l 對應於 0.068-0.137 mol/l Mismatch agent: 20-40 g/l corresponds to 0.068-0.137 mol/l
乙醛酸：2-20 g/l 對應於 0.027-0.270 mol/l Glyoxylic acid: 2-20 g/l corresponds to 0.027-0.270 mol/l
在本發明中，錯合劑(就此而論意謂錯合劑總量，亦即若使用一種以上錯合劑，則為所有錯合劑之莫耳數之和)與銅離子之莫耳比處於1.1：1至5：1，更佳1.5：1至5：1之範圍內。已顯示當使用此莫耳比時，亦即當錯合劑(特定言之為EDDS)以相對於銅過量之莫耳濃度使用時，本發明之溶液具有較佳效能。在本發明中，當將乙醛酸用作還原劑時，顯示錯合劑(特定言之為EDDS)與銅至少1.1：1之莫耳比為錯合銅離子所必需。莫耳比<1：1引起氫氧化銅沈澱且可能未發生鍍銅。另一方面，>5：1之莫耳比會在鍍銅製程中引起浴不穩定性及在基板表面上之高氣泡形成。 In the present invention, the amount of the wrong agent (in this case, the total amount of the wrong agent, that is, the sum of the molar numbers of all the wrong agents if one or more of the complexing agents are used) and the molar ratio of the copper ions are at 1.1:1. Up to 5:1, better in the range of 1.5:1 to 5:1. It has been shown that the solution of the present invention has a better performance when this molar ratio is used, i.e., when a miscible agent (specifically, EDDS) is used in excess of the molar concentration of copper. In the present invention, when glyoxylic acid is used as the reducing agent, it is necessary to exhibit a mismatching agent (specifically, EDDS) and a molar ratio of at least 1.1:1 of copper to the copper ion. A molar ratio of <1:1 causes copper hydroxide to precipitate and copper plating may not occur. On the other hand, a molar ratio of >5:1 causes bath instability and high bubble formation on the substrate surface during the copper plating process.
在另一實施例中，錯合劑(就此而論意謂錯合劑總量)與銅離子之莫耳比為2：1至5：1，更佳為3：1至5：1。若在沈積期間攪動銅浴，較佳用空氣攪動，且當除乙醛酸外亦使用另一還原劑(亦稱為「增強劑」)時，其中該另一還原劑較 佳選自乙醇酸、低磷酸或甲酸，最佳為乙醇酸，則此實施例為尤其有利的。 In another embodiment, the molar ratio of the cross-linking agent (in this case, the total amount of the cross-linking agent) to the copper ion is from 2:1 to 5:1, more preferably from 3:1 to 5:1. If the copper bath is agitated during deposition, it is preferably agitated with air, and when another reducing agent (also referred to as "enhancer") is used in addition to glyoxylic acid, the other reducing agent is more This embodiment is particularly advantageous since it is preferably selected from the group consisting of glycolic acid, low phosphoric acid or formic acid, most preferably glycolic acid.
本發明之溶液可包含且不一定包含其他組分，例如穩定劑、界面活性劑、添加劑(作為速率控制添加劑)、晶粒微化添加劑、pH值緩衝劑、pH值調節劑及增強劑。此等其他組分例如描述於以下文件(以全文引用的方式併入)中：US 4,617,205(特定言之為第6欄第17行至第7欄第25行之揭示內容)、US 7,220,296(特定言之為第4欄第63行至第6欄第26行)、US 2008/0223253(特定言之參看段落0033及0038)。 The solution of the present invention may and need not include other components such as stabilizers, surfactants, additives (as rate controlling additives), grain micronization additives, pH buffers, pH adjusters, and enhancers. Such other components are described, for example, in the following documents (incorporated by reference in their entirety): US 4, 617, 205 (specifically, the disclosure of column 6, line 17 to column 7, line 25), US 7,220,296 (specific It is referred to as column 4, line 63 to column 6, line 26), US 2008/0223253 (see paragraphs 0033 and 0038 for specific words).
穩定劑為針對本體溶液中不期望之外鍍(outplating)來穩定化無電電鍍溶液之化合物。術語「外鍍」意謂非特定及/或不受控制之銅沈積。銅(II)還原應僅在所需基板表面上發生而非在整個浴中不特定。穩定化功能可例如藉由充當催化劑毒物之物質(例如含有硫或其他硫族化物之化合物)或藉由形成銅(I)錯合物、由此抑制形成氧化銅(I)之化合物來實現。 The stabilizer is a compound that stabilizes the electroless plating solution against undesired outplating in the bulk solution. The term "external plating" means non-specific and/or uncontrolled copper deposition. Copper (II) reduction should occur only on the surface of the desired substrate and not in the entire bath. The stabilizing function can be achieved, for example, by a substance that acts as a catalyst poison (for example, a compound containing sulfur or other chalcogenide) or by forming a copper (I) complex, thereby inhibiting the formation of a compound of copper (I) oxide.
適合穩定劑為(不限於)聯吡啶基(2,2'-聯吡啶基、4,4'聯吡啶基)、啡啉、巰基-苯并噻唑、硫脲或其衍生物(如二乙基硫脲)、氰化物(如NaCN、KCN、K4[Fe(CN)6])、硫氰酸鹽、碘化物、乙醇胺、巰基-苯并***、Na2S2O3、聚合物(如聚丙烯醯胺、聚丙烯酸酯、聚乙二醇或聚丙二醇及其共聚物)，其中2,2'-聯吡啶基(縮寫為「DP」)、二乙基-硫脲、K4[Fe(CN)6]、NaCN及巰基-苯并噻唑為尤其適合的。 Suitable stabilizers are (not limited to) bipyridyl (2,2'-bipyridyl, 4,4'bipyridyl), phenanthroline, decyl-benzothiazole, thiourea or derivatives thereof (eg diethyl Thiourea), cyanide (such as NaCN, KCN, K 4 [Fe(CN) 6 ]), thiocyanate, iodide, ethanolamine, mercapto-benzotriazole, Na 2 S 2 O 3 , polymer ( Such as polyacrylamide, polyacrylate, polyethylene glycol or polypropylene glycol and copolymers thereof, of which 2,2'-bipyridyl (abbreviated as "DP"), diethyl-thiourea, K 4 [ Fe(CN) 6 ], NaCN and mercapto-benzothiazole are particularly suitable.
在一個實施例中，主要由於環境及職業健康原因，穩定劑係選自無氰化物之穩定劑。因此，本發明之溶液較佳無氰化物。就此而論，2,2'-聯吡啶基為較佳穩定劑。聯吡啶基較佳以1-10 mg/l之量添加。 In one embodiment, the stabilizer is selected from the group consisting of cyanide-free stabilizers, primarily for environmental and occupational health reasons. Therefore, the solution of the present invention is preferably free of cyanide. In this connection, 2,2'-bipyridyl is a preferred stabilizer. The bipyridyl group is preferably added in an amount of from 1 to 10 mg/l.
歐洲申請案EP1876262揭示一種無電銅浴，其含有一或多種硫代羧酸作為必需組分。EP1876262中提及之硫代化合物包括具有式HS-(CX1)r-(CHX2)s-COOH之化合物，其中X1為-H或-COOH；X2為-H或-SH；r及s為正整數，其中r為0至2，或0或1；且s為1或2。EP1876262中提及之硫代化合物的特定實例為硫代乙醇酸、硫代丙酸、硫代蘋果酸及二硫代二丁二酸。根據EP1876262，此等硫代羧酸與乙醛酸及其鹽可相容且藉由防止形成氧化銅來穩定化無電銅組合物。根據EP1876262，硫代化合物之必需最少量為0.01 ppm。在本發明中，顯示當EP1876262中一般地及特定地提及之硫代羧酸組分免於使用或至少低於EP1876262中提及之限度時，無電銅浴之效能較佳。可存在痕量的如EP1876262中一般地及特定地提及之硫代羧酸，前提為該量低於0.01 ppm。然而，較佳不將硫代羧酸添加至本發明之溶液中，亦即該浴不含有EP1876262中一般地及特定地提及之任何硫代羧酸。 European application EP 1816262 discloses an electroless copper bath containing one or more thiocarboxylic acids as an essential component. The thio compounds mentioned in EP 1 876 262 include compounds having the formula HS-(CX1)r-(CHX2)s-COOH, wherein X1 is -H or -COOH; X2 is -H or -SH; r and s are positive integers Where r is 0 to 2, or 0 or 1; and s is 1 or 2. Specific examples of thio compounds mentioned in EP1876262 are thioglycolic acid, thiopropionic acid, thiomalic acid and dithiodisuccinic acid. According to EP1876262, these thiocarboxylic acids are compatible with glyoxylic acid and its salts and stabilize the electroless copper composition by preventing the formation of copper oxide. According to EP1876262, the minimum necessary amount of thio compounds is 0.01 ppm. In the present invention, it is shown that the efficacy of the electroless copper bath is better when the thiocarboxylic acid component generally and specifically mentioned in EP1876262 is exempt from use or at least below the limits mentioned in EP1876262. Trace amounts of thiocarboxylic acids, as generally and specifically mentioned in EP1876262, may be present, provided that the amount is less than 0.01 ppm. Preferably, however, no thiocarboxylic acid is added to the solution of the invention, i.e., the bath does not contain any of the thiocarboxylic acids generally and specifically mentioned in EP1876262.
在另一態樣中，本發明係關於一種無電鍍銅製程，該製程包含使基板與如上所述之無電鍍銅溶液接觸。 In another aspect, the invention is directed to an electroless copper process comprising contacting a substrate with an electroless copper solution as described above.
舉例而言，基板可浸漬或浸沒於本發明之溶液中。在該製程中，可將基板之整個表面或僅所選部分鍍銅。 For example, the substrate can be impregnated or immersed in the solution of the invention. In this process, the entire surface of the substrate or only selected portions may be plated with copper.
較佳在使用期間攪動溶液。特定言之，可使用工作攪動及/或溶液攪動。較佳攪動種類為溶液之空氣攪動。空氣攪動可藉由將空氣鼓泡通過使用中之溶液來達成。 Preferably, the solution is agitated during use. In particular, working agitation and/or solution agitation can be used. The preferred agitation type is air agitation of the solution. Air agitation can be achieved by bubbling air through the solution in use.
該製程將進行一段充足時間以得到所需厚度之沈積物，所需厚度又將視特定應用而定。 The process will be carried out for a sufficient period of time to obtain a deposit of the desired thickness, which in turn will depend on the particular application.
所設想之本發明之一個應用將尤其適用於製備印刷電路板。根據本發明製程之無電銅沈積尤其可用於穿鍍(through-plating)印刷電路板中之孔、表面、溝槽、盲微通道。雙側或多層板(剛性或可撓性的)可藉助於本發明來電鍍。 One application of the invention envisaged will be particularly suitable for the preparation of printed circuit boards. Electroless copper deposition in accordance with the process of the present invention is particularly useful for through-plating holes, surfaces, trenches, blind microchannels in printed circuit boards. Double or multi-layer sheets (rigid or flexible) can be electroplated by means of the invention.
本發明之製程可適用於提供厚度在0.1 μm至25 μm之範圍內，較佳在0.25 μm與3 μm之間的無電銅沈積物。 The process of the present invention can be adapted to provide electroless copper deposits having a thickness in the range of from 0.1 μm to 25 μm, preferably between 0.25 μm and 3 μm.
一般用於印刷電路板製造之基板最經常為環氧樹脂或環氧玻璃複合物。但可使用其他物質，特別為酚醛樹脂、聚四氟乙烯(PTFE)、聚醯亞胺、聚苯醚、雙順丁烯二酸三嗪-樹脂(BT樹脂)、氰酸酯及聚碸。 Substrates commonly used in the manufacture of printed circuit boards are most often epoxy or epoxy glass composites. However, other substances can be used, in particular phenolic resin, polytetrafluoroethylene (PTFE), polyimide, polyphenylene ether, bis-maleic acid triazine-resin (BT resin), cyanate ester and polyfluorene.
除在印刷電路板製造中應用該製程外，亦可發現該製程一般適用於電鍍非導電性基板，包括塑膠，諸如丙烯腈丁二烯苯乙烯(ABS)及聚碳酸酯；陶瓷及玻璃。 In addition to the application of this process in the manufacture of printed circuit boards, the process is generally found to be suitable for electroplating non-conductive substrates, including plastics such as acrylonitrile butadiene styrene (ABS) and polycarbonate; ceramics and glass.
在本發明製程之一個實施例中，該製程係在20-60℃、較佳20-55℃、更佳20-50℃、甚至更佳20-45℃且最佳20-40℃範圍內之溫度下進行。因為使用目前先進技術之基於甲醛之溶液，對於良好電鍍效能，尤其對於足夠銅沈積速率，必需有較高溫度，所以此實施例極為有利。 In one embodiment of the process of the present invention, the process is in the range of 20-60 ° C, preferably 20-55 ° C, more preferably 20-50 ° C, even more preferably 20-45 ° C and most preferably 20-40 ° C. Perform at temperature. This embodiment is extremely advantageous because of the use of formaldehyde-based solutions of the current state of the art, which are necessary for good plating performance, especially for sufficient copper deposition rates.
欲鍍銅之基板，亦即基板表面，尤其係非金屬表面，可藉由此項技術之技能範圍內的手段來預處理(例如US 4,617,205第8欄中所述)，以使其針對銅沈積具有更高可接受性或自催化性。表面之全部或所選部分可經預處理。然而，並非在每一情況下均必需預處理且視基板及表面之種類而定。在預處理中，可能敏化基板，隨後在其上沈積無電銅。此舉可藉由使催化金屬(諸如貴金屬，例如鈀)吸附於基板表面上來達成。 The substrate to be plated, i.e., the surface of the substrate, especially the non-metallic surface, may be pretreated by means within the skill of the art (e.g., as described in column 8 of US 4,617,205) for copper deposition. Higher acceptability or autocatalytic. All or selected portions of the surface may be pretreated. However, it is not necessary to pretreat in each case and depending on the type of substrate and surface. In the pretreatment, the substrate may be sensitized, followed by deposition of electroless copper thereon. This can be achieved by adsorbing a catalytic metal such as a noble metal such as palladium on the surface of the substrate.
預處理製程主要視參數(如基板、所需應用及銅表面之所需性質)而定。 The pretreatment process is primarily dependent on parameters such as the substrate, the desired application, and the desired properties of the copper surface.
尤其用於印刷電路板層壓物及其他適合基板之例示性及非限制性預處理製程可包含以下步驟：a)使基板與活化劑溶液接觸，該溶液含有膠態或離子催化金屬，諸如貴金屬，較佳為鈀，使得基板表面變得具催化性，及視情況，尤其若活化劑含有離子催化金屬，則b)使基板與還原劑接觸，其中離子活化劑之金屬離子經還原為元素金屬，或若活化劑含有膠態催化金屬，則c)使基板與加速劑接觸，其中將膠體(例如保護性膠體)之組分自催化金屬移除。 Exemplary and non-limiting pretreatment processes, particularly for printed circuit board laminates and other suitable substrates, can include the steps of: a) contacting the substrate with an activator solution containing a colloidal or ion catalyzed metal, such as a precious metal. Preferably, the palladium is such that the surface of the substrate becomes catalytic, and optionally, if the activator contains an ion-catalyzed metal, b) contacting the substrate with a reducing agent, wherein the metal ion of the ion activator is reduced to an elemental metal Or if the activator contains a colloidal catalytic metal, c) contacting the substrate with an accelerator wherein the components of the colloid (eg, protective colloid) are removed from the catalytic metal.
可視情況以任何組合執行，較佳在上述步驟a)之前之其他步驟為： It may be performed in any combination as appropriate, preferably other steps before step a) above are:
i.清潔及調節基板至增大吸附。用清潔劑移除有機物 及其他殘餘物。清潔劑亦可含有使表面準備用於活化步驟，亦即增強催化劑吸附及產生較均勻活化之表面的其他物質(調節劑)。 i. Clean and adjust the substrate to increase adsorption. Remove organic matter with detergent And other residues. The cleaning agent may also contain other materials (regulators) that prepare the surface for the activation step, i.e., enhance the adsorption of the catalyst and produce a more uniformly activated surface.
ii.蝕刻該基板以自銅表面、尤其自孔之內層移除氧化物。此舉可藉由基於過硫酸鹽或過氧化物之蝕刻系統來進行。 Ii. Etching the substrate to remove oxide from the copper surface, especially from the inner layer of the hole. This can be done by a persulfate or peroxide based etching system.
iii.使基板與預浸漬溶液(諸如鹽酸溶液或硫酸溶液)接觸，該預浸漬溶液中視情況含有鹼金屬鹽(諸如氯化鈉)。預浸漬液用以保護活化劑免於帶入及污染。 Iii. contacting the substrate with a pre-dip solution such as a hydrochloric acid solution or a sulfuric acid solution, which optionally contains an alkali metal salt such as sodium chloride. The pre-dip solution serves to protect the activator from carry-in and contamination.
在另一種類之預處理製程中，採用過錳酸鹽蝕刻步驟。隨附實例中描述使用過錳酸鹽蝕刻步驟之所謂去污製程(Desmear process)。去污製程可與上述步驟組合。特定言之，去污製程可在上述預處理製程之步驟a)之前，或在執行步驟i)-iii)中一或多者之情況下在上述步驟i)-iii)之前執行。亦可執行去污製程來替代步驟i)及ii)。 In another type of pretreatment process, a permanganate etching step is employed. The so-called Desmear process using the permanganate etching step is described in the accompanying examples. The decontamination process can be combined with the above steps. In particular, the decontamination process can be performed prior to step a) above, or in the case of performing one or more of steps i) - iii), prior to steps i) - iii) above. A decontamination process can also be performed instead of steps i) and ii).
在尤其適於顯示器應用之金屬化及玻璃基板之金屬化的預處理製程中，僅使表面與預浸漬溶液及活化劑溶液接觸，接著與本發明之溶液接觸。在預浸漬步驟之前與清潔液及黏著增強劑接觸為視情況選用之步驟，其可預先進行。 In a pretreatment process that is particularly suitable for metallization of display applications and metallization of glass substrates, only the surface is contacted with the prepreg solution and the activator solution, followed by contact with the solution of the present invention. The step of contacting the cleaning liquid and the adhesion enhancer prior to the pre-impregnation step is optionally carried out, which may be carried out in advance.
可在鍍銅之前以下列步驟進行經常用於玻璃基板之另一製程：欲電鍍之玻璃表面展現作為晶種之金屬粒子。金屬粒子可藉由濺鍍技術帶至表面上。例示性晶種為由以下構成之粒子：銅、鈦、鉬、鋯、鋁、鉻、鎢、鈮、鉭或其混 合物或合金。另一晶種可為金屬氧化物，或混合金屬氧化物，例如氧化銦錫。此製程亦可用於塑膠基板，例如由聚對苯二甲酸乙二酯製得之基板。 Another process that is often used for glass substrates can be carried out in the following steps before copper plating: the surface of the glass to be electroplated exhibits metal particles as seed crystals. Metal particles can be brought to the surface by sputtering techniques. An exemplary seed crystal is a particle composed of copper, titanium, molybdenum, zirconium, aluminum, chromium, tungsten, rhenium, ruthenium or the like. Compound or alloy. Another seed crystal may be a metal oxide, or a mixed metal oxide such as indium tin oxide. The process can also be applied to plastic substrates such as those made from polyethylene terephthalate.
使該經預處理之玻璃表面與含有離子催化金屬(諸如貴金屬，較佳為鈀)之活化劑溶液接觸，使得表面變得具催化性。藉由晶種金屬使離子催化金屬還原於表面上。在此製程中，可省略添加另一還原劑。此製程尤其用於針對顯示器應用之玻璃基板的鍍銅中。 Contacting the pretreated glass surface with an activator solution containing an ion catalyzed metal such as a noble metal, preferably palladium, renders the surface catalytic. The ion-catalyzed metal is reduced to the surface by the seed metal. In this process, the addition of another reducing agent may be omitted. This process is especially useful for copper plating of glass substrates for display applications.
例示性預處理製程或其單一步驟必要時可組合成替代性預處理製程。 An exemplary pretreatment process or a single step thereof can be combined into an alternative pretreatment process as necessary.
在另一態樣中，本發明係關於如上所述之無電鍍銅溶液用於電鍍以下各物之用途：印刷電路板、晶圓、積體電路基板、MID(模製互連裝置)組件、顯示器(諸如液晶顯示器、TFT顯示器、電漿顯示器、電致發光顯示器(ELD)及電鉻顯示器(ECD)，特定言之用於以下各物之顯示器：電子裝置或TV、顯示組件、平板感測器，諸如X射線成像裝置)，或塑膠零件，諸如用於功能性或裝飾性目的之塑膠零件。 In another aspect, the invention relates to the use of an electroless copper solution as described above for electroplating the following: printed circuit boards, wafers, integrated circuit substrates, MID (Molded Interconnect) components, Display (such as liquid crystal display, TFT display, plasma display, electroluminescent display (ELD) and electrochromic display (ECD), specifically for display of: electronic device or TV, display component, flat panel sensing Devices, such as X-ray imaging devices, or plastic parts, such as plastic parts for functional or decorative purposes.
現藉由以下實例更詳細地描述本發明。闡述此等實例以說明本發明，但不應視為限制本發明。 The invention will now be described in more detail by the following examples. These examples are set forth to illustrate the invention, but are not to be construed as limiting the invention.
電鍍於通孔中之無電銅的覆蓋性可使用工業標準背光測試(Backlight Test)來評估，其中將無電電鍍之試片切開，以便當經強光源檢視時不完全覆蓋之區域經偵測為亮點[US 2008/0038450 A1]。 The coverage of electroless copper plated in the vias can be evaluated using an industry standard Backlight Test in which the electrolessly plated test pieces are cut so that areas that are not completely covered when viewed by a strong light source are detected as bright spots. [US 2008/0038450 A1].
銅沈積物之品質係由在習知光學顯微鏡下觀察到之光量來測定。 The quality of the copper deposit is determined by the amount of light observed under a conventional optical microscope.
背光量測之結果係以D1至D10標度給出，其中D1意謂最差結果且D10意謂最佳結果。圖3展示顯示D1至D10結果之參考樣本。 The results of the backlight measurements are given on the D1 to D10 scale, where D1 means the worst result and D10 means the best result. Figure 3 shows a reference sample showing the results of D1 to D10.
操作溫度：38-50℃ Operating temperature: 38-50 ° C
沈積速率：約0.6 μm/10 min。 Deposition rate: about 0.6 μm/10 min.
在此實例中，在常見去污製程中處理測試樣本以清潔孔壁表面及內層銅表面。另外，粗糙化樹脂表面以達成良好銅黏著性。 In this example, the test sample is processed in a common decontamination process to clean the pore wall surface and the inner copper surface. In addition, the surface of the resin is roughened to achieve good copper adhesion.
去污製程為多級製程，其步驟展示於圖1中。 The decontamination process is a multi-stage process, the steps of which are shown in Figure 1.
膨脹劑由有機溶劑混合物製成。在此步驟期間，移除鑽污跡(drill smear)及其他雜質。60-80℃之高溫促進膨脹劑浸潤，從而產生膨脹表面。因此，隨後塗覆之過錳酸鹽溶液可能產生較強侵蝕。之後，還原溶液(反應調節劑)自表面移除在過錳酸鹽步驟期間產生之二氧化錳。 The expansion agent is made of a mixture of organic solvents. During this step, drill smear and other impurities are removed. The high temperature of 60-80 ° C promotes the expansion of the expansion agent, thereby producing an expanded surface. Therefore, the subsequently coated permanganate solution may cause strong erosion. Thereafter, the reducing solution (reaction modifier) removes manganese dioxide produced during the permanganate step from the surface.
在PTH(電鍍通孔)製程中，準備不導電材料用於銅沈積。圖2展示PTH製程之活化步驟。 In the PTH (Plated Through Hole) process, a non-conductive material is prepared for copper deposition. Figure 2 shows the activation steps of the PTH process.
清潔劑用以移除有機物且調節表面以用於後續活化步驟。 A cleaning agent is used to remove the organics and adjust the surface for subsequent activation steps.
蝕刻清潔劑自孔中銅內層之表面移除氧化物。用作蝕刻清潔劑之物質係選自硫酸與過氧化氫之混合物，或選自過氧二硫酸鹽或選自過氧單硫酸鹽。蝕刻清潔液除蝕刻組分外亦可含有添加劑及/或穩定劑。 The etch cleaner removes oxide from the surface of the copper inner layer in the hole. The substance used as the etching cleaning agent is selected from a mixture of sulfuric acid and hydrogen peroxide, or is selected from peroxodisulfate or selected from peroxymonosulfate. The etching cleaning solution may contain additives and/or stabilizers in addition to the etching component.
以鈀活化面板及孔表面係在含有膠態或離子性催化金屬(諸如貴金屬，較佳為鈀)之活化劑中進行，使得表面變得具催化性。在一個可能之配置中，活化劑含有由有機配位體錯合之鈀離子。字首預浸漬(Predip)應保護活化劑以免帶入及污染。 The palladium-activated panel and the pore surface are carried out in an activator containing a colloidal or ionic catalytic metal such as a noble metal, preferably palladium, to render the surface catalytic. In one possible configuration, the activator contains palladium ions that are mismatched by the organic ligand. Predip (Predip) should protect the activator from being carried in and contaminated.
活化製程之最後步驟為還原劑。於彼處，鈀離子經還原為具有高催化活性之元素鈀。在還原劑步驟之後，用本發明之溶液進行無電銅沈積。還原劑與離子金屬化合物組合用作活化劑。其採用如次磷酸鹽、氫硼化物、胺基氫硼化物之還原劑。 The final step in the activation process is the reducing agent. At one point, palladium ions are reduced to elemental palladium with high catalytic activity. After the reducing agent step, electroless copper deposition is carried out using the solution of the present invention. A reducing agent is used as an activator in combination with an ionic metal compound. It employs a reducing agent such as hypophosphite, borohydride, or amine borohydride.
對於無電銅沈積，藉由以表1中概述之順序將浴組分添 加至適量水中來產生浴構成。使用空氣攪動。操作溫度在38-50℃之間變化。又，沈積時間經設定為10-60分鐘以達成所需銅厚度。 For electroless copper deposition, the bath components were added in the order outlined in Table 1. Add to the right amount of water to create a bath composition. Use air to agitate. The operating temperature varies between 38-50 °C. Again, the deposition time is set to 10-60 minutes to achieve the desired copper thickness.
沈積速度(對FR4材料(例如Matsushita MC 100 EX)所量測)：約0.6μm/10min。 Deposition rate (measured for FR4 material (eg, Matsushita MC 100 EX)): about 0.6 μm/10 min.
起泡趨勢(測試材料：來自Ajinomoto之ABF GX-92)：低或無 Foaming tendency (test material: ABF GX-92 from Ajinomoto): low or no
覆蓋性(FR4與GX-92)：良好 Coverage (FR4 and GX-92): Good
顏色(FR4與GX-92)：橙紅色 Color (FR4 and GX-92): orange red
對覆蓋銅之具有通孔之FR4測試背光。 FR4 test backlight with through holes covering copper.
使測試面板經歷整個去污製程(下表)。 The test panel is subjected to the entire decontamination process (below).
基於離子活化劑系統之活化製程： Activation process based on ion activator system:
下表中描述銅浴之構成實例。 An example of the composition of the copper bath is described in the following table.
操作溫度：38℃ Operating temperature: 38 ° C
沈積速率：0.6μm/10min。 Deposition rate: 0.6 μm/10 min.
起泡趨勢：無 Foaming trend: none
覆蓋性：良好 Coverage: good
背光D8 Backlight D8
顏色：橙紅色 Color: orange red
操作溫度：45℃ Operating temperature: 45 ° C
沈積速率：0.5μm/10min Deposition rate: 0.5μm/10min
背光：D7 Backlight: D7
浴穩定性：良好 Bath stability: good
覆蓋性：良好 Coverage: good
顏色：橙紅色 Color: orange red
缺點：非生物可降解之錯合劑 Disadvantages: non-biodegradable complex
操作溫度：60℃ Operating temperature: 60 ° C
沈積速率：0.3μm/10min Deposition rate: 0.3μm/10min
背光：D8 Backlight: D8
浴穩定性：低 Bath stability: low
覆蓋性：良好 Coverage: good
顏色：橙紅色 Color: orange red
缺點：低沈積速率 Disadvantages: low deposition rate
操作溫度：38℃ Operating temperature: 38 ° C
沈積速率：0.3μm/10min Deposition rate: 0.3μm/10min
背光：D8-D9 Backlight: D8-D9
浴穩定性：低 Bath stability: low
起泡趨勢：低 Foaming trend: low
覆蓋性：良好 Coverage: good
顏色：橙紅色 Color: orange red
缺點：需要高錯合劑濃度且沈積速率低 Disadvantages: high concentration of mixed agent is required and deposition rate is low
操作溫度：50℃ Operating temperature: 50 ° C
沈積速率：0.4μm/10min Deposition rate: 0.4μm/10min
背光：D4-D5 Backlight: D4-D5
浴穩定性：極低 Bath stability: very low
覆蓋性：不良 Coverage: bad
顏色：微深橙紅色 Color: micro deep orange red
缺點：不良銅沈積及極低浴活性 Disadvantages: poor copper deposition and very low bath activity
概述：當將乙醛酸用作還原劑時，常見生物可降解之錯合劑(如酒石酸鹽)不能再滿足浴要求。上文測試之含乙醛酸之 比較性生物可降解錯合劑顯示低沈積速率及/或需要高錯合劑濃度。所測試之其他生物可降解錯合劑根本未顯示銅沈積或關於覆蓋性、沈積速度及起泡趨勢顯示不良結果。相反，(S,S)-乙二胺-N,N'-二丁二酸((S,S)-EDDS)為生物可降解的且滿足電鍍工業之要求。含有EDDS之本發明溶液之特徵在於其良好浴效能、良好覆蓋性、高沈積速度及低起泡趨勢。由於EDDS之強錯合性質，本發明之銅浴之穩定性比用其他生物可降解錯合劑好得多。 Overview: When glyoxylic acid is used as a reducing agent, common biodegradable complexing agents (such as tartrate) can no longer meet bath requirements. Glyoxylic acid containing the above test Comparative biodegradable complexes exhibit low deposition rates and/or require high levels of complexing agents. Other biodegradable complexes tested did not show copper deposition at all or showed poor results with respect to coverage, deposition rate and foaming tendency. In contrast, (S,S)-ethylenediamine-N,N'-disuccinic acid ((S,S)-EDDS) is biodegradable and meets the requirements of the electroplating industry. The solution of the invention containing EDDS is characterized by good bath performance, good coverage, high deposition rate and low foaming tendency. Due to the strong mismatch nature of EDDS, the copper bath of the present invention is much more stable than other biodegradable complexes.
操作溫度：38℃ Operating temperature: 38 ° C
沈積速率：0.8μm/10min Deposition rate: 0.8μm/10min
背光：D6 Backlight: D6
浴穩定性：良好 Bath stability: good
覆蓋性：良好 Coverage: good
顏色：橙紅色 Color: orange red
起泡：不起泡 Foaming: no bubbles
操作溫度：38℃ Operating temperature: 38 ° C
沈積速率：0.4μm/10min Deposition rate: 0.4μm/10min
背光：D4 Backlight: D4
浴穩定性：良好 Bath stability: good
覆蓋性：不良，可觀察到鈍化 Coverage: poor, observable passivation
顏色：微深橙紅色 Color: micro deep orange red
起泡：無 Foaming: none
當比較實例3.1.1與3.1.2時，關於在相同電鍍條件下之銅沈積速率，含有EDDS之鍍銅浴比含有EDTA之浴快兩倍。此外，用EDDS達成較佳覆蓋性。 When comparing Examples 3.1.1 and 3.1.2, the copper plating bath containing EDDS was twice as fast as the bath containing EDTA for the copper deposition rate under the same plating conditions. In addition, better coverage is achieved with EDDS.
操作溫度：38℃ Operating temperature: 38 ° C
沈積速率：1.1μm/10min Deposition rate: 1.1μm/10min
背光：D7 Backlight: D7
浴穩定性：良好 Bath stability: good
覆蓋性：良好 Coverage: good
顏色：橙紅色 Color: orange red
起泡：不起泡 Foaming: no bubbles
操作溫度：38℃ Operating temperature: 38 ° C
沈積速率：0.9μm/10min Deposition rate: 0.9μm/10min
背光：D6 Backlight: D6
浴穩定性：低 Bath stability: low
覆蓋性：不良、輕微鈍化 Coverage: poor, slightly passivated
顏色：微深橙紅色 Color: micro deep orange red
起泡：是 Foaming: yes
結果：含EDDS/甲醛之浴顯示比含EDTA/甲醛之浴略高之沈積速率。但當EDTA由EDDS替代時(參看實例3.1.1及3.1.2)，沈積速率的增大比用乙醛酸低得多。因此，在含甲醛之浴中，EDDS可相當於或稍微優於EDTA。然而，以乙醛酸作為還原劑，EDDS顯示比EDTA好得多的結果(沈積速率增大約100%)，其無法鑒於先前技術來預見。 Results: The bath containing EDDS/formaldehyde showed a slightly higher deposition rate than the bath containing EDTA/formaldehyde. However, when EDTA is replaced by EDDS (see Examples 3.1.1 and 3.1.2), the deposition rate increases much less than with glyoxylic acid. Thus, in a bath containing formaldehyde, the EDDS can be equivalent or slightly better than EDTA. However, with glyoxylic acid as the reducing agent, EDDS showed much better results than EDTA (deposition rate increased by about 100%), which could not be foreseen in view of the prior art.
莫耳比EDDS：Cu之變化 Moerby EDDS: Change of Cu
操作溫度：36℃ Operating temperature: 36 ° C
沈積速率：0.6μm/10min Deposition rate: 0.6μm/10min
至少必需1.1：1之莫耳比EDDS：Cu以錯合鹼性溶液中之銅離子。莫耳比<1.1：1引起氫氧化銅沈澱。因此，可能無鍍 銅。 At least a molar ratio of 1.1:1 to EDDS:Cu is required to misalign the copper ions in the alkaline solution. Mohr ratio <1.1:1 causes precipitation of copper hydroxide. Therefore, there may be no plating copper.
莫耳比>5：1引起浴不穩定性及PCB材料上之高起泡趨勢。沈積顏色為深橙紅色且背光係在D7之所需值下。 Mobi ratio >5:1 causes bath instability and high foaming tendency on PCB material. The deposited color is dark orange red and the backlight is at the desired value of D7.
可在用浴6(6：1之莫耳比EDDS：Cu)無電鍍銅後發現燒杯上不受控制之銅沈積。浴穩定性不夠。 Uncontrolled copper deposition on the beaker can be found after electroless copper plating in bath 6 (6:1 molar ratio EDDS:Cu). Bath stability is not enough.
測試無電銅浴中EDDS與乙醛酸之不同莫耳比，如以下各表中所示。 The different molar ratios of EDDS to glyoxylic acid in the electroless copper bath were tested as shown in the following tables.
Cu、錯合劑及還原劑之莫耳濃度及質量 Mo concentration and quality of Cu, misc and reducing agent
測試面板經歷整個去污製程(表2)及基於離子活化劑系統之活化製程(表3)，如實例1中所述。 The test panels were subjected to the entire decontamination process (Table 2) and an activation process based on the ion activator system (Table 3) as described in Example 1.
以下參數應用於無電銅浴中之無電電鍍： The following parameters apply to electroless plating in an electroless copper bath:
- T=38℃ - T=38°C
- 虛設電鍍：10-15分鐘 - Dummy plating: 10-15 minutes
- 曝露時間：10分鐘 - Exposure time: 10 minutes
- 測試材料：除實例1中已描述之GX-92(短去污：2',4',4')及FR4外，亦使用由以下材料製成之測試面板。 - Test material: In addition to the GX-92 (short decontamination: 2', 4', 4') and FR4 which have been described in Example 1, test panels made of the following materials were also used.
ABS(短去污：2',4',2')用於測試覆蓋性及鈍化；R1755C(去污：5',10',5')用於背光測試。 ABS (short decontamination: 2', 4', 2') was used to test coverage and passivation; R1755C (decontamination: 5', 10', 5') was used for backlight testing.
在下表中，展示沈積測試之結果。 In the table below, the results of the deposition test are shown.
在所有浴中，浴穩定性均在一日後降低。次日，發生氫氧化銅沈澱。為提高浴穩定性，推薦至少1.1：1之EDDS：銅比率。但本發明之實驗顯示乙醛酸：EDDS莫耳比對基板上之銅沈積品質的影響。 In all baths, bath stability decreased after one day. The next day, copper hydroxide precipitation occurred. To improve bath stability, an EDDS:copper ratio of at least 1.1:1 is recommended. However, the experiments of the present invention show the effect of glyoxylic acid: EDDS molar ratio on the copper deposition quality on the substrate.
測試顯示銅沈積品質隨著乙醛酸濃度提高而降低。無電銅浴中之乙醛酸濃度較高時，銅-乙醛酸錯合物可能與Cu-EDDS錯合物競爭形成且乙醛酸亦起到錯合劑而非還原劑之作用。 Tests have shown that copper deposition quality decreases as the concentration of glyoxylic acid increases. When the concentration of glyoxylic acid in the electroless copper bath is high, the copper-glyoxylate complex may compete with the Cu-EDDS complex and the glyoxylic acid also acts as a binder rather than a reducing agent.
儘管乙醛酸濃度足夠高以致起到兩種作用(錯合劑與還原劑)，但用銅-乙醛酸錯合物之還原過程似乎受到限制。形成銅-乙醛酸錯合物會引起浴不穩定性以及覆蓋銅的材料上之鈍化。此處，鈍化意謂銅表面變得對無電鍍銅製程無活性；無電鍍銅製程在鈍化表面上終止。當乙醛酸：EDDS之莫耳比為4.6：1或4.6：1以上時，銅沈積品質降低。初始反應性、銅覆蓋性及鈍化視乙醛酸：EDDS之莫耳比 而定。 Although the glyoxylic acid concentration is sufficiently high to serve two purposes (a complexing agent and a reducing agent), the reduction process with a copper-glyoxylate complex seems to be limited. The formation of a copper-glyoxylate complex can cause bath instability and passivation on the copper-coated material. Here, passivation means that the copper surface becomes inactive to the electroless copper process; the electroless copper process terminates on the passivated surface. When the molar ratio of glyoxylic acid:EDDS is 4.6:1 or more, the copper deposition quality is lowered. Initial reactivity, copper coverage and passivated glyoxylic acid: erDS molar ratio And set.
錯合劑在無電鍍銅製程中起重要作用。並非每一種錯合劑均可用於還原過程。錯合劑EDDS與銅形成可輕易還原之錯合物。在低於4.6：1之乙醛酸：EDDS比率下，特定言之在3.6：1或低於3.6：1下，沈積品質(覆蓋性、背光)極好。 The wrong agent plays an important role in the electroless copper plating process. Not every compounding agent can be used in the reduction process. The wrong agent EDDS forms a complex with copper that can be easily reduced. At a glyoxylic acid:EDDS ratio of less than 4.6:1, specifically at 3.6:1 or below 3.6:1, the deposition quality (coverage, backlight) is excellent.
含/不含硫代羧酸之EDTA與EDDS之比較 Comparison of EDTA with EDDS with or without thiocarboxylic acid
在實驗中將硫代乙醇酸用作硫代羧酸。 Thioglycolic acid was used as the thiocarboxylic acid in the experiment.
操作溫度：55℃ Operating temperature: 55 ° C
硫代乙醇酸引起無電銅沈積之深色。沈積速率因在無電 銅浴中使用硫代乙醇酸而降低。 The thioglycolic acid causes a dark color of electroless copper deposition. Deposition rate due to no electricity The copper bath is reduced by the use of thioglycolic acid.
樣本：濺鍍有Ti/Cu晶種之玻璃 Sample: Glass sputtered with Ti/Cu seeds
圖4展示針對不同錯合劑所獲得之銅厚度之結果。 Figure 4 shows the results of copper thickness obtained for different complexing agents.
圖1用於清潔表面之去污多級製程之步驟，圖2用於活化之電鍍通孔製程之步驟，圖3針對背光量測之參考樣本，顯示D1至D10之結果，圖4使用具有不同錯合劑之浴時玻璃基板上之銅厚度。 Figure 1 is a step of cleaning the surface of the multi-stage cleaning process, Figure 2 is used for the step of activating the plated through hole process, and Figure 3 is for the reference sample of the backlight measurement, showing the results of D1 to D10, and Figure 4 is used differently. The thickness of the copper on the glass substrate during the bath of the wrong agent.
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|---|---|---|---|---|
| EP2784181B1 (en) * | 2013-03-27 | 2015-12-09 | ATOTECH Deutschland GmbH | Electroless copper plating solution |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP6180419B2 (en) | 2017-08-16 |
| CN104040026A (en) | 2014-09-10 |
| WO2013050332A8 (en) | 2013-07-11 |
| EP2764135A2 (en) | 2014-08-13 |
| JP2014528517A (en) | 2014-10-27 |
| US20140242264A1 (en) | 2014-08-28 |
| WO2013050332A3 (en) | 2014-03-13 |
| KR20140090145A (en) | 2014-07-16 |
| WO2013050332A2 (en) | 2013-04-11 |
| KR101953940B1 (en) | 2019-03-04 |
| TW201323654A (en) | 2013-06-16 |
| CN104040026B (en) | 2019-01-01 |
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