TW202000988A - Electroless copper plating compositions and methods for electroless plating copper on substrates - Google Patents

Abstract

Stable electroless copper plating baths include pyridinium compounds to improve rate of copper deposition on substrates. The copper from the electroless plating baths can be plated at low temperatures and at high plating rates.

Description

無電鍍銅組成物及用於在基材上無電鍍銅之方法Electroless copper composition and method for electroless copper on substrate

本發明涉及無電鍍銅組成物和用於在基材上無電鍍銅的方法，其中無電鍍銅在低溫下具有高的無電鍍銅速率，並且無電鍍銅組成物係穩定的。更具體地，本發明涉及無電鍍銅組成物和用於在基材上無電鍍銅的方法，其中無電鍍銅在低溫下具有高的無電鍍銅速率，並且無電鍍銅組成物係穩定的，並且其中無電鍍銅組成物包含吡啶鎓化合物或其鹽。The present invention relates to an electroless copper composition and a method for electroless copper plating on a substrate, wherein the electroless copper has a high electroless copper rate at a low temperature, and the electroless copper composition is stable. More specifically, the present invention relates to an electroless copper composition and a method for electroless copper plating on a substrate, wherein the electroless copper has a high electroless copper rate at a low temperature, and the electroless copper composition is stable, And the electroless copper plating composition contains a pyridinium compound or a salt thereof.

無電鍍銅浴廣泛用於金屬化工業中用於在各種類型的基材上沈積銅。例如，在印刷電路板的製造中，無電銅浴用於在通孔壁和電路通道上沈積銅，作為後續電解鍍銅的基礎。無電鍍銅也用於裝飾性塑膠工業中用於在非導電表面上沈積銅，作為根據需要進一步鍍銅、鎳、金、銀和其他金屬的基礎。目前商業上使用的無電銅浴含有水溶性二價銅化合物，用於螯合二價銅離子的螯合劑或錯合劑，例如羅謝爾鹽和乙二胺四乙酸鈉鹽，還原劑，例如甲醛和甲醛先質或衍生物，以及各種添加劑，以使浴更穩定，調整鍍速和改善銅沈積。Electroless copper baths are widely used in the metallization industry for depositing copper on various types of substrates. For example, in the manufacture of printed circuit boards, electroless copper baths are used to deposit copper on via walls and circuit channels as a basis for subsequent electrolytic copper plating. Electroless copper is also used in the decorative plastics industry to deposit copper on non-conductive surfaces as a basis for further plating copper, nickel, gold, silver, and other metals as needed. The electroless copper baths currently used commercially contain water-soluble divalent copper compounds, chelating agents or complexing agents for chelating divalent copper ions, such as Rochelle salt and sodium salt of ethylenediaminetetraacetic acid, and reducing agents such as formaldehyde And formaldehyde precursors or derivatives, and various additives to make the bath more stable, adjust the plating speed and improve copper deposition.

然而，應該理解，無電銅浴中的每種組分都對鍍層電位有影響，因此必須調節濃度以保持特定成分和操作條件的最理想的鍍層電位。影響內部刷鍍電壓，沈積品質和速率的其他因素包括溫度，攪拌程度，上述基本成分的類型和濃度。However, it should be understood that each component in the electroless copper bath has an effect on the coating potential, so the concentration must be adjusted to maintain the optimal coating potential for the specific composition and operating conditions. Other factors that affect the internal brush plating voltage, deposition quality and rate include temperature, degree of agitation, type and concentration of the above basic ingredients.

在無電鍍銅浴中，該等組分被連續消耗，使得浴處於恒定的變化狀態，因此必須定期補充消耗的組分。在長時段內控制浴以保持高鍍速於基本均勻的銅沈積係非常困難的。通常，等於或大於0.6 µm/5 min的無電鍍銅速率係非常需要的（較佳的是對於目前的水平鍍敷應用需要的）但很難實現，尤其是在低無電鍍敷溫度下，例如低於40°C。在幾個金屬更換（metal turnover，MTO）上消耗和補充浴組分也可能導致浴不穩定性，例如，藉由副產物的積累導致浴不穩定性。因此，這種浴，特別是那些具有高鍍層電位的浴，即高活性浴，往往會變得不穩定並隨著使用而自發分解。這種無電銅浴不穩定性可導致沿表面的不均勻或不連續的鍍銅。例如，在印刷電路板的製造中，重要的是在通孔壁上無電鍍銅，使得壁上的銅沈積基本上連續且均勻，並且銅沈積中的斷裂或縫隙最小，較佳的是沒有。銅沈積的這種不連續性最終可能導致包括有缺陷的印刷電路板的任何電氣設備的功能失常。In an electroless copper plating bath, these components are continuously consumed, so that the bath is in a constant changing state, so the consumed components must be replenished regularly. It is very difficult to control the bath for a long period of time to maintain a high plating rate over a substantially uniform copper deposition system. Generally, an electroless copper rate equal to or greater than 0.6 µm/5 min is highly desirable (preferably for current horizontal plating applications) but is difficult to achieve, especially at low electroless plating temperatures, such as Below 40°C. Consumption and replenishment of bath components on several metal turnovers (MTO) may also cause bath instability, for example, by accumulation of by-products. Therefore, such baths, especially those with high plating potential, that is, highly active baths, tend to become unstable and decompose spontaneously with use. This electroless copper bath instability can lead to uneven or discontinuous copper plating along the surface. For example, in the manufacture of printed circuit boards, it is important to electroless copper on the walls of the through holes so that the copper deposition on the walls is substantially continuous and uniform, and the cracks or gaps in the copper deposition are minimal, preferably none. This discontinuity of copper deposition may ultimately lead to malfunction of any electrical equipment including defective printed circuit boards.

為了解決上述穩定性問題，已經將分類在「穩定劑」標籤下的各種化學化合物引入無電鍍銅浴中。已經用於無電鍍銅浴的穩定劑的實例係含硫化合物，例如二硫化物和硫醇。然而，許多穩定劑降低了無電鍍銅速率，並且在高濃度下也可以是催化劑毒物，因此降低了鍍速或抑制了鍍敷並損害了鍍浴的性能。低鍍速對無電鍍銅性能有害。無電鍍銅速率也與溫度有關，因此當高穩定劑濃度降低速率時，提高鍍敷溫度可以提高速率。然而，提高操作溫度可以藉由增加副產物的積累以及藉由提高副反應的副產物產生速率來降低無電銅浴的穩定性，從而抵消了增加穩定劑濃度的一些效果。結果，在大多數情況下，所使用的穩定劑的量必須在保持高鍍速和在長時段內實現穩定的無電浴之間進行仔細的折衷。In order to solve the above stability problem, various chemical compounds classified under the "stabilizer" label have been introduced into electroless copper baths. Examples of stabilizers that have been used in electroless copper baths are sulfur-containing compounds such as disulfides and thiols. However, many stabilizers reduce the rate of electroless copper plating, and can also be a catalyst poison at high concentrations, thus reducing the plating rate or inhibiting plating and impairing the performance of the plating bath. Low plating speed is harmful to electroless copper performance. The rate of electroless copper plating is also related to temperature, so when the rate of high stabilizer concentration decreases, increasing the plating temperature can increase the rate. However, increasing the operating temperature can reduce the stability of the electroless copper bath by increasing the accumulation of by-products and by increasing the by-product generation rate of the by-products, thereby counteracting some of the effects of increasing the concentration of the stabilizer. As a result, in most cases, the amount of stabilizer used must be carefully compromised between maintaining a high plating rate and achieving a stable electroless bath for a long period of time.

替代性地，「促進劑」添加劑可結合到無電浴配製物中。理想地，促進劑添加劑不影響無電鍍浴的穩定性，使得可以在保持浴檢查中的穩定性的同時實現較高的鍍速；或使得在較低的溫度下實現此種相同的鍍速，這通常也獲得更加穩定的浴。較低的無電鍍浴溫度（例如藉由降低電鍍化學物質的被動消耗速率）降低了無電鍍浴的成本。此外，由降低工作溫度所提供的更加穩定的配製物導致較低的維護需要。最終，降低施鍍溫度可降低無電鍍沈積中內應力的積聚，使得金屬化製程更適於高粘合應用。因此，無電鍍銅中的速率加速係降低工作溫度，降低銅沈積（如柔性基材上）內部應力和降低金屬化總運行成本的關鍵策略。Alternatively, "accelerator" additives can be incorporated into the electroless bath formulation. Ideally, the accelerator additive does not affect the stability of the electroless plating bath, so that a higher plating rate can be achieved while maintaining stability in the bath inspection; or such a same plating rate can be achieved at a lower temperature, This usually also results in a more stable bath. Lower electroless plating bath temperature (for example, by reducing the passive consumption rate of electroplating chemicals) reduces the cost of electroless plating baths. In addition, the more stable formulation provided by lowering the operating temperature leads to lower maintenance requirements. Ultimately, lowering the plating temperature can reduce the accumulation of internal stress in electroless deposition, making the metallization process more suitable for high adhesion applications. Therefore, the rate acceleration in electroless copper is the key strategy to reduce the operating temperature, reduce the internal stress of copper deposition (such as on flexible substrates), and reduce the total operating cost of metallization.

因此，需要一種用於無電鍍銅浴的添加劑，其能夠在低溫下進行高速率的無電鍍銅，以在基材上提供光亮和均勻的銅沈積。Therefore, there is a need for an additive for electroless copper baths that can perform high-rate electroless copper plating at low temperatures to provide bright and uniform copper deposition on the substrate.

本發明涉及一種無電鍍銅組成物，其包含一種或多種銅離子源，一種或多種吡啶鎓化合物，一種或多種錯合劑，一種或多種還原劑，和視情況一種或多種pH調節劑，其中該無電鍍銅組成物的pH大於7。The invention relates to an electroless copper composition comprising one or more copper ion sources, one or more pyridinium compounds, one or more complexing agents, one or more reducing agents, and optionally one or more pH adjusting agents, wherein the The pH of the electroless copper composition is greater than 7.

本發明還涉及一種無電鍍銅方法，包括： a) 提供包含電介質的基材； b) 將催化劑施加到該包含電介質的基材上； c) 將無電鍍銅組成物施加到該包含電介質的基材上，其中該無電鍍銅組成物包含一種或多種銅離子源，一種或多種吡啶鎓化合物，一種或多種錯合劑，一種或多種還原劑，和視情況一種或多種pH調節劑，其中該無電鍍銅組成物的pH大於7；以及 d) 用該無電鍍銅組成物在該包含電介質的基材上無電鍍銅。The invention also relates to an electroless copper plating method, including: a) Provide a substrate containing dielectric; b) apply the catalyst to the substrate containing the dielectric; c) applying the electroless copper composition to the dielectric-containing substrate, wherein the electroless copper composition comprises one or more sources of copper ions, one or more pyridinium compounds, one or more complexing agents, one or more reducing agents Agent, and optionally one or more pH adjusting agents, wherein the pH of the electroless copper composition is greater than 7; and d) Use the electroless copper composition to electroless copper on the dielectric-containing substrate.

吡啶鎓化合物可在低於或等於40°C的低鍍敷溫度下提高無電鍍銅速率。本發明的無電鍍銅組成物和方法甚至在低鍍敷溫度下還能夠實現良好的通孔壁覆蓋。低鍍敷溫度降低了藉由不希望的副反應或分解發生的無電鍍銅組成物添加劑的消耗，從而提供了更穩定的無電鍍銅組成物，並降低了無電鍍銅製程的操作成本。Pyridinium compounds can increase the rate of electroless copper plating at low plating temperatures less than or equal to 40°C. The electroless copper plating composition and method of the present invention can achieve good through-hole wall coverage even at low plating temperatures. The low plating temperature reduces the consumption of additives for the electroless copper composition that occurs through undesirable side reactions or decomposition, thereby providing a more stable electroless copper composition and reducing the operating cost of the electroless copper process.

本發明的無電鍍銅組成物在吡啶鎓化合物的寬濃度範圍內係穩定的。用於吡啶鎓化合物濃縮的寬操作視窗意味著不需要仔細監測吡啶鎓化合物濃度，使得無電鍍銅組成物的性能基本上不會改變，無論組成物組分如何被補充和消耗。The electroless copper composition of the present invention is stable over a wide concentration range of pyridinium compounds. The wide operating window for pyridinium compound concentration means that there is no need to carefully monitor the pyridinium compound concentration, so that the performance of the electroless copper composition does not change substantially regardless of how the composition components are replenished and consumed.

如本說明書通篇所使用的，除非上下文另有明確說明，否則下面給出的縮寫具有以下含義：g = 克；mg = 毫克；mL = 毫升；L = 升；cm = 釐米；mm = 毫米；μm = 微米；ppm = 百萬分率 = mg/L；°C =攝氏度；g/L = 克/升；DI = 去離子的；C =碳元素；Pd = 鈀；Pd(II) = +2氧化態的鈀離子；Pd° = 相對於其離子態還原為其金屬態的鈀；wt% = 重量百分比；並且T_g =玻璃化轉變溫度。As used throughout this specification, unless the context clearly indicates otherwise, the abbreviations given below have the following meanings: g = grams; mg = milligrams; mL = milliliters; L = liters; cm = centimeters; mm = millimeters; μm = micron; ppm = parts per million = mg/L; °C = degrees Celsius; g/L = grams/liter; DI = deionized; C = carbon; Pd = palladium; Pd(II) = +2 Palladium ion in oxidized state; Pd° = palladium reduced to its metal state relative to its ionic state; wt% = weight percent; and _Tg = glass transition temperature.

除非另有說明，否則所有量均為重量百分比。所有數值範圍都是包含的，並且可以按任何順序組合，除非這種數值範圍被限制為加起來最高100%係合乎邏輯的。Unless otherwise stated, all amounts are weight percent. All numerical ranges are inclusive and can be combined in any order, unless such numerical ranges are restricted to add up to 100% is logical.

在整個說明書中，術語「鍍敷」和「沈積」可互換使用。在整個說明書中，術語「組成物」和「浴」可互換使用。除非在說明書中另外描述為具有取代基，否則術語「烷基」係指僅由碳和氫組成並具有以下通式的有機化學基團：C_n H_2n+1 。術語「平均值」等於樣本的平均值。除非另有說明，否則所有量均為重量百分比。所有數值範圍都是包含的，並且可以按任何順序組合，除非這種數值範圍被限制為加起來最高100%係合乎邏輯的。Throughout the specification, the terms "plating" and "deposition" are used interchangeably. Throughout the specification, the terms "composition" and "bath" are used interchangeably. Unless otherwise described in the specification as having a substituent, the term "alkyl" refers to an organic chemical group consisting only of carbon and hydrogen and having the following general formula: C _n H _2n+1 . The term "average" is equal to the average of the sample. Unless otherwise stated, all amounts are weight percent. All numerical ranges are inclusive and can be combined in any order, unless such numerical ranges are restricted to add up to 100% is logical.

本發明的無電鍍銅組成物包括一種或多種銅離子源，一種或多種吡啶鎓化合物，一種或多種錯合劑；一種或多種還原劑；水；以及視情況一種或多種pH調節劑，其中無電鍍銅組成物的pH值大於7。The electroless copper composition of the present invention includes one or more copper ion sources, one or more pyridinium compounds, one or more complexing agents; one or more reducing agents; water; and optionally one or more pH adjusting agents, wherein electroless plating The pH value of the copper composition is greater than 7.

較佳的是，一種或多種吡啶化合物具有下式：

(I) 其中R₁ 選自由以下各項組成的組：直鏈或支鏈的取代或未取代的(C₁ -C₁₀ )烷基、取代或未取代的(C₆ -C₁₀ )芳基、取代或未取代的(C₆ -C₁₀ )雜環芳香族基團和取代或未取代的苄基，其中取代基選自由羥基、硫酸酯、胺基、醯胺、羰基和羧基組成的組；並且R₂ 選自由以下各項組成的組：氫、羥基、硫酸酯、羰基、羧基、乙烯基、胺基和醯胺。更較佳的是，R₁ 選自由以下各項組成的組：直鏈或支鏈的取代和未取代的(C₂ -C₄ )烷基和取代或未取代的C₆ 雜環芳香族基團，其中取代基選自由羥基和硫酸酯組成的組；並且更較佳的是，R₂ 選自由氫、羥基和硫酸酯組成的組；並且最較佳的是，R₁ 選自由直鏈的取代或未取代的(C₂ -C₄ )烷基組成的組，其中較佳的取代基為硫酸酯；並且最較佳的是，R₂ 為氫。較佳的是，具有式 (I) 的吡啶鎓化合物包含相對陰離子以中和吡啶鎓化合物的正電荷。Preferably, one or more pyridine compounds have the following formula:

(I) wherein R _{1 is} selected from the group consisting of linear or branched substituted or unsubstituted (C ₁ -C ₁₀ )alkyl, substituted or unsubstituted (C ₆ -C ₁₀ )aryl , Substituted or unsubstituted (C ₆ -C ₁₀ ) heterocyclic aromatic groups and substituted or unsubstituted benzyl groups, wherein the substituents are selected from the group consisting of hydroxyl, sulfate, amine, amide, carbonyl and carboxyl ; And R _{2 is} selected from the group consisting of hydrogen, hydroxyl, sulfate, carbonyl, carboxy, vinyl, amine, and amide. More preferably, R _{1 is} selected from the group consisting of linear or branched substituted and unsubstituted (C ₂ -C ₄ ) alkyl and substituted or unsubstituted C ₆ heterocyclic aromatic groups Group, wherein the substituent is selected from the group consisting of hydroxy and sulfate; and more preferably, R _{2 is} selected from the group consisting of hydrogen, hydroxy, and sulfate; and most preferably, R _{1 is} selected from the group consisting of linear In the group consisting of substituted or unsubstituted (C ₂ -C ₄ ) alkyl groups, the preferred substituent is sulfate; and most preferably, R ₂ is hydrogen. Preferably, the pyridinium compound having formula (I) contains a relatively anion to neutralize the positive charge of the pyridinium compound.

較佳的是，上述吡啶鎓化合物為氫氧化物鹽、硫酸鹽、四氟硼酸鹽、六氟磷酸鹽、硝酸鹽、甲酸鹽、乙酸鹽、酒石酸鹽或鹵鹽，其中鹵素選自由氯化物、溴化物、氟化物和碘化物組成的組。更較佳的是，該鹽為鹵鹽，選自由以下各項組成之群組：氯化物和溴化物，最較佳的是，鹵鹽係氯化物。本發明的三種較佳的吡啶鎓化合物的實例為鹽1-丁基吡啶鎓氯化物和1-(3-磺丙基)吡啶鎓氫氧化物內鹽（還稱為1-(3-磺丙基)吡啶鎓）和1-(4-吡啶基)吡啶鎓氯化物。Preferably, the above pyridinium compound is a hydroxide salt, sulfate, tetrafluoroborate, hexafluorophosphate, nitrate, formate, acetate, tartrate or halogen salt, wherein the halogen is selected from chloride , Bromide, fluoride and iodide. More preferably, the salt is a halogen salt selected from the group consisting of chloride and bromide, and most preferably, the halogen salt is chloride. Examples of three preferred pyridinium compounds of the present invention are the salts 1-butylpyridinium chloride and 1-(3-sulfopropyl)pyridinium hydroxide internal salt (also known as 1-(3-sulfopropyl Group) pyridinium) and 1-(4-pyridyl)pyridinium chloride.

以0.5 ppm或更大，較佳的是從1 ppm至50 ppm、更較佳的是從2 ppm至30 ppm、甚至更較佳的是從2.5 ppm至20 ppm、最較佳的是從5 ppm至20 ppm的量包含本發明的吡啶鎓化合物。0.5 ppm or more, preferably from 1 ppm to 50 ppm, more preferably from 2 ppm to 30 ppm, even more preferably from 2.5 ppm to 20 ppm, most preferably from 5 The amount of ppm to 20 ppm contains the pyridinium compound of the present invention.

銅離子和相對陰離子的來源包括但不限於水溶性鹵化物、硝酸鹽、乙酸鹽、硫酸鹽和銅的其他有機和無機鹽。一種或多種這種銅鹽的混合物可用於提供銅離子。實例係硫酸銅如五水合硫酸銅，氯化銅，硝酸銅，氫氧化銅和胺基磺酸銅。較佳的是，本發明的無電鍍銅組成物中的一種或多種銅離子源的範圍為0.5 g/L至30 g/L，更較佳的是為1 g/L至25 g/L，甚至更較佳的是為5 g/L至20 g/L，進一步較佳的是為5 g/L至15 g/L，最較佳的是為10 g/L至15 g/L。Sources of copper ions and relative anions include, but are not limited to, water-soluble halides, nitrates, acetates, sulfates, and other organic and inorganic salts of copper. A mixture of one or more such copper salts can be used to provide copper ions. Examples are copper sulfates such as copper sulfate pentahydrate, copper chloride, copper nitrate, copper hydroxide and copper sulfamate. Preferably, the range of one or more copper ion sources in the electroless copper composition of the present invention is 0.5 g/L to 30 g/L, more preferably 1 g/L to 25 g/L, Even more preferred is 5 g/L to 20 g/L, further preferred is 5 g/L to 15 g/L, and most preferred is 10 g/L to 15 g/L.

錯合劑包括但不限於酒石酸鉀鈉，酒石酸鈉，水楊酸鈉，乙二胺四乙酸（EDTA）的鈉鹽，氮川乙酸（nitriloacetic acid）及其鹼金屬鹽，葡萄糖酸，葡萄糖酸鹽，三乙醇胺，改性乙二胺四乙酸，S,S-乙二胺二琥珀酸，乙內醯脲和乙內醯脲衍生物。乙內醯脲衍生物包括但不限於1-甲基乙內醯脲、1,3-二甲基乙內醯脲和5,5-二甲基乙內醯脲。較佳的是，錯合劑選自酒石酸鉀鈉，酒石酸鈉，氮川乙酸及其鹼金屬鹽如氮川乙酸的鈉鹽和鉀鹽，乙內醯脲和乙內醯脲衍生物中的一種或多種。較佳的是，EDTA及其鹽不包括在本發明的無電鍍銅組成物中。更較佳的是，錯合劑選自酒石酸鉀鈉、酒石酸鈉、氮川乙酸、氮川乙酸鈉鹽和乙內醯脲衍生物。甚至更較佳的是，錯合劑選自酒石酸鉀鈉、酒石酸鈉、1-甲基乙內醯脲、1,3-二甲基乙內醯脲和5,5-二甲基乙內醯脲。進一步較佳的是，錯合劑選自酒石酸鉀鈉和酒石酸鈉。最較佳的是，錯合劑係酒石酸鉀鈉（羅謝爾鹽）。Complexing agents include but are not limited to potassium sodium tartrate, sodium tartrate, sodium salicylate, sodium salt of ethylenediaminetetraacetic acid (EDTA), nitriloacetic acid and its alkali metal salts, gluconic acid, gluconate, Triethanolamine, modified ethylenediaminetetraacetic acid, S,S-ethylenediamine disuccinic acid, hydantoin and hydantoin derivatives. Hydantoin derivatives include but are not limited to 1-methylhydantoin, 1,3-dimethylhydantoin and 5,5-dimethylhydantoin. Preferably, the complexing agent is selected from one of potassium sodium tartrate, sodium tartrate, nitroacetic acid and its alkali metal salts such as sodium and potassium salts of nitroacetic acid, hydantoin and hydantoin derivatives or Multiple. Preferably, EDTA and its salts are not included in the electroless copper composition of the present invention. More preferably, the complexing agent is selected from the group consisting of potassium sodium tartrate, sodium tartrate, nitroacetic acid, nitroacetic acid sodium salt, and hydantoin derivatives. Even more preferably, the complexing agent is selected from potassium sodium tartrate, sodium tartrate, 1-methylhydantoin, 1,3-dimethylhydantoin and 5,5-dimethylhydantoin . It is further preferred that the complexing agent is selected from potassium sodium tartrate and sodium tartrate. Most preferably, the complexing agent is potassium sodium tartrate (Rochelle salt).

錯合劑以下述量包含在本發明的無電鍍銅組成物中：10 g/L至150 g/L，較佳的是為20 g/L至150 g/L，更較佳的是為30 g/L至100 g/L，甚至更較佳的是為35 g/L至80 g/L，最較佳的是為35 g/l至55 g/L。The complexing agent is included in the electroless copper plating composition of the present invention in the following amounts: 10 g/L to 150 g/L, preferably 20 g/L to 150 g/L, more preferably 30 g /L to 100 g/L, even more preferably 35 g/L to 80 g/L, most preferably 35 g/l to 55 g/L.

還原劑包括但不限於醛，例如甲醛，甲醛先質，甲醛衍生物如多聚甲醛，硼氫化物如硼氫化鈉，取代的硼氫化物，硼烷如二甲胺硼烷（DMAB），糖如葡萄糖（grape sugar）（葡糖（glucose）），葡萄糖（glucose），山梨糖醇，纖維素，蔗糖，甘露醇和葡糖酸內酯，次磷酸鹽及其鹽如次磷酸鈉，對苯二酚，鄰苯二酚，間苯二酚，氫醌，連苯三酚，偏苯三酚，間苯三酚，愈創木酚，沒食子酸，乙醛酸，3,4-二羥基苯甲酸，苯酚磺酸，甲酚磺酸，對苯二酚磺酸（hydroquinonsulfonic acid），鄰苯二酚磺酸，鈦試劑和所有上述還原劑的鹽。較佳的是，還原劑選自甲醛，甲醛衍生物，甲醛先質，硼氫化物和次磷酸鹽及其鹽，對苯二酚，鄰苯二酚，間苯二酚和沒食子酸。更較佳的是，還原劑選自甲醛、甲醛衍生物、甲醛先質和次磷酸鈉。最較佳的是，還原劑係甲醛。Reducing agents include but are not limited to aldehydes, such as formaldehyde, formaldehyde precursors, formaldehyde derivatives such as paraformaldehyde, borohydrides such as sodium borohydride, substituted borohydrides, boranes such as dimethylamine borane (DMAB), sugar Such as glucose (glucose), glucose, sorbitol, cellulose, sucrose, mannitol and gluconolactone, hypophosphite and its salts such as sodium hypophosphite, terephthalic acid Phenol, catechol, resorcinol, hydroquinone, pyrogallol, pyrogallol, resorcinol, guaiacol, gallic acid, glyoxylic acid, 3,4-dihydroxy Benzoic acid, phenolsulfonic acid, cresolsulfonic acid, hydroquinonsulfonic acid, hydroquinonsulfonic acid, catecholsulfonic acid, titanium reagents and salts of all the above reducing agents. Preferably, the reducing agent is selected from formaldehyde, formaldehyde derivatives, formaldehyde precursors, borohydride and hypophosphite salts and their salts, hydroquinone, catechol, resorcinol and gallic acid. More preferably, the reducing agent is selected from formaldehyde, formaldehyde derivatives, formaldehyde precursors and sodium hypophosphite. Most preferably, the reducing agent is formaldehyde.

還原劑以下述量包括在本發明的無電鍍銅組成物中：0.5 g/L至100 g/L，較佳的是為0.5 g/L至60 g/L，更較佳的是為1 g/L至50 g/L，甚至更較佳的是為1 g/L至20 g/L，進一步較佳的是為1 g/L至10 g/L，最較佳的是為1 g/L至5 g/L。The reducing agent is included in the electroless copper plating composition of the present invention in the following amount: 0.5 g/L to 100 g/L, preferably 0.5 g/L to 60 g/L, more preferably 1 g /L to 50 g/L, even more preferably 1 g/L to 20 g/L, still more preferably 1 g/L to 10 g/L, most preferably 1 g/L L to 5 g/L.

本發明的無電鍍銅組成物的pH大於7。較佳的是，本發明的無電鍍銅組成物的pH大於7.5。更較佳的是，無電鍍銅組成物的pH範圍為8至14，甚至更較佳的是10至14，進一步較佳的是11至13，最較佳的是12至13。The pH of the electroless copper composition of the present invention is greater than 7. Preferably, the pH of the electroless copper composition of the present invention is greater than 7.5. More preferably, the pH range of the electroless copper composition is 8 to 14, even more preferably 10 to 14, even more preferably 11 to 13, and most preferably 12 to 13.

視情況，但較佳的是，一種或多種pH調節劑可包括在本發明的無電鍍銅組成物中，以將無電鍍銅組成物的pH調節至鹼性pH。酸和鹼可用於調節pH，包括有機和無機酸和鹼。較佳的是，無機酸或無機鹼或其混合物用於調節本發明的無電鍍銅組成物的pH。適用於無電鍍銅組成物的pH的無機酸包括，例如，磷酸、硝酸、硫酸和鹽酸。適用於調節無電鍍銅組成物的pH的無機鹼包含例如氫氧化銨、氫氧化鈉、氫氧化鉀和氫氧化鋰。較佳的是，使用氫氧化鈉、氫氧化鉀或其混合物來調節無電鍍銅組成物的pH，最較佳的是，使用氫氧化鈉來調節本發明的無電鍍銅組成物的pH。Optionally, but preferably, one or more pH adjusting agents may be included in the electroless copper plating composition of the present invention to adjust the pH of the electroless copper plating composition to an alkaline pH. Acids and bases can be used to adjust pH, including organic and inorganic acids and bases. Preferably, an inorganic acid or inorganic base or a mixture thereof is used to adjust the pH of the electroless copper composition of the present invention. Inorganic acids suitable for the pH of the electroless copper composition include, for example, phosphoric acid, nitric acid, sulfuric acid, and hydrochloric acid. Inorganic bases suitable for adjusting the pH of the electroless copper composition include, for example, ammonium hydroxide, sodium hydroxide, potassium hydroxide, and lithium hydroxide. Preferably, sodium hydroxide, potassium hydroxide, or a mixture thereof is used to adjust the pH of the electroless copper composition, and most preferably, sodium hydroxide is used to adjust the pH of the electroless copper composition of the present invention.

視情況，但較佳的是，一種或多種穩定劑可包括在本發明的無電鍍銅組成物中。穩定劑包括但不限於2,2'-聯吡啶和衍生物，4,4'-聯吡啶，啡啉和啡啉衍生物，硫代蘋果酸，2,2'-二硫代二琥珀酸，巰基琥珀酸，半胱胺酸，蛋胺酸，硫堇，硫脲，苯并噻唑，巰基苯并噻唑，2,2'-硫代二乙酸，3,3'-硫代二丙酸，3,3'-二硫代二丙酸，硫代硫酸鹽和二醇如聚丙二醇和聚乙二醇。Optionally, but preferably, one or more stabilizers may be included in the electroless copper composition of the present invention. Stabilizers include but are not limited to 2,2'-bipyridine and derivatives, 4,4'-bipyridine, morpholine and morpholine derivatives, thiomalic acid, 2,2'-dithiodisuccinic acid, Mercaptosuccinic acid, cysteine, methionine, thionine, thiourea, benzothiazole, mercaptobenzothiazole, 2,2'-thiodiacetic acid, 3,3'-thiodipropionic acid, 3 , 3'-dithiodipropionic acid, thiosulfate and glycols such as polypropylene glycol and polyethylene glycol.

這種視情況的穩定劑以下述量包括在本發明的無電鍍銅組成物中：0.1 ppm至20 ppm，較佳的是0.5 ppm至10 ppm，更較佳的是0.5 ppm至5 ppm，最較佳的是0.5 ppm至2 ppm。This optional stabilizer is included in the electroless copper plating composition of the present invention in the following amounts: 0.1 ppm to 20 ppm, preferably 0.5 ppm to 10 ppm, more preferably 0.5 ppm to 5 ppm, most It is preferably 0.5 ppm to 2 ppm.

視情況，但較佳的是，一種或多種輔助促進劑可包括在本發明的無電鍍銅組成物中。這種促進劑包括但不限於若干游離氮鹼如胍，胍衍生物如鹽酸胍，吡啶和吡啶衍生物如胺基吡啶，二烷基胺和三烷基胺如三甲胺和三乙胺，N,N,N′,N′-四(2-羥丙基)乙二胺和乙二胺四乙酸，和鎳(II)鹽如硫酸鎳(II)。較佳的輔助促進劑的實例係鹽酸胍。Optionally, but preferably, one or more auxiliary accelerators may be included in the electroless copper composition of the present invention. Such accelerators include but are not limited to several free nitrogen bases such as guanidine, guanidine derivatives such as guanidine hydrochloride, pyridine and pyridine derivatives such as aminopyridine, dialkylamines and trialkylamines such as trimethylamine and triethylamine, N , N, N′, N′-tetrakis (2-hydroxypropyl) ethylenediamine and ethylenediaminetetraacetic acid, and nickel (II) salts such as nickel (II) sulfate. An example of a preferred auxiliary accelerator is guanidine hydrochloride.

可以下述量包括這種促進劑：0.1 ppm至500 ppm，較佳的是0.2至15 ppm，更較佳的是0.3 ppm至10 ppm，最較佳的是0.3 ppm至5 ppm。Such accelerators may be included in the following amounts: 0.1 ppm to 500 ppm, preferably 0.2 to 15 ppm, more preferably 0.3 ppm to 10 ppm, and most preferably 0.3 ppm to 5 ppm.

視情況，一種或多種表面活性劑可包括在本發明的無電鍍銅組成物中。這種表面活性劑包括離子表面活性劑，如陽離子和陰離子表面活性劑，非離子和兩性表面活性劑。也可以使用表面活性劑的混合物。表面活性劑可以0.001 g/L至50 g/L的量，較佳的是0.01 g/L至50 g/L的量包括在組成物中。As the case may be, one or more surfactants may be included in the electroless copper plating composition of the present invention. Such surfactants include ionic surfactants, such as cationic and anionic surfactants, nonionic and amphoteric surfactants. Mixtures of surfactants can also be used. The surfactant may be included in the composition in an amount of 0.001 g/L to 50 g/L, preferably in an amount of 0.01 g/L to 50 g/L.

陽離子表面活性劑包括但不限於四烷基鹵化銨、烷基三甲基鹵化銨、羥乙基烷基咪唑啉、烷基咪唑鎓、鹵化烷基苯甲烴銨（alkylbenzalkonium halide）、烷基胺乙酸鹽、烷基胺油酸鹽和烷基胺基乙基甘胺酸。Cationic surfactants include but are not limited to tetraalkylammonium halides, alkyltrimethylammonium halides, hydroxyethylalkylimidazoline, alkylimidazolium, alkylbenzalkonium halide, alkylamines Acetate, alkylamine oleate and alkylaminoethylglycine.

陰離子表面活性劑包括但不限於烷基苯磺酸鹽、烷基或烷氧基萘磺酸鹽、烷基二苯基醚磺酸鹽、烷基醚磺酸鹽、烷基硫酸酯、聚氧乙烯烷基醚硫酸酯、聚氧乙烯烷基酚醚硫酸酯、高級醇磷酸單酯、聚氧化烯烷基醚磷酸（磷酸鹽）和烷基磺基琥珀酸鹽。Anionic surfactants include but are not limited to alkyl benzene sulfonate, alkyl or alkoxy naphthalene sulfonate, alkyl diphenyl ether sulfonate, alkyl ether sulfonate, alkyl sulfate, polyoxy Ethylene alkyl ether sulfate, polyoxyethylene alkyl phenol ether sulfate, higher alcohol phosphate monoester, polyoxyalkylene alkyl ether phosphate (phosphate) and alkyl sulfosuccinate.

兩性表面活性劑包括但不限於2-烷基-N-羧甲基或乙基-N-羥乙基或甲基咪唑鎓甜菜鹼，2-烷基-N-羧甲基或乙基-N-羧甲氧基乙基咪唑鎓甜菜鹼，二甲基烷基甜菜鹼，N-烷基-b-胺基丙酸或其鹽，和脂肪酸醯胺丙基二甲基胺基乙酸甜菜鹼。Amphoteric surfactants include but are not limited to 2-alkyl-N-carboxymethyl or ethyl-N-hydroxyethyl or methylimidazolium betaine, 2-alkyl-N-carboxymethyl or ethyl-N -Carboxymethoxyethyl imidazolium betaine, dimethyl alkyl betaine, N-alkyl-b-aminopropionic acid or its salt, and fatty acid amidopropyl dimethylaminoacetic acid betaine.

較佳的是，表面活性劑係非離子的。非離子表面活性劑包括但不限於烷基苯氧基聚乙氧基乙醇，具有20至150個重複單元的聚氧乙烯聚合物和聚氧乙烯與聚氧丙烯的無規和嵌段共聚物，以及多胺如聚烯丙基胺。Preferably, the surfactant is nonionic. Nonionic surfactants include but are not limited to alkylphenoxypolyethoxyethanol, polyoxyethylene polymers with 20 to 150 repeating units, and random and block copolymers of polyoxyethylene and polyoxypropylene, And polyamines such as polyallylamine.

視情況，一種或多種晶粒細化劑可包括在本發明的無電鍍銅組成物中。晶粒細化劑包括但不限於氰化物和含氰化物的無機鹽如亞鐵氰化鉀，2-巰基苯并噻唑，2,2'-聯吡啶和2,2'-聯吡啶衍生物，1,10-啡啉和1,10-啡啉衍生物，釩氧化物如偏釩酸鈉，和鎳鹽如硫酸鎳(II)。以熟悉該項技術者所熟知的量包括晶粒細化劑。As appropriate, one or more grain refiners may be included in the electroless copper composition of the present invention. Grain refiners include but are not limited to cyanide and cyanide-containing inorganic salts such as potassium ferrocyanide, 2-mercaptobenzothiazole, 2,2'-bipyridine and 2,2'-bipyridine derivatives, 1,10-morpholine and 1,10-morpholine derivatives, vanadium oxides such as sodium metavanadate, and nickel salts such as nickel (II) sulfate. The grain refiner is included in an amount well known to those skilled in the art.

較佳的是，本發明的無電鍍銅組成物由以下各項組成：一種或多種銅離子源（包含對應的陰離子）、一種或多種具有式 (I) 的吡啶鎓化合物或其鹽、一種或多種複合劑、一種或多種還原劑、水、視情況一種或多種pH調節劑、視情況一種或多種穩定劑、視情況一種或多種助促進劑、視情況一種或多種表面活性劑以及視情況一種或多種晶粒細化劑，其中無電鍍銅組成物的pH為10-14。Preferably, the electroless copper composition of the present invention is composed of one or more sources of copper ions (including corresponding anions), one or more pyridinium compounds of formula (I) or salts thereof, one or Multiple complexing agents, one or more reducing agents, water, optionally one or more pH adjusting agents, optionally one or more stabilizers, optionally one or more promoters, optionally one or more surfactants, and optionally one Or a variety of grain refiners, of which the pH of the electroless copper composition is 10-14.

更較佳的是，本發明的無電鍍銅組成物由以下各項組成：一種或多種銅離子源（包含對應的陰離子）、一種或多種具有式 (I) 的吡啶鎓化合物或其鹽（其中該鹽選自由氫氧化物、氯化物和溴化物鹽組成的組）、一種或多種複合劑、一種或多種還原劑、水、一種或多種pH調節劑、一種或多種穩定劑、可選地一種或多種助促進劑、可選地一種或多種表面活性劑以及可選地一種或多種晶粒細化劑，其中無電鍍銅組成物的pH為11-13。More preferably, the electroless copper composition of the present invention is composed of one or more sources of copper ions (including the corresponding anions), one or more pyridinium compounds of formula (I) or salts thereof (wherein The salt is selected from the group consisting of hydroxide, chloride and bromide salts), one or more complexing agents, one or more reducing agents, water, one or more pH adjusting agents, one or more stabilizers, optionally one Or more promoters, optionally one or more surfactants, and optionally one or more grain refiners, wherein the pH of the electroless copper composition is 11-13.

最較佳的是，本發明的無電鍍銅組成物由以下各項組成：一種或多種銅離子源（包含對應的陰離子）、一種或多種吡啶鎓化合物（其選自由氯化1-丁基吡啶鎓、1-(3-磺丙基)吡啶鎓氫氧化物和1-(4-吡啶基)吡啶鎓氯化物組成的組）、一種或多種複合劑、一種或多種還原劑、水、一種或多種pH調節劑、一種或多種穩定劑、可選地一種或多種助促進劑、可選地一種或多種表面活性劑以及可選地一種或多種晶粒細化劑，其中無電鍍銅組成物的pH為12-13。Most preferably, the electroless copper composition of the present invention consists of one or more sources of copper ions (including the corresponding anions), one or more pyridinium compounds (which are selected from 1-butylpyridine chloride Onium, 1-(3-sulfopropyl)pyridinium hydroxide and 1-(4-pyridyl)pyridinium chloride), one or more complexing agents, one or more reducing agents, water, one or Various pH adjusters, one or more stabilizers, optionally one or more promoters, optionally one or more surfactants, and optionally one or more grain refiners, of which electroless copper composition The pH is 12-13.

本發明的無電銅組成物和方法可用於在各種基材上無電鍍銅，例如電介質、半導體、金屬包覆和未包覆的基材如印刷電路板。這種金屬包覆和未包覆的印刷電路板可包括熱固性樹脂，熱塑性樹脂及其組合，包括纖維如玻璃纖維，前述的浸漬實施方式。較佳的是，基材係具有多個通孔的金屬包覆的印刷電路或佈線板、穿孔（via）或其組合。本發明的無電鍍銅組成物和方法可用於製造印刷電路板的水平和垂直過程二者，較佳的是，本發明的無電鍍銅組成物和方法用於水平過程。The electroless copper composition and method of the present invention can be used for electroless copper plating on various substrates, such as dielectrics, semiconductors, metal-coated and uncoated substrates such as printed circuit boards. Such metal-coated and uncoated printed circuit boards may include thermosetting resins, thermoplastic resins and combinations thereof, including fibers such as glass fibers, and the aforementioned impregnation embodiments. Preferably, the substrate is a metal-coated printed circuit or wiring board with multiple through holes, vias, or a combination thereof. The electroless copper composition and method of the present invention can be used in both horizontal and vertical processes for manufacturing printed circuit boards. Preferably, the electroless copper composition and method of the present invention are used in horizontal processes.

熱塑性樹脂包括但不限於縮醛樹脂，丙烯酸類如丙烯酸甲酯，纖維素樹脂如乙酸乙酯，丙酸纖維素，乙酸丁酸纖維素和硝酸纖維素，聚醚，尼龍，聚乙烯，聚苯乙烯，苯乙烯共混物如丙烯腈苯乙烯和共聚物和丙烯腈-丁二烯-苯乙烯共聚物，聚碳酸酯，聚三氟氯乙烯，和乙烯基聚合物和共聚物如乙酸乙烯酯，乙烯醇，乙烯醇縮丁醛，氯乙烯，氯乙烯-乙酸酯共聚物，偏二氯乙烯和乙烯醇縮甲醛。Thermoplastic resins include but are not limited to acetal resins, acrylics such as methyl acrylate, cellulose resins such as ethyl acetate, cellulose propionate, cellulose acetate butyrate and cellulose nitrate, polyether, nylon, polyethylene, polyphenylene Ethylene, styrene blends such as acrylonitrile styrene and copolymers and acrylonitrile-butadiene-styrene copolymers, polycarbonate, polychlorotrifluoroethylene, and vinyl polymers and copolymers such as vinyl acetate , Vinyl alcohol, vinyl butyral, vinyl chloride, vinyl chloride-acetate copolymer, vinylidene chloride and vinyl formal.

熱固性樹脂包括但不限於鄰苯二甲酸烯丙酯，呋喃，三聚氰胺-甲醛，苯酚-甲醛和苯酚-糠醛共聚物，單獨或混合有丁二烯丙烯腈共聚物或丙烯腈-丁二烯-苯乙烯共聚物，聚丙烯酸酯，矽氧烷，脲甲醛，環氧樹脂，烯丙基樹脂，鄰苯二甲酸甘油酯和聚酯。Thermosetting resins include, but are not limited to, allyl phthalate, furan, melamine-formaldehyde, phenol-formaldehyde and phenol-furfural copolymers, alone or mixed with butadiene acrylonitrile copolymer or acrylonitrile-butadiene-benzene Ethylene copolymers, polyacrylates, silicones, urea formaldehyde, epoxy resins, allyl resins, glycerol phthalate and polyester.

本發明的無電鍍銅組成物和方法可用於具有低和高T_g 樹脂的無電鍍銅基材。低T_g 樹脂的T_g 低於160°C，高T_g 樹脂的T_g 為160°C及以上。通常，高T_g 樹脂的T_g 為160°C至280°C，或例如170°C至240°C。高T_g 聚合物樹脂包括但不限於聚四氟乙烯（PTFE）和聚四氟乙烯共混物。這種共混物包括例如PTFE與聚伸苯基氧化物和氰酸酯。包括具有高Tg的樹脂的其他種類的聚合物樹脂包括但不限於環氧樹脂，例如雙官能和多官能環氧樹脂，雙馬來醯亞胺/三𠯤和環氧樹脂（BT環氧），環氧/聚伸苯基氧化物樹脂，丙烯腈丁二烯苯乙烯，聚碳酸酯（PC），聚伸苯基氧化物（PPO），聚苯醚（PPE），聚苯硫醚（PPS），聚碸（PS），聚醯胺，聚酯如聚對苯二甲酸乙二醇酯（PET）和聚對苯二甲酸丁二醇酯（PBT），聚醚酮（PEEK），液晶聚合物，聚胺酯，聚醚醯亞胺，環氧化物及其複合物。The electroless copper composition and method of the present invention can be used for electroless copper substrates with low and high T _g resins. Low T _g resins have a T _g below 160°C, and high T _g resins have a T _g of 160°C and above. Typically, T _g T _g of the resin is high 160 ° C to 280 ° C, e.g. 170 ° C or to 240 ° C. High T _g polymer resins include but are not limited to polytetrafluoroethylene (PTFE) and polytetrafluoroethylene blends. Such blends include, for example, PTFE with polyphenylene oxide and cyanate esters. Other types of polymer resins including resins with high Tg include, but are not limited to, epoxy resins, such as bifunctional and multifunctional epoxy resins, bismaleimide/triamine and epoxy resin (BT epoxy), Epoxy/polyphenylene oxide resin, acrylonitrile butadiene styrene, polycarbonate (PC), polyphenylene oxide (PPO), polyphenylene oxide (PPE), polyphenylene sulfide (PPS) , Polysulfone (PS), Polyamide, polyesters such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), polyether ketone (PEEK), liquid crystal polymer , Polyurethane, Polyetherimide, Epoxide and their complexes.

在使用本發明的無電銅組成物的無電鍍銅方法中，視情況，將基材清潔或脫脂，視情況，粗糙化或微粗糙化，視情況，將基材蝕刻或微蝕刻，視情況，將溶劑溶脹施加到基材上，對通孔進行去污，並且可視情況使用各種漂洗和抗變色處理。In the electroless copper plating method using the electroless copper composition of the present invention, the base material is cleaned or degreased as appropriate, roughened or slightly roughened as appropriate, and the base material is etched or slightly etched as appropriate, as appropriate, Solvent swelling is applied to the substrate, the through holes are decontaminated, and various rinsing and anti-tarnish treatments are used as appropriate.

較佳的是，用本發明的無電鍍銅組成物和方法進行無電鍍銅的基材係具有介電材料的金屬包覆基材和多個通孔，例如印刷電路板。視情況，用水沖洗板並將其清潔和脫脂，然後對通孔壁進行去污。準備或軟化電介質或對通孔去污可以藉由施加溶劑溶脹開始。儘管較佳的是，無電鍍銅的方法係用於鍍敷通孔壁，但是可以設想，無電鍍銅的方法也可以用於過孔（via）的無電鍍銅壁。Preferably, the base material for electroless copper plating using the electroless copper composition and method of the present invention is a metal-coated base material having a dielectric material and a plurality of through holes, such as a printed circuit board. If necessary, rinse the board with water, clean and degrease, and then decontaminate the through-hole wall. Preparation or softening of the dielectric or decontamination of the through hole can be started by applying solvent swelling. Although it is preferred that the method of electroless copper plating be used for plating through-hole walls, it is conceivable that the method of electroless copper plating can also be used for electroless copper walls of vias.

可以使用常規的溶劑溶脹。具體類型可以根據介電材料的類型而變化。可以進行小的實驗以確定哪種溶劑溶脹適合於特定的介電材料。電介質的T_g 通常決定了所使用的溶劑溶脹的類型。溶劑溶脹包括但不限於乙二醇醚及其相關的醚乙酸酯。可以使用熟悉該項技術者熟知的常規量的二醇醚及其相關的醚乙酸酯。市售溶劑溶脹的實例係CIRCUPOSIT™調理劑3302A、CIRCUPOSIT™ Hole Prep 3303和CIRCUPOSIT™ Hole Prep 4120溶液（可從陶氏化學公司（Dow Electronic Materials）獲得）。Conventional solvents can be used for swelling. The specific type may vary according to the type of dielectric material. Small experiments can be conducted to determine which solvent swelling is suitable for a particular dielectric material. T _g dielectric generally determines the type of solvent used for swelling. Solvent swelling includes but is not limited to glycol ethers and their related ether acetates. It is possible to use conventional amounts of glycol ethers and related ether acetates which are well known to those skilled in the art. Examples of commercially available solvent swells are CIRCUPOSIT™ Conditioner 3302A, CIRCUPOSIT™ Hole Prep 3303 and CIRCUPOSIT™ Hole Prep 4120 solutions (available from Dow Electronic Materials).

溶劑溶脹後，視情況，可以施加助劑。可以使用常規助劑。這種助劑包括硫酸、鉻酸、鹼性過錳酸鹽或電漿蝕刻。較佳的是使用鹼性過錳酸鹽作為助劑。市售助劑的實例係CIRCUPOSIT™助劑4130和CIRCUPOSIT™ MLB助劑3308溶液（可從陶氏化學公司（Dow Electronic Materials）獲得）。視情況，用水沖洗基材和通孔。After the solvent swells, depending on the situation, additives can be applied. Conventional additives can be used. Such additives include sulfuric acid, chromic acid, alkaline permanganate, or plasma etching. It is preferable to use alkaline permanganate as an auxiliary agent. Examples of commercially available auxiliaries are CIRCUPOSIT™ auxiliaries 4130 and CIRCUPOSIT™ MLB auxiliaries 3308 solutions (available from Dow Electronic Materials). If necessary, rinse the substrate and through holes with water.

如果使用助劑，則應用中和劑以中和助劑留下的任何殘留物。可以使用常規的中和劑。較佳的是，中和劑係含有一種或多種胺的酸性水溶液或3wt%過氧化氫和3wt%硫酸的溶液。市售中和劑的實例係CIRCUPOSIT™ MLB中和劑216-5。視情況，用水沖洗基材和通孔，然後乾燥。If an auxiliary agent is used, a neutralizing agent should be applied to neutralize any residue left by the auxiliary agent. Conventional neutralizing agents can be used. Preferably, the neutralizing agent is an acidic aqueous solution containing one or more amines or a solution of 3 wt% hydrogen peroxide and 3 wt% sulfuric acid. An example of a commercially available neutralizer is CIRCUPOSIT™ MLB neutralizer 216-5. If necessary, rinse the substrate and through holes with water, and then dry.

中和後施加酸或鹼性調理劑。可以使用常規的調理劑。這種調理劑可包括一種或多種陽離子表面活性劑、非離子表面活性劑、錯合劑和pH調節劑或緩衝劑。市售酸調理劑的實例係CIRCUPOSIT™調理劑3320A和3327溶液（可從陶氏化學公司（Dow Advanced Materials）獲得）。合適的鹼性調理劑包括但不限於含有一種或多種季胺和多胺的含水鹼性表面活性劑溶液。市售鹼性表面活性劑的實例係CIRCUPOSIT™調理劑231、3325、813和860配製物（可從陶氏化學公司（Dow Electronic Materials）獲得）。視情況，用水沖洗基材和通孔。Apply acid or alkaline conditioning agent after neutralization. Conventional conditioning agents can be used. Such conditioning agents may include one or more cationic surfactants, nonionic surfactants, complexing agents, and pH adjusters or buffers. Examples of commercially available acid conditioners are CIRCUPOSIT™ conditioner 3320A and 3327 solutions (available from Dow Advanced Materials). Suitable alkaline conditioning agents include, but are not limited to, aqueous alkaline surfactant solutions containing one or more quaternary amines and polyamines. Examples of commercially available alkaline surfactants are CIRCUPOSIT™ conditioning agents 231, 3325, 813, and 860 formulations (available from Dow Electronic Materials). If necessary, rinse the substrate and through holes with water.

視情況，可以在調理之後進行微蝕刻。可以使用常規的微蝕刻組成物。設計微蝕刻以在暴露的金屬（例如內層和表面蝕刻）上清潔和提供微粗糙的金屬表面，以增強無電鍍銅和隨後的電鍍的後續粘附。微蝕刻包括但不限於60 g/L至120 g/L過硫酸鈉或氧基單過硫酸（oxymonopersulfate）鈉或鉀和硫酸（2%）混合物，或通用硫酸/過氧化氫。市售微蝕刻組成物的實例係CIRCUPOSIT™ Microetch 3330蝕刻溶液和PREPOSIT™ 748蝕刻溶液（均可從陶氏化學公司（Dow Electronic Materials）獲得）。視情況，用水沖洗基材。Depending on the situation, micro-etching may be performed after conditioning. A conventional micro-etching composition can be used. Micro-etching is designed to clean and provide a micro-rough metal surface on exposed metals (such as inner layers and surface etching) to enhance the subsequent adhesion of electroless copper and subsequent electroplating. Microetching includes but is not limited to 60 g/L to 120 g/L sodium persulfate or a mixture of sodium or potassium oxymonopersulfate and sulfuric acid (2%), or general sulfuric acid/hydrogen peroxide. Examples of commercially available micro-etching compositions are CIRCUPOSIT™ Microetch 3330 etching solution and PREPOSIT™ 748 etching solution (both available from Dow Electronic Materials). If necessary, rinse the substrate with water.

視情況，然後可以將預浸料施加到微蝕刻的基材和通孔。預浸料的實例包括但不限於有機鹽，例如酒石酸鉀鈉或檸檬酸鈉，0.5%至3%硫酸或硝酸或25 g/L至75 g/L氯化鈉的酸性溶液。可商購預浸液的實例為酸性Pre-Dip CIRCUPOSIT™ 6520溶液。As appropriate, the prepreg can then be applied to the micro-etched substrate and vias. Examples of prepregs include, but are not limited to, organic salts such as potassium sodium tartrate or sodium citrate, 0.5% to 3% sulfuric acid or nitric acid, or an acidic solution of 25 g/L to 75 g/L sodium chloride. An example of a commercially available prepreg solution is the acidic Pre-Dip CIRCUPOSIT™ 6520 solution.

然後將催化劑施加到基材上。雖然可以設想可以使用任何包括催化金屬的適用於無電鍍金屬的常規催化劑，但較佳的是，在本發明的方法中使用鈀催化劑。催化劑可以是非離子鈀催化劑，例如膠體鈀-錫催化劑，或催化劑可以是離子鈀。如果催化劑係膠體鈀-錫催化劑，則進行加速步驟以從催化劑中剝離錫並暴露鈀金屬以進行無電鍍銅。如果催化劑係膠體鈀-錫催化劑，則在催化劑吸附後進行加速步驟，例如，藉由使用鹽酸，硫酸或四氟硼酸作為促進劑以0.5%-10%在水中進行加速以從催化劑中剝離錫並暴露鈀金屬，從而進行無電鍍銅。如果催化劑係離子催化劑，則加速步驟不包括在該方法中，而是在施加離子催化劑之後將還原劑施加到基材上以將離子催化劑的金屬離子還原成其金屬態，例如將Pd(II)離子還原成Pd°金屬。合適的市售膠體鈀-錫催化劑的實例係CIRCUPOSIT™ 3340催化劑和CATAPOSITÔ 44催化劑（可從陶氏化學公司（Dow Electronic Materials）獲得）。市售鈀離子催化劑的實例係CIRCUPOSIT™ 6530催化劑。催化劑可以藉由將基材浸入催化劑溶液中，或藉由將催化劑溶液噴塗在基材上，或使用常規設備藉由將催化劑溶液霧化在基材上來施加。催化劑可以在室溫至80°C，較佳的是30°C至60°C的溫度下施加。在施加催化劑之後，視情況用水沖洗基材和通孔。The catalyst is then applied to the substrate. Although it is conceivable that any conventional catalyst suitable for electroless metals including catalytic metals can be used, it is preferred that a palladium catalyst is used in the method of the present invention. The catalyst may be a non-ionic palladium catalyst, such as a colloidal palladium-tin catalyst, or the catalyst may be ionic palladium. If the catalyst is a colloidal palladium-tin catalyst, an acceleration step is performed to strip tin from the catalyst and expose the palladium metal for electroless copper plating. If the catalyst is a colloidal palladium-tin catalyst, an acceleration step is performed after the catalyst is adsorbed, for example, by using hydrochloric acid, sulfuric acid, or tetrafluoroboric acid as an accelerator to accelerate 0.5%-10% in water to strip tin from the catalyst and Palladium metal is exposed to perform electroless copper plating. If the catalyst is an ion catalyst, the acceleration step is not included in the method, but a reducing agent is applied to the substrate after applying the ion catalyst to reduce the metal ion of the ion catalyst to its metal state, for example, Pd(II) The ions are reduced to Pd° metal. Examples of suitable commercially available colloidal palladium-tin catalysts are CIRCUPOSIT™ 3340 catalyst and CATAPOSITÔ 44 catalyst (available from Dow Electronic Materials). An example of a commercially available palladium ion catalyst is CIRCUPOSIT™ 6530 catalyst. The catalyst can be applied by immersing the substrate in the catalyst solution, or by spraying the catalyst solution on the substrate, or by using conventional equipment by atomizing the catalyst solution on the substrate. The catalyst can be applied at a temperature from room temperature to 80°C, preferably from 30°C to 60°C. After applying the catalyst, the substrate and the through holes are rinsed with water as appropriate.

已知將金屬離子還原成金屬的常規還原劑可用於將催化劑的金屬離子還原成其金屬態。這種還原劑包括但不限於二甲胺硼烷（DMAB）、硼氫化鈉、抗壞血酸、異抗壞血酸、次磷酸鈉、水合肼、甲酸和甲醛。以將基本上所有金屬離子還原為金屬的量包含還原劑。這種量係熟悉該項技術者所熟知的。如果催化劑係離子催化劑，則在將催化劑施加到基材上之後和金屬化之前施加還原劑。Conventional reducing agents known to reduce metal ions to metals can be used to reduce the metal ions of the catalyst to its metal state. Such reducing agents include, but are not limited to, dimethylamine borane (DMAB), sodium borohydride, ascorbic acid, isoascorbic acid, sodium hypophosphite, hydrazine hydrate, formic acid, and formaldehyde. The reducing agent is included in an amount that reduces substantially all metal ions to metal. This amount is well known to those skilled in the art. If the catalyst is an ionic catalyst, the reducing agent is applied after the catalyst is applied to the substrate and before metallization.

然後使用本發明的無電鍍銅組成物將通孔的基材和壁鍍銅。本發明的無電鍍銅方法可在40°C或更低的溫度下進行。較佳的是，本發明的無電鍍銅方法在室溫至40°C的溫度下進行，更較佳的是，無電鍍銅在室溫至35°C下進行，甚至更較佳的是在30°C至35°C下進行，最較佳的是在30°C至34°C下進行。可以將基材浸入本發明的無電鍍銅組成物中，或者可以將無電鍍銅組成物噴塗在基材上。本發明的使用本發明的無電鍍銅組成物進行無電鍍銅的方法在pH大於7的鹼性環境中進行。較佳的是，本發明的無電鍍銅方法在大於7.5的pH下進行，更較佳的是，無電鍍銅在8至14，甚至更較佳的是10至14，更較佳的是11至13，最較佳的是12至13的pH下進行。Then, the substrate and the wall of the through hole are copper-plated using the electroless copper composition of the present invention. The electroless copper plating method of the present invention can be performed at a temperature of 40°C or lower. Preferably, the electroless copper plating method of the present invention is performed at a temperature of room temperature to 40°C, more preferably, electroless copper plating is performed at a temperature of room temperature to 35°C, and even more preferably at It is carried out at 30°C to 35°C, most preferably at 30°C to 34°C. The substrate may be immersed in the electroless copper composition of the present invention, or the electroless copper composition may be sprayed on the substrate. The method of the present invention for performing electroless copper plating using the electroless copper composition of the present invention is performed in an alkaline environment having a pH greater than 7. Preferably, the electroless copper plating method of the present invention is performed at a pH greater than 7.5, more preferably, the electroless copper plating is at 8 to 14, even more preferably 10 to 14, and even more preferably 11 To 13, most preferably at a pH of 12 to 13.

較佳的是，本發明的無電鍍銅鍍速在低於或等於40℃的溫度下等於或大於0.6 µm/5 min.，更較佳的是，本發明的無電鍍銅鍍速在低於或等於35℃的溫度下等於或大於0.65 µm/5 min.，例如0.65 µm/5 min.至1 µm/5 min.，甚至更較佳的是等於或大於0.7 µm/5 min.，例如0.75 µm/5 min.至1 µm/5 min.，或例如0.75 µm/5 min.至0.8 µm/5 min.，最較佳的是，無電鍍銅在30℃至34℃的溫度下進行。Preferably, the electroless copper plating rate of the present invention is equal to or greater than 0.6 µm/5 min at a temperature lower than or equal to 40°C. More preferably, the electroless copper plating rate of the present invention is below At a temperature of or equal to 35°C, it is equal to or greater than 0.65 µm/5 min., such as 0.65 µm/5 min. to 1 µm/5 min., and even more preferably equal to or greater than 0.7 µm/5 min., such as 0.75 µm/5 min. to 1 µm/5 min., or for example 0.75 µm/5 min. to 0.8 µm/5 min., most preferably, electroless copper plating is performed at a temperature of 30°C to 34°C.

使用本發明的無電鍍銅組成物進行無電鍍銅的方法使得能夠具有良好的平均背光值，以用於印刷電路板的通孔的無電鍍銅。這種平均背光值較佳的是大於或等於4.5，更較佳的是為4.6至5，甚至更較佳的是為4.7至5，最較佳的是為4.8至5。這種高平均背光值使得本發明的使用本發明的無電鍍銅組成物進行無電鍍銅的方法能夠用於商業無電鍍銅，其中印刷電路板工業基本上需要4.5和更大的背光值。本發明的無電鍍銅金屬組成物和方法即使在高鍍速下也能在寬濃度範圍的吡啶鎓化合物或其鹽上實現均勻、光亮的銅沈積。The method of electroless copper plating using the electroless copper composition of the present invention makes it possible to have a good average backlight value for electroless copper plating of through holes of a printed circuit board. This average backlight value is preferably greater than or equal to 4.5, more preferably 4.6 to 5, even more preferably 4.7 to 5, and most preferably 4.8 to 5. This high average backlight value enables the method of the present invention for electroless copper plating using the electroless copper composition of the present invention to be used in commercial electroless copper plating, where the printed circuit board industry basically requires a backlight value of 4.5 and greater. The electroless copper metal composition and method of the present invention can achieve uniform and bright copper deposition on a wide concentration range of pyridinium compounds or their salts even at high plating rates.

以下實例不是為了限制本發明的範圍，而是為了進一步說明本發明。 實例1 含有吡啶鎓化合物的無電鍍銅鍍浴的無電鍍銅鍍速The following examples are not intended to limit the scope of the invention, but to further illustrate the invention. Example 1 Electroless copper plating rate of electroless copper plating bath containing pyridinium compound

製備十（10）種無電鍍銅鍍浴。所有十種浴均包含以下組分： 1. 10 g/L五水合硫酸銅 2. 40 g/L羅謝爾鹽 3. 8 g/L氫氧化鈉 4. 4 g/L甲醛 5. 0.5 ppm 2,2’-二硫代二琥珀酸 6. 水（餘量）Ten (10) electroless copper plating baths were prepared. All ten baths contain the following components: 1. 10 g/L copper sulfate pentahydrate 2. 40 g/L Rochelle salt 3. 8 g/L sodium hydroxide 4. 4 g/L formaldehyde 5. 0.5 ppm 2,2’-dithiodisuccinic acid 6. Water (surplus)

每個浴的pH為13。以表1中所指示的量向九（9）種無電鍍組成物中添加以下吡啶鎓化合物中的一種。浴10為對照，其中未添加吡啶鎓化合物。 [表1]

The pH of each bath was 13. One of the following pyridinium compounds was added to the nine (9) electroless plating compositions in the amounts indicated in Table 1. Bath 10 is a control in which no pyridinium compound is added. [Table 1]

每種浴用於在NP140材料（南亞，台灣）的裸露環氧樹脂襯底上鍍銅。在無電鍍銅之前，首先根據以下製程處理每種環氧樹脂基材： (1) 在40°C下施加調理劑231，持續1.5分鐘； (2) 在室溫下用去離子水沖洗2分鐘； (3) 在室溫下施加硝酸預浸料pH = 2，持續0.5分鐘； (4) 在室溫下用去離子水沖洗2分鐘； (5) 在40°C下施加100 ppm的CIRCUPOSIT™ 6530離子鈀催化劑，持續1分鐘； (6) 在室溫下用去離子水沖洗1分鐘； (7) 在32°C下，施加5 g/L硼酸和0.6 g/L二甲胺硼烷水溶液，持續1分鐘；以及 (8) 在室溫下用去離子水沖洗1分鐘。Each bath is used to plate copper on bare epoxy substrate of NP140 material (South Asia, Taiwan). Before electroless copper plating, first treat each epoxy resin substrate according to the following process: (1) Apply Conditioner 231 at 40°C for 1.5 minutes; (2) Rinse with deionized water at room temperature for 2 minutes; (3) Apply nitric acid prepreg pH = 2 at room temperature for 0.5 minutes; (4) Rinse with deionized water at room temperature for 2 minutes; (5) Apply 100 ppm CIRCUPOSIT™ 6530 ionized palladium catalyst at 40°C for 1 minute; (6) Rinse with deionized water for 1 minute at room temperature; (7) At 32°C, apply 5 g/L boric acid and 0.6 g/L dimethylamine borane in water for 1 minute; and (8) Rinse with deionized water for 1 minute at room temperature.

在34°C下進行無電鍍銅5分鐘。鍍速藉由在無電鍍銅之前使用常規實驗室分析天平稱量每個基材然後在鍍敷之後稱量每個基材來確定。然後使用每個基材重量的差異，使用層壓板表面積（25 cm² ）和銅沈積密度（8.92 g/cm³ ）來計算沈積厚度，並藉由除以鍍敷時間長度將該值轉換為鍍速。每個浴的鍍速示於表2中。 [表2]

Conduct electroless copper plating at 34°C for 5 minutes. The plating speed is determined by weighing each substrate using a conventional laboratory analytical balance before electroless copper plating and then weighing each substrate after plating. Then, using the difference in the weight of each substrate, the laminate surface area (25 cm ² ) and copper deposition density (8.92 g/cm ³ ) were used to calculate the deposition thickness, and the value was converted to the plating rate by dividing by the plating time length . The plating speed of each bath is shown in Table 2. [Table 2]

在無電鍍銅鍍浴中包含1-丁基吡啶鎓氯化物、1-(3-磺丙基)吡啶鎓氫氧化物或1-(4-吡啶基)吡啶鎓氯化物提高了鍍速。在2.5 ppm、10 ppm和20 ppm的濃度下，含有1-丁基吡啶鎓氯化物和1-(3-磺丙基)吡啶鎓氫氧化物的浴的銅沈積在基本上所有環氧樹脂襯底上呈現為明亮且均勻的。由含有1-(4-吡啶基)吡啶鎓氯化物的浴電鍍的銅表現出明亮和均勻的區域，具有極少粗糙的沈積斑塊。從對照浴中鍍敷的銅沈積顯示出大面積的不規則和粗糙的黑色沈積，其具有較小的光亮沈積區域。 實例2（對比例） 含有吡啶（游離氮鹼）的無電鍍銅鍍浴的無電鍍銅鍍速The inclusion of 1-butylpyridinium chloride, 1-(3-sulfopropyl)pyridinium hydroxide or 1-(4-pyridyl)pyridinium chloride in the electroless copper plating bath increases the plating rate. At concentrations of 2.5 ppm, 10 ppm and 20 ppm, the copper of the bath containing 1-butylpyridinium chloride and 1-(3-sulfopropyl)pyridinium hydroxide is deposited on essentially all epoxy resin linings The bottom is bright and uniform. Copper plated from a bath containing 1-(4-pyridyl)pyridinium chloride exhibits bright and uniform areas with very few rough patches of deposition. The copper deposit plated from the control bath showed a large area of irregular and rough black deposits with smaller bright deposit areas. Example 2 (Comparative example) Electroless copper plating rate of electroless copper plating bath containing pyridine (free nitrogen base)

製備三（3）個無電鍍銅鍍浴。所有三個浴包括以下組分： 1. 10 g/L五水合硫酸銅 2. 40 g/L羅謝爾鹽 3. 8 g/L氫氧化鈉 4. 4 g/L甲醛 5. 0.5 ppm 2,2’-二硫代二琥珀酸 6. 水（餘量）Prepare three (3) electroless copper plating baths. All three baths include the following components: 1. 10 g/L copper sulfate pentahydrate 2. 40 g/L Rochelle salt 3. 8 g/L sodium hydroxide 4. 4 g/L formaldehyde 5. 0.5 ppm 2,2’-dithiodisuccinic acid 6. Water (surplus)

每個浴的pH為13。以2.5 ppm（對比浴1）、10 ppm（對比浴2）或20 ppm（對比浴3）的量向浴添加吡啶。The pH of each bath was 13. Add pyridine to the bath in amounts of 2.5 ppm (Comparative Bath 1), 10 ppm (Comparative Bath 2), or 20 ppm (Comparative Bath 3).

每個浴用於在環氧基材上鍍銅。如實例1中所述，在準備無電鍍銅電鍍時處理環氧樹脂基材。在34°C下進行無電鍍銅5分鐘。隨後如實例1中所述的測定鍍速。每個浴的鍍速示於表3中。 [表3]

Each bath is used to plate copper on an epoxy substrate. As described in Example 1, the epoxy resin substrate was treated in preparation for electroless copper plating. Conduct electroless copper plating at 34°C for 5 minutes. The plating rate was then determined as described in Example 1. The plating speed of each bath is shown in Table 3. [table 3]

儘管在2.5 ppm下吡啶的鍍速高於實例1中的對照，但在較高的濃度10 ppm和20 ppm下，鍍速下降至低於對照的鍍速。吡啶的鍍速小於實例1中無電鍍銅浴的鍍速。銅沈積具有明亮均勻區域和粗糙陰暗區域的混合物。 實例3 含有吡啶鎓化合物和鹽酸胍的無電鍍銅鍍浴的無電鍍銅鍍速Although the plating rate of pyridine at 2.5 ppm is higher than that of the control in Example 1, at higher concentrations of 10 ppm and 20 ppm, the plating rate drops to lower than that of the control. The plating rate of pyridine is lower than that of the electroless copper bath in Example 1. The copper deposit has a mixture of bright uniform areas and rough dark areas. Example 3 Electroless copper plating rate of electroless copper plating bath containing pyridinium compound and guanidine hydrochloride

製備十四（14）個無電鍍銅鍍浴。所有十四個浴包括以下組分： 1. 10 g/L五水合硫酸銅 2. 40 g/L羅謝爾鹽 3. 8 g/L氫氧化鈉 4. 4 g/L甲醛 5. 0.5 ppm 2,2’-二硫代二琥珀酸 6. 0.36 ppm鹽酸胍 7. 水（餘量）Fourteen (14) electroless copper plating baths were prepared. All fourteen baths include the following components: 1. 10 g/L copper sulfate pentahydrate 2. 40 g/L Rochelle salt 3. 8 g/L sodium hydroxide 4. 4 g/L formaldehyde 5. 0.5 ppm 2,2’-dithiodisuccinic acid 6. 0.36 ppm guanidine hydrochloride 7. Water (surplus)

每個浴的pH為13。以表4中所指示的量向十三（13）個無電鍍組成物中添加以下吡啶鎓化合物中的一種。浴24為對照，其中未添加吡啶鎓化合物。 [表4]

The pH of each bath was 13. To the thirteen (13) electroless plating compositions, one of the following pyridinium compounds was added in the amounts indicated in Table 4. Bath 24 is a control in which no pyridinium compound is added. [Table 4]

每個浴用於在裸露環氧基材上鍍銅。如實例1所述，在無電鍍銅之前處理每個環氧基材。在34°C下進行無電鍍銅5分鐘。如上文實例1中所述測定鍍速。每個浴的鍍速示於表5中。 [表5]

Each bath is used to plate copper on bare epoxy substrate. As described in Example 1, each epoxy substrate was processed before electroless copper plating. Conduct electroless copper plating at 34°C for 5 minutes. The plating rate was determined as described in Example 1 above. The plating speed of each bath is shown in Table 5. [table 5]

在無電鍍銅鍍浴中包含1-丁基吡啶鎓氯化物、1-(3-磺丙基)吡啶鎓氫氧化物或1-(4-吡啶基)吡啶鎓氯化物相比包含鹽酸胍的對照提高了鍍速。含有1-丁基吡啶鎓氯化物和1-(3-磺丙基)吡啶鎓氫氧化物的浴的銅沈積在基本上所有環氧樹脂襯底上呈現為明亮且均勻的。由含有1-(4-吡啶基)吡啶鎓氯化物的浴電鍍的銅表現出明亮和均勻的區域，具有極少粗糙的沈積斑塊。從對照浴鍍敷的銅沈積顯示出與較大區域的不規則和粗糙沈積混合的較小區域的光亮沈積。 實例4（對比例） 含有吡啶（游離氮鹼）和鹽酸胍的無電鍍銅鍍浴的無電鍍銅鍍速Containing 1-butylpyridinium chloride, 1-(3-sulfopropyl)pyridinium hydroxide, or 1-(4-pyridyl)pyridinium chloride in the electroless copper plating bath compared to those containing guanidine hydrochloride The control increases the plating speed. The copper deposits of the bath containing 1-butylpyridinium chloride and 1-(3-sulfopropyl)pyridinium hydroxide appear bright and uniform on essentially all epoxy resin substrates. Copper plated from a bath containing 1-(4-pyridyl)pyridinium chloride exhibits bright and uniform areas with very few rough patches of deposition. The copper deposit plated from the control bath showed a bright deposit in a smaller area mixed with irregular and rough deposits in a larger area. Example 4 (Comparative example) Electroless copper plating rate of electroless copper plating bath containing pyridine (free nitrogen base) and guanidine hydrochloride

製備五（5）個無電鍍銅鍍浴。所有五個浴包括以下組分： 1. 10 g/L五水合硫酸銅 2. 40 g/L羅謝爾鹽 3. 8 g/L氫氧化鈉 4. 4 g/L甲醛 5. 0.5 ppm 2,2’-二硫代二琥珀酸 6. 0.36 ppm鹽酸胍 7. 水（餘量）Five (5) electroless copper plating baths were prepared. All five baths include the following components: 1. 10 g/L copper sulfate pentahydrate 2. 40 g/L Rochelle salt 3. 8 g/L sodium hydroxide 4. 4 g/L formaldehyde 5. 0.5 ppm 2,2’-dithiodisuccinic acid 6. 0.36 ppm guanidine hydrochloride 7. Water (surplus)

每個浴的pH為13。以2.5 ppm（對比浴4）、5 ppm（對比浴5）、10 ppm（對比浴6）、15 ppm（對比浴7）或20 ppm（對比浴8）的量向浴中添加吡啶。The pH of each bath was 13. Add pyridine to the bath in amounts of 2.5 ppm (Comparative Bath 4), 5 ppm (Comparative Bath 5), 10 ppm (Comparative Bath 6), 15 ppm (Comparative Bath 7), or 20 ppm (Comparative Bath 8).

每個浴用於在環氧基材上鍍銅。如實例1中所述，在無電鍍銅之前處理環氧樹脂基材。在34°C下進行無電鍍銅5分鐘。如上文實例1中所述測定鍍速。每個浴的鍍速示於表6中。 [表6]

Each bath is used to plate copper on an epoxy substrate. As described in Example 1, the epoxy resin substrate was treated before electroless copper plating. Conduct electroless copper plating at 34°C for 5 minutes. The plating rate was determined as described in Example 1 above. The plating speed of each bath is shown in Table 6. [Table 6]

即使與促進劑鹽酸胍組合，含有鹼吡啶的無電鍍銅浴的最高鍍速略高於0.60 µm/5 min。通常，提高無電鍍浴中的吡啶濃度顯示出無電鍍銅鍍速降低的趨勢。銅沈積具有明亮且均勻的區域，間雜有粗糙陰暗區域。 實例5 含有吡啶鎓化合物的本發明含水鹼性無電銅組成物的背光實驗Even in combination with the accelerator guanidine hydrochloride, the maximum plating speed of electroless copper baths containing alkali pyridine is slightly higher than 0.60 µm/5 min. Generally, increasing the pyridine concentration in an electroless plating bath shows a tendency for the electroless copper plating rate to decrease. The copper deposits have bright and uniform areas, with rough and dark areas interspersed. Example 5 Backlight experiment of aqueous alkaline electroless copper composition of the present invention containing pyridinium compound

製備本發明的以下含水鹼性無電銅組成物，其具有下表7中公開的組分和量。 [表7]

The following aqueous alkaline electroless copper composition of the present invention was prepared having the components and amounts disclosed in Table 7 below. [Table 7]

如使用可從飛世爾科技（Fisher Scientific）獲得的常規pH計所測量的，含水鹼性無電銅組成物的pH在室溫下的pH = 13。As measured using a conventional pH meter available from Fisher Scientific, the pH of the aqueous alkaline electroless copper composition is pH=13 at room temperature.

提供具有多個通孔的六（6）個不同FR/4玻璃環氧板：TUC-662、SY-1141、IT-180、370HR、EM825和NPGN。板係八層銅包覆板。TUC-662獲自台灣積聯科技（Taiwan Union Technology），SY-1141獲自盛益（Shengyi）。IT-180獲自聯茂電子股份有限公司（ITEQ Corp.），NPGN獲自南亞（NanYa），370HR獲自Isola，EM825獲自億利達機械製品有限公司（Elite Materials Corporation）。板的T_g 值範圍為140°C至180°C。每塊板為5cm x 10cm。Six (6) different FR/4 glass epoxy boards with multiple through holes are provided: TUC-662, SY-1141, IT-180, 370HR, EM825, and NPGN. The board is an eight-layer copper-clad board. TUC-662 was obtained from Taiwan Union Technology, and SY-1141 was obtained from Shengyi. IT-180 was obtained from ITEQ Corp., NPGN was obtained from NanYa, 370HR was obtained from Isola, and EM825 was obtained from Elite Materials Corporation. The _Tg value of the board ranges from 140°C to 180°C. Each board is 5cm x 10cm.

如下處理每個板的通孔： 1. 在80°C下用CIRCUPOSIT™ Hole Prep 3303溶液對每塊板的通孔去污6分鐘； 2. 然後用流動的自來水沖洗每個板的通孔2分鐘； 3. 然後在80°C下用CIRCUPOSIT™ MLB Promoter 3308過錳酸鹽水溶液處理通孔8分鐘； 4. 然後將通孔在流動的自來水中沖洗4分鐘； 5. 然後在室溫下用3wt%硫酸/3wt%過氧化氫中和劑處理通孔2分鐘； 6. 然後用流動的自來水沖洗每個板的通孔2分鐘； 7. 然後在60°C下用CIRCUPOSIT™調理劑231鹼性溶液處理每個板的通孔1.5分鐘； 8. 然後用流動的自來水沖洗通孔2分鐘； 9. 然後在室溫下用過硫酸鈉/硫酸蝕刻溶液處理通孔1分鐘； 10. 然後用流動的去離子水沖洗每個板的通孔1分鐘； 11. 然後在室溫下將面板浸入酸性Pre-Dip CIRCUPOSIT™ 6520中持續0.5 min.並隨後在40℃下浸入CIRCUPOSIT™ 6530催化劑（其為離子含水鹼性鈀催化劑濃縮物（可購自陶氏電子材料公司））持續1 min.，其中催化劑用足夠量的碳酸鈉、氫氧化鈉或硝酸緩衝以實現9-9.5的催化劑pH； 12. 然後在室溫下用流動的去離子水沖洗每個板的通孔1分鐘； 13. 然後在32°C下將板浸入0.6 g/L二甲胺硼烷和5 g/L硼酸溶液中1分鐘以將鈀離子還原成鈀金屬 14. 然後用流動的去離子水沖洗每個板的通孔1分鐘； 15. 然後將板浸入表7的無電鍍銅組成物中，並將銅在34°C下，在pH 13下鍍敷，並將銅沈積在通孔壁上5分鐘； 16. 然後用流動的自來水沖洗鍍銅板4分鐘； 17. 然後用壓縮空氣乾燥每個鍍銅板；並且 18. 使用下面描述的背光處理檢查板的通孔壁的鍍銅覆蓋。Process the through holes of each board as follows: 1. Decontaminate the through holes of each board with CIRCUPOSIT™ Hole Prep 3303 solution at 80°C for 6 minutes; 2. Then rinse the through holes of each plate with running tap water for 2 minutes; 3. Then treat the through hole with CIRCUPOSIT™ MLB Promoter 3308 permanganate aqueous solution at 80°C for 8 minutes; 4. Then rinse the through hole in flowing tap water for 4 minutes; 5. Then treat the through hole with 3wt% sulfuric acid/3wt% hydrogen peroxide neutralizer at room temperature for 2 minutes; 6. Then rinse the through holes of each plate with running tap water for 2 minutes; 7. Then treat the through holes of each plate with CIRCUPOSIT™ Conditioner 231 alkaline solution at 60°C for 1.5 minutes; 8. Then rinse the through hole with running tap water for 2 minutes; 9. Then treat the through hole with sodium persulfate/sulfuric acid etching solution at room temperature for 1 minute; 10. Then rinse the through holes of each plate with flowing deionized water for 1 minute; 11. The panel is then immersed in the acidic Pre-Dip CIRCUPOSIT™ 6520 at room temperature for 0.5 min. and then immersed in the CIRCUPOSIT™ 6530 catalyst (which is an ionized aqueous alkaline palladium catalyst concentrate (available from Dow) at 40°C Electronic Materials Company)) for 1 min., where the catalyst is buffered with a sufficient amount of sodium carbonate, sodium hydroxide or nitric acid to achieve a catalyst pH of 9-9.5; 12. Then rinse the through holes of each plate with flowing deionized water at room temperature for 1 minute; 13. Then immerse the plate in a solution of 0.6 g/L dimethylamine borane and 5 g/L boric acid at 32°C for 1 minute to reduce palladium ions to palladium metal 14. Then rinse the through holes of each plate with flowing deionized water for 1 minute; 15. The board was then immersed in the electroless copper composition of Table 7, and the copper was plated at 34°C and pH 13 and the copper was deposited on the wall of the through hole for 5 minutes; 16. Then rinse the copper plate with running tap water for 4 minutes; 17. Then dry each copper plate with compressed air; and 18. Use the backlighting described below to inspect the copper plating of the through-hole walls of the board.

每個板在盡可能最接近通孔中心處橫切以暴露鍍銅壁。從每個面板獲取距通孔中心不超過3 mm厚的橫截面，放置在具有50X放大倍數的常規光學顯微鏡下，其中光源置於樣品後面。銅沈積的品質由顯微鏡下透過樣品的可見光量確定。在鍍通孔內，透射光僅在具有不完全無電鍍覆蓋率的區域可見。如果沒有光投射並且該截面看起來完全係黑色的，則在背光量表上評級為5，表示通孔壁的完全銅覆蓋。如果光穿過整個區域而沒有任何暗區，則表明通孔壁上極少至沒有銅金屬沈積，並且該截面的評級為0。如果截面具有一些暗區域以及亮區域，則它們的評級在0到5之間。每個板材至少檢查10個通孔並對其評級。背光值為4.5和更大表示鍍敷工業中的商業上可接受的催化劑。Each board is cut as close as possible to the center of the through hole to expose the copper plated wall. A cross section not thicker than 3 mm from the center of the through hole was taken from each panel and placed under a conventional optical microscope with a magnification of 50X, where the light source was placed behind the sample. The quality of the copper deposit is determined by the amount of visible light that passes through the sample under the microscope. Within plated-through holes, transmitted light is only visible in areas with incomplete electroless plating coverage. If there is no light projection and the cross-section looks completely black, it is rated 5 on the backlight scale, indicating complete copper coverage of the via wall. If the light passes through the entire area without any dark areas, it means that there is very little to no copper metal deposition on the walls of the vias, and the cross-sectional rating is 0. If the cross-section has some dark areas and bright areas, their ratings are between 0 and 5. Check at least 10 through holes for each board and rate them. A backlight value of 4.5 and greater indicates a commercially acceptable catalyst in the plating industry.

每種類型的FR/4玻璃環氧板的平均背光值公開在下表中。 [表8]

The average backlight value of each type of FR/4 glass epoxy board is disclosed in the table below. [Table 8]

總體而言，兩個浴示出了極其良好的背光值。Overall, the two baths showed extremely good backlight values.

無no

無no

無no

Claims (11)

一種無電鍍銅組成物，其包含一種或多種銅離子源，一種或多種吡啶鎓化合物，一種或多種錯合劑，一種或多種還原劑，和視情況一種或多種pH調節劑，其中該無電鍍銅組成物的pH大於7。An electroless copper composition comprising one or more copper ion sources, one or more pyridinium compounds, one or more complexing agents, one or more reducing agents, and optionally one or more pH adjusting agents, wherein the electroless copper The pH of the composition is greater than 7. 如申請專利範圍第1項所述之無電鍍銅組成物，其中該一種或多種吡啶鎓化合物或其鹽的量為至少0.5 ppm。The electroless copper composition as described in item 1 of the patent application scope, wherein the amount of the one or more pyridinium compounds or salts thereof is at least 0.5 ppm. 如申請專利範圍第1項所述之無電鍍銅組成物，其中該一種或多種吡啶化合物具有下式：

(I) 其中R₁ 選自由以下各項組成的組：直鏈或支鏈的取代或未取代的(C₁ -C₁₀ )烷基、取代或未取代的(C₆ -C₁₀ )芳基、取代或未取代的(C₆ -C₁₀ )雜環芳香族基團和取代或未取代的苄基；並且R₂ 選自由以下各項組成的組：氫、羥基、硫酸酯、胺基、羰基、羧基、乙烯基和醯胺。The electroless copper composition as described in item 1 of the patent application scope, wherein the one or more pyridine compounds have the following formula:

(I) wherein R _{1 is} selected from the group consisting of linear or branched substituted or unsubstituted (C ₁ -C ₁₀ )alkyl, substituted or unsubstituted (C ₆ -C ₁₀ )aryl , Substituted or unsubstituted (C ₆ -C ₁₀ ) heterocyclic aromatic group and substituted or unsubstituted benzyl; and R _{2 is} selected from the group consisting of hydrogen, hydroxyl, sulfate, amine, Carbonyl, carboxyl, vinyl and amide. 如申請專利範圍第1項所述之無電鍍銅組成物，其中該一種或多種錯合劑選自酒石酸鉀鈉，酒石酸鈉，水楊酸鈉，乙二胺四乙酸的鈉鹽，氮川乙酸及其鹼金屬鹽，葡萄糖酸，葡萄糖酸鹽，三乙醇胺，改性乙二胺四乙酸，S,S-乙二胺二琥珀酸，乙內醯脲和乙內醯脲衍生物。The electroless copper composition as described in item 1 of the patent application scope, wherein the one or more complexing agents are selected from the group consisting of potassium sodium tartrate, sodium tartrate, sodium salicylate, sodium salt of ethylenediaminetetraacetic acid, nitroacetic acid and Its alkali metal salts, gluconic acid, gluconate, triethanolamine, modified ethylenediaminetetraacetic acid, S,S-ethylenediamine disuccinic acid, hydantoin and hydantoin derivatives. 如申請專利範圍第1項所述之無電鍍銅組成物，其中該一種或多種還原劑選自醛、硼氫化物、取代的硼氫化物、硼烷、糖和次磷酸鹽。The electroless copper composition as described in item 1 of the patent application scope, wherein the one or more reducing agents are selected from the group consisting of aldehyde, borohydride, substituted borohydride, borane, sugar and hypophosphite. 如申請專利範圍第1項所述之無電鍍銅組成物，其還包含一種或多種選自輔助促進劑、晶粒細化劑和穩定劑的化合物。The electroless copper composition as described in item 1 of the scope of the patent application, which further contains one or more compounds selected from auxiliary accelerators, grain refiners and stabilizers. 一種無電鍍銅方法，其包括： a) 提供包含電介質的基材； b) 將催化劑施加到該包含電介質的基材上； c) 將無電鍍銅組成物施加到該包含電介質的基材上，其中該無電鍍銅組成物包含一種或多種銅離子源，一種或多種吡啶鎓化合物，一種或多種錯合劑，一種或多種還原劑，和視情況一種或多種pH調節劑，其中該無電鍍銅組成物的pH大於7；並且 d) 用該無電鍍銅組成物在該包含電介質的基材上無電鍍銅。An electroless copper plating method, including: a) Provide a substrate containing dielectric; b) apply the catalyst to the substrate containing the dielectric; c) applying the electroless copper composition to the dielectric-containing substrate, wherein the electroless copper composition comprises one or more sources of copper ions, one or more pyridinium compounds, one or more complexing agents, one or more reducing agents Agent, and optionally one or more pH adjusting agents, wherein the pH of the electroless copper composition is greater than 7; and d) Use the electroless copper composition to electroless copper on the dielectric-containing substrate. 如申請專利範圍第7項所述之方法，其中該一種或多種吡啶鎓化合物或其鹽的量為至少0.5 ppm。The method as described in item 7 of the patent application range, wherein the amount of the one or more pyridinium compounds or salts thereof is at least 0.5 ppm. 如申請專利範圍第7項所述之方法，其中該無電鍍銅組成物進一步包括一種或多種選自穩定劑和輔助促進劑的化合物。The method as described in item 7 of the patent application scope, wherein the electroless copper plating composition further includes one or more compounds selected from stabilizers and auxiliary accelerators. 如申請專利範圍第7項所述之方法，其中該無電鍍銅組成物處於40°C或更低下。The method as described in item 7 of the patent application scope, wherein the electroless copper composition is at 40°C or lower. 如申請專利範圍第7項所述之方法，其中該催化劑係鈀催化劑。The method as described in item 7 of the patent application scope, wherein the catalyst is a palladium catalyst.