TWI606140B - Electroless copper plating bath and electroless copper plating method for increasing hardness of copper plating - Google Patents

Electroless copper plating bath and electroless copper plating method for increasing hardness of copper plating Download PDF

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TWI606140B
TWI606140B TW105138386A TW105138386A TWI606140B TW I606140 B TWI606140 B TW I606140B TW 105138386 A TW105138386 A TW 105138386A TW 105138386 A TW105138386 A TW 105138386A TW I606140 B TWI606140 B TW I606140B
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copper plating
electroless copper
agent
leveling agent
concentration
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TW105138386A
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Chinese (zh)
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TW201723223A (en
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Ming-Guo Wei
Yan-Jin Lin
Chun-Ru Lin
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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
    • 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
    • C23C18/405—Formaldehyde

Description

無電鍍銅鍍液及增加銅鍍層硬度的無電鍍銅方法Electroless copper plating bath and electroless copper plating method for increasing the hardness of copper plating

本發明是有關於一種銅鍍液及鍍銅方法，特別是指一種無電鍍銅鍍液及無電鍍銅方法。The invention relates to a copper plating solution and a copper plating method, in particular to an electroless copper plating solution and an electroless copper plating method.

無電鍍(electroless plating)，又稱化學鍍(chemical plating)或自催化電鍍(auto-catalytic plating)，其是在高分子的物體表面，以化學氧化還原之方式，形成一層厚度約在0.2至2微米的連續金屬層，使非導體的物體表面能被導通，以利後續電鍍的作業。此種鍍銅方式，具有鍍層均勻、鍍層孔率低、操作簡單、可鍍在非導體上…等優點，常在塑膠上進行，又或者用於印刷電路板(PCB)之穿孔鍍層，以及MID(Molded Interconnect Device)製程。Electroless plating, also known as chemical plating or auto-catalytic plating, is formed on the surface of a polymer object by chemical redox to form a layer having a thickness of about 0.2 to 2. The micron continuous metal layer enables the surface of the non-conductor object to be turned on for subsequent electroplating operations. The copper plating method has the advantages of uniform plating, low plating porosity, simple operation, plating on non-conductors, etc., and is often performed on plastic, or used for perforated plating of printed circuit boards (PCB), and MID. (Molded Interconnect Device) process.

所謂的MID製程，是透過雷射雕刻技術在非導電基材上雕刻出3D立體線路，之後，再以無電鍍銅的方式，在前述所雕刻出的內凹線路中直接鍍出超過8微米厚的銅鍍層(通常為12微米)，接著再披覆上一層薄的金層、銀層或銅保護劑，以防止銅鍍層氧化。MID製程已廣泛用於智慧型手機、IPad或傳輸元件中的天線製造，主要能提供足夠之電通量以利訊號之傳輸。然而，手機訊號之傳輸由原先之2G、3G，演進至現今的4G，天線在精準度上的要求越來越嚴苛，而在作業時，銅鍍層難免會遭受碰撞而產生刻痕，又或者再進行組裝時，因硬度不足，使得與其他元件相接觸時鍍層表面產生缺陷。然而，現今多採用高頻訊號，其是行走在導電體的表面，當表面產生刻痕或者其他缺陷，將對天線的表現有不利的影響。The so-called MID process is to engrave a 3D three-dimensional line on a non-conductive substrate by laser engraving technology, and then directly plate the above-mentioned engraved recessed line to a thickness of more than 8 μm by electroless copper plating. The copper plating (usually 12 microns) is then coated with a thin layer of gold, silver or copper to prevent oxidation of the copper coating. The MID process has been widely used in the manufacture of antennas in smart phones, IPads or transmission components, and is primarily capable of providing sufficient electrical flux for signal transmission. However, the transmission of mobile phone signals has evolved from the original 2G and 3G to the current 4G. The accuracy of the antenna is becoming more and more stringent. In operation, the copper plating will inevitably be subject to collision and nicking, or When the assembly is performed again, the surface of the plating layer is defective when it comes into contact with other elements due to insufficient hardness. However, high frequency signals are often used today, which are walking on the surface of the electrical conductor. When the surface is scored or other defects, it will have an adverse effect on the performance of the antenna.

無電鍍是採用化學氧化還原之方式成長金屬層，因此金屬原子之間的堆疊較不緊密，且沒有特定的排列方向，導致硬度較低，有改進的需要。Electroless plating is the use of chemical redox to grow the metal layer, so the stacking between the metal atoms is less tight, and there is no specific alignment direction, resulting in lower hardness and improved needs.

因此，本發明之目的，即在提供一種無電鍍銅鍍液，其能使無電鍍銅層具有較高的硬度。Accordingly, it is an object of the present invention to provide an electroless copper plating bath which imparts a higher hardness to an electroless copper plating layer.

於是，本發明無電鍍銅鍍液，含有溶劑、銅離子、錯合劑、還原劑、整平劑，及增硬劑，其中，整平劑選自聚亞胺、咪唑系季銨鹽材料或其等的組合，增硬劑選自鉈離子、碲離子、硒離子，或上述任意的組合。Therefore, the electroless copper plating solution of the present invention contains a solvent, a copper ion, a complexing agent, a reducing agent, a leveling agent, and a hardening agent, wherein the leveling agent is selected from the group consisting of polyimine, imidazole quaternary ammonium salt material or In combination, the hardening agent is selected from the group consisting of cerium ions, cerium ions, selenium ions, or any combination thereof.

銅離子係源自水溶性銅鹽。前述水溶性銅鹽選自硫酸銅、氯化銅、硝酸銅、甲基磺酸銅，或上述任意的組合。The copper ion is derived from a water-soluble copper salt. The water-soluble copper salt is selected from the group consisting of copper sulfate, copper chloride, copper nitrate, copper methanesulfonate, or any combination thereof.

本發明所採用的增硬劑屬離子型，在鍍液中以離子之形式存在，並能形成負電集團而與銅共析出。較佳地，鉈離子是源自甲酸鉈(Thallium formate)，碲離子是源自二氧化碲(Tellurium dioxide)，硒離子是源自硒氰酸鉀(Potassium selenocyanate)。The hardening agent used in the present invention is of an ionic type, exists in the form of ions in the plating solution, and can form a negative electricity group and co-precipitate with copper. Preferably, the cerium ion is derived from Thallium formate, the cerium ion is derived from Tellurium dioxide, and the selenium ion is derived from Potassium selenocyanate.

為使鍍層具有更佳的硬度且維持鍍層的性質。因此較佳地，增硬劑之濃度為0.001至0.1g/L(即：1至100ppm)，而更佳地，增硬劑之濃度為0.002至0.05g/L(即：2至50ppm)。In order to make the coating have better hardness and maintain the properties of the coating. Therefore, preferably, the concentration of the hardening agent is 0.001 to 0.1 g/L (i.e., 1 to 100 ppm), and more preferably, the concentration of the hardening agent is 0.002 to 0.05 g/L (i.e., 2 to 50 ppm).

整平劑能減小鍍層微觀凹凸不平幅度，使鍍層表面平整光滑。本發明是採用聚亞胺、咪唑系季銨鹽材料作為整平劑，其本身穩定，較不易被裂解或反應而喪失效果。較佳地，該聚亞胺的數目平均分子量範圍為100至3000。該聚亞胺例如但不限於聚乙烯亞胺(即：polyethylenimine)。該咪唑系季銨鹽材料例如但不限於咪唑系季銨鹽化合物或咪唑系季銨鹽聚合物。該咪唑系季銨鹽化合物例如但不限於由包含咪唑系化合物與季胺化劑的組分進行季銨化(quaterisation)反應所形成的水溶性產物。該咪唑系季銨鹽聚合物例如但不限於由該咪唑系季銨鹽化合物經聚合反應所形成的產物。該咪唑系季銨鹽聚合物例如但不限於咪唑/環氧氯丙烷共聚物(即：imidazole/epichlorohydrin copolymer)。該咪唑系化合物可單一使用或混合多種使用，且該咪唑系化合物例如但不限於咪唑(imidazole)、1-甲基咪唑(1-methylimidazole)、1-乙基咪唑(1-ethylimidazole)、2-甲基咪唑(2-methylimidazole)、1,5-二甲基咪唑(1,5-dimethylimidazole)、1-乙基-2甲基咪唑 (1-ethyl-2-methylimidazole)、1-甲氧基咪唑(1-oxymethylimidazole)，或 1-乙烯基咪唑(1-vinyl imidazole)等。該季銨化劑可單一使用或混合多種使用，且該季銨化劑例如但不限於環氧氯丙烷(epichlorohydrin)、一氯乙酸(monochloroacetic acid)、氯化苄(benzyl chloride)、氯乙醯胺(chloroacetoamide)、 3-胺基苯甲醯氯(3-aminobenzyl chloride)、二氯甘油(dichloroglycerine)、碘甲烷 (methyl iodide)、烯丙基氯(allyl chloride)、二氯乙烷(dichloroethane)，或單氯丙烷(monochloropropane)等。以該咪唑系化合物的用量為1莫耳計，該季銨化劑的用量範圍為1莫耳至1.5莫耳。該季銨化反應的操作溫度範圍為40℃至100℃。該季銨化反應的操作時間範圍為0.5至4小時。較佳地，該整平劑的聚亞胺為聚乙烯亞胺，該整平劑的咪唑系季銨鹽材料為咪唑/環氧氯丙烷共聚物。The leveling agent can reduce the micro unevenness of the coating layer and make the surface of the coating smooth and smooth. The invention adopts a polyimine and an imidazole-based quaternary ammonium salt material as a leveling agent, which is stable in itself and is less susceptible to being cracked or reacted to lose the effect. Preferably, the polyimine has a number average molecular weight ranging from 100 to 3,000. The polyimine is for example but not limited to polyethyleneimine (ie polyethylenimine). The imidazole-based quaternary ammonium salt material is, for example but not limited to, an imidazole-based quaternary ammonium salt compound or an imidazole-based quaternary ammonium salt polymer. The imidazole-based quaternary ammonium salt compound is, for example but not limited to, a water-soluble product formed by a quaterisation reaction of a component comprising an imidazole-based compound and a quaternizing agent. The imidazole-based quaternary ammonium salt polymer is, for example but not limited to, a product formed by polymerization of the imidazole-based quaternary ammonium salt compound. The imidazole-based quaternary ammonium salt polymer is, for example but not limited to, an imidazole/epichlorohydrin copolymer (i.e., imidazole/epichlorohydrin copolymer). The imidazole compound may be used singly or in combination, and the imidazole compound is, for example but not limited to, imidazole, 1-methylimidazole, 1-ethylimidazole, 2- 2-methylimidazole, 1,5-dimethylimidazole, 1-ethyl-2-methylimidazole, 1-methoxyimidazole (1-oxymethylimidazole), or 1-vinyl imidazole (1-vinyl imidazole). The quaternizing agent may be used singly or in combination, and the quaternizing agent is, for example but not limited to, epichlorohydrin, monochloroacetic acid, benzyl chloride, chloroacetic acid. Chloroacetoamide, 3-aminobenzyl chloride, dichloroglycerine, methyl iodide, allyl chloride, dichloroethane , or monochloropropane, etc. The quaternizing agent is used in an amount ranging from 1 mole to 1.5 moles, based on the amount of the imidazole compound. The quaternization reaction has an operating temperature in the range of from 40 °C to 100 °C. The quaternization reaction has an operating time ranging from 0.5 to 4 hours. Preferably, the leveling agent of the polyimide is polyethyleneimine, and the imidazole quaternary ammonium salt material of the leveling agent is an imidazole/epichlorohydrin copolymer.

較佳地，前述整平劑的分子量為介於100至3000。更佳的，前述整平劑的分子量為介於200至2000。又更佳地，前述整平劑的分子量為介於150至1500。Preferably, the aforementioned leveling agent has a molecular weight of from 100 to 3,000. More preferably, the aforementioned leveling agent has a molecular weight of from 200 to 2,000. Still more preferably, the aforementioned leveling agent has a molecular weight of from 150 to 1,500.

當整平劑的濃度低於0.01g/L時，平整效果不足，但濃度超過0.8g/L後會降低鍍層成長的速度。因此較佳地，該整平劑的濃度為0.01至0.8g/L(即：10至800ppm)。更佳地該整平劑的濃度為0.02至0.3g/L(即：20至300ppm)。When the concentration of the leveling agent is less than 0.01 g/L, the leveling effect is insufficient, but when the concentration exceeds 0.8 g/L, the growth rate of the plating layer is lowered. Therefore, preferably, the leveling agent has a concentration of 0.01 to 0.8 g/L (i.e., 10 to 800 ppm). More preferably, the leveling agent has a concentration of 0.02 to 0.3 g/L (i.e., 20 to 300 ppm).

當整平劑為聚亞胺時，其濃度較佳地為0.01至0.2g/L(即：10至200ppm)，最佳為0.02至0.15g/L(即：20至150ppm)。當整平劑為咪唑系季銨鹽材料時，其濃度較佳地為0.02至0.8g/L(即：20至800ppm)，最佳為0.05至0.3g/L(即：50至300ppm)。When the leveling agent is a polyimine, the concentration thereof is preferably from 0.01 to 0.2 g/L (i.e., from 10 to 200 ppm), most preferably from 0.02 to 0.15 g/L (i.e., from 20 to 150 ppm). When the leveling agent is an imidazole-based quaternary ammonium salt material, its concentration is preferably 0.02 to 0.8 g/L (i.e., 20 to 800 ppm), most preferably 0.05 to 0.3 g/L (i.e., 50 to 300 ppm).

錯合劑係與金屬離子形成錯合物，能有效提高鍍液穩定性、調整金屬析出的速度，以及改善鍍層的性質。較佳地，該錯合劑選自乙二胺四乙酸四鈉鹽、乙二胺四乙酸(即：Ethylenediaminetetraacetic acid)、N,N,N',N'-四-(2-羥基丙基)-乙烯二胺(即：N,N,N',N'-tetrakis-(2-hydroxypropyl)-ethylenediamine)，或酒石酸鉀鈉(即：Potassium sodium tartrate)。The complexing agent forms a complex with the metal ions, which can effectively improve the stability of the plating solution, adjust the rate of metal precipitation, and improve the properties of the plating layer. Preferably, the complexing agent is selected from the group consisting of tetrasodium ethylenediaminetetraacetate, ethylenediaminetetraacetic acid, N, N, N', N'-tetrakis (2-hydroxypropyl)- Ethylene diamine (i.e., N, N, N', N'-tetrakis-(2-hydroxypropyl)-ethylenediamine), or sodium potassium tartrate (i.e., Potassium sodium tartrate).

當待鍍物表面有氣體析出時，為加速氣體的排出，能加入潤濕劑進行改善。潤濕劑能避免氣體與金屬沈積並列進行，降低針孔的形成。較佳地，無電鍍銅鍍液還含有潤濕劑。更佳地，潤濕劑選自聚醚、聚烯醇或聚磷酸脂(即：Polyphosphoester)。該聚醚例如但不限於聚乙二醇。該聚磷酸脂例如但不限於聚壬基酚聚氧乙烯醚磷酸酯(即：polyoxyethylene nonylphenyl ether branched phosphate)。When gas is deposited on the surface of the object to be plated, in order to accelerate the discharge of the gas, a wetting agent can be added for improvement. The wetting agent prevents gas and metal deposition from juxtaposed, reducing the formation of pinholes. Preferably, the electroless copper plating bath further contains a wetting agent. More preferably, the wetting agent is selected from the group consisting of polyethers, polyenols or polyphosphates (i.e., Polyphosphoester). The polyether is for example but not limited to polyethylene glycol. The polyphosphate is, for example but not limited to, polyoxyethylene nonylphenyl ether branched phosphate.

為了穩定鍍液，能透過添加安定劑的方式，控制鍍液的活性，避免劣化。較佳地，無電鍍銅鍍液還含有安定劑。安定劑選自氰化物(即：Cyanide)或2,2'-聯吡啶(即：2,2'-Bipyridine)。該氰化物例如但不限於亞鐵氰化鉀(Potassium ferrocyanide)。In order to stabilize the plating solution, the activity of the plating solution can be controlled by adding a stabilizer to avoid deterioration. Preferably, the electroless copper plating bath further contains a stabilizer. The stabilizer is selected from the group consisting of cyanide (ie, Cyanide) or 2,2'-bipyridine (ie, 2,2'-Bipyridine). The cyanide is, for example but not limited to, Potassium ferrocyanide.

本發明所採用的還原劑可以為任何在無電鍍銅中習知的組分。而較佳地，該還原劑選自甲醛(即：Formaldehyde)、乙醛酸(即：Glyoxylic acid)、聯胺(即：Hydrazine)、硼氫化鈉(即：Sodium borohydride)、二甲基胺硼烷(即：Dimethylamine borane)、N,N-二乙基胺硼烷(即：N,N-diethylamine borane)，或次磷酸鈉(即：Sodium hypophosphite)。The reducing agent employed in the present invention may be any of the components conventionally known in electroless copper plating. Preferably, the reducing agent is selected from the group consisting of formaldehyde (ie, Formaldehyde), glyoxylic acid (ie, Glyoxylic acid), hydrazine (ie, Hydrazine), sodium borohydride (ie, sodium borohydride), and dimethylamine boron. Alkane (ie: Dimethylamine borane), N,N-diethylamine borane (or N,N-diethylamine borane), or sodium hypophosphite (ie: Sodium hypophosphite).

本發明之另一目的，即在提供一種增加化學銅硬度的無電鍍銅方法，其能使無電鍍銅層具有較高的硬度。Another object of the present invention is to provide an electroless copper plating method which increases the hardness of chemical copper, which enables the electroless copper plating layer to have a higher hardness.

於是，本發明增加銅鍍層硬度的無電鍍銅方法，包含以下步驟:取一試片經前處理後，再浸入如前述之無電鍍銅鍍液，以成長銅鍍層。Therefore, the method for increasing the hardness of the copper plating layer of the present invention comprises the steps of: taking a test piece after pretreatment, and then immersing the electroless copper plating solution as described above to grow the copper plating layer.

鍍層厚度的控制，是透過先計算每單位小時鍍層成長的厚度(即：鍍層成長速率)，再以浸泡時間的控制來調整鍍層厚度。較佳地，鍍層成長速率為4至6微米/小時，更佳地，鍍層成長速率為4.5至5.5微米/小時。對應前述鍍層成長速率，該試片的浸泡時間控制在2至3小時。The thickness of the coating is controlled by first calculating the thickness of the plating growth per unit hour (ie, the growth rate of the coating), and then adjusting the thickness of the coating by the control of the immersion time. Preferably, the plating growth rate is 4 to 6 μm / hr, and more preferably, the plating growth rate is 4.5 to 5.5 μm / hr. The immersion time of the test piece is controlled to 2 to 3 hours in accordance with the aforementioned plating growth rate.

無電鍍銅鍍液的溫度影響到鍍層成長的速度，當溫度低於40°C之時，成長過慢，而當溫度高於60°C之時，則有耗能的問題。因此較佳地，該無電鍍銅鍍液的溫度控制在40至60°C。更佳地，該無電鍍銅鍍液的溫度控制在45至55°C。The temperature of the electroless copper plating bath affects the growth rate of the plating layer. When the temperature is lower than 40 ° C, the growth is too slow, and when the temperature is higher than 60 ° C, there is a problem of energy consumption. Therefore, preferably, the temperature of the electroless copper plating bath is controlled at 40 to 60 °C. More preferably, the temperature of the electroless copper plating bath is controlled at 45 to 55 °C.

本發明之功效在於：透過添加增硬劑，提高鍍層硬度，並再選用特定的整平劑，迫使銅離子有較為一致的排列，讓所添加的增硬劑均勻地分佈於銅晶粒的周圍，讓鍍層的硬度更為提升。The effect of the invention is: by adding a hardening agent, increasing the hardness of the coating layer, and then selecting a specific leveling agent, forcing the copper ions to have a relatively uniform arrangement, so that the added hardening agent is uniformly distributed around the copper crystal grains. To increase the hardness of the coating.

本發明無電鍍銅鍍液，含有溶劑、銅離子、錯合劑、還原劑、整平劑，及增硬劑，其中，整平劑選自聚亞胺、咪唑系季銨鹽材料或其等的組合，增硬劑選自鉈離子、碲離子、硒離子，或上述任意的組合。The electroless copper plating solution of the invention comprises a solvent, a copper ion, a complexing agent, a reducing agent, a leveling agent, and a hardening agent, wherein the leveling agent is selected from the group consisting of polyimine, imidazole quaternary ammonium salt material or the like In combination, the hardening agent is selected from the group consisting of cerium ions, cerium ions, selenium ions, or any combination thereof.

在鹼性鍍液中，增硬劑(鉈離子、碲離子、硒離子)會形成負電集團，並吸附於待鍍物表面而與銅共同析出，以增加鍍層的硬度。本發明再透過選用聚亞胺、咪唑系季銨鹽材料作為整平劑，讓其吸附於待鍍物表面，迫使銅離子在待鍍物表面以較為一致的方式排列，並促使增硬劑分散均勻，讓鍍層的硬度更進一步地提升。透過本發明的無電鍍銅鍍液所製得的鍍層，具有較高的硬度，Hv值能大於170。In the alkaline plating solution, a hardening agent (cerium ion, cerium ion, selenium ion) forms a negative electricity group and is adsorbed on the surface of the object to be plated and precipitated together with copper to increase the hardness of the plating layer. The invention further adopts a polyimine and an imidazole quaternary ammonium salt material as a leveling agent to adsorb on the surface of the object to be plated, forcing copper ions to be arranged in a relatively uniform manner on the surface of the object to be plated, and promoting the dispersion of the hardening agent. Evenly, the hardness of the coating is further improved. The coating obtained by the electroless copper plating bath of the present invention has a high hardness and an Hv value of more than 170.

本發明將就以下實施例作進一步說明，但應瞭解的是，該等實施例僅為例示說明之用，而不應被解釋為本發明實施之限制。The invention is further described in the following examples, but it should be understood that these examples are for illustrative purposes only and are not to be construed as limiting.

[[ 實施例Example 1]1]

鍍液製備Plating solution preparation

取5.29g的氯化銅(即：含有2.5g的銅離子)放入1L之燒杯中，並加入0.6L的水，溶解後加入乙二胺四乙酸四鈉鹽(EDTA-4Na)作為錯合劑，攪拌至溶解，並加入氫氧化鈉(NaOH)調整pH值至12.5以上，再加熱至55°C，隨後加入0.1g的聚壬基酚聚氧乙烯醚磷酸酯(購自RHODIA，品名為RHODAFAC® RE-610)作為潤濕劑，以及0.004g的2,2'-聯吡啶(購自Merck)作為安定劑，接著，再加入0.1g的咪唑/環氧氯丙烷共聚物(購自BASF，品名為Lugavan® IZE)作為整平劑，以及加入作為增硬劑之甲酸鉈共0.055g(即：含有0.045g的鉈離子)，待其等溶解後，再加入16g且重量百分濃度為24wt%的甲醛作為還原劑，並加水至鍍液中使整體體積為1L，最後放入銅箔片試鍍5分鐘進行活化，即完成無電鍍銅鍍液之製備。Take 5.29g of copper chloride (ie: containing 2.5g of copper ions) into a 1L beaker, add 0.6L of water, dissolve and add ethylenediaminetetraacetic acid tetrasodium salt (EDTA-4Na) as a wrong agent Stir until dissolved, and add sodium hydroxide (NaOH) to adjust the pH to above 12.5, then heat to 55 ° C, then add 0.1g of polydecylphenol ethoxylate phosphate (purchased from RHODIA, the product name is RHODAFAC ® RE-610) as a wetting agent, and 0.004 g of 2,2'-bipyridine (available from Merck) as a stabilizer, followed by the addition of 0.1 g of an imidazole/epichlorohydrin copolymer (available from BASF, The product name is Lugavan® IZE) as a leveling agent, and a total of 0.055 g of cesium formate as a hardening agent (ie, containing 0.045 g of cerium ion), after which it is dissolved, 16 g is added and the weight concentration is 24 wt. % formaldehyde is used as a reducing agent, and water is added to the plating solution to make the whole volume 1L. Finally, the copper foil is placed on the copper foil for 5 minutes for activation, that is, the preparation of the electroless copper plating solution is completed.

樣品製備Sample Preparation

試片前處理步驟：取一電解銅箔試片(長*寬為5cm*5cm、厚度為18.5微米、Ra=0.192)，浸入陰極電解脫脂液，並在60C的溫度下以4ASD之電流密度進行脫脂5分鐘，後取出試片水洗，再於常溫下浸泡濃度為10v/v%之稀硫酸2分鐘，待時間到達後取出水洗之，完成前處理步驟。Pre-treatment steps: Take an electrolytic copper foil test piece (length * width 5cm * 5cm, thickness 18.5 microns, Ra = 0.122), immersed in the cathode electrolytic degreasing solution, and at 60 The temperature of C was degreased at a current density of 4 ASD for 5 minutes, and then the test piece was washed with water, and then dilute sulfuric acid having a concentration of 10 v/v% was immersed at room temperature for 2 minutes. After the time was reached, the water was washed out to complete the pretreatment step.

速率估算Rate estimation

取一完成前處理的試片，將之浸入前述配製好的無電鍍銅鍍液，於55°C之溫度下浸泡30分鐘，再取出該試片並以水清洗及乾燥，而後量取厚度，估算出每30分鐘銅鍍層成長的速率。本實施例之速率約為5.5至6微米/小時。Taking a pre-processed test piece, immersing it in the prepared electroless copper plating solution, immersing it at a temperature of 55 ° C for 30 minutes, taking out the test piece, washing and drying with water, and then measuring the thickness, Estimate the rate of growth of the copper plating every 30 minutes. The rate of this embodiment is about 5.5 to 6 microns per hour.

無電鍍銅Electroless copper

取另一完成前處理的試片，將之浸入前述配製好的無電鍍銅鍍液，於55°C之溫度下浸泡，每過30分鐘即分析水位、銅離子、還原劑及氫氧化鈉之濃度，不足者即進行補充，待該試片浸泡2至3小時，於銅鍍層達厚度達12微米之後，再取出該試片並以水清洗及乾燥。Take another test piece before completion, immerse it in the prepared electroless copper plating solution, soak it at 55 ° C, and analyze the water level, copper ion, reducing agent and sodium hydroxide every 30 minutes. The concentration is insufficient to be supplemented. After the test piece is immersed for 2 to 3 hours, after the copper plating layer reaches a thickness of 12 μm, the test piece is taken out and washed with water and dried.

樣品測試test sample

取前述鍍銅後的試片，以奈米壓印測試系統(Nano Indenter，購自國科企業有限公司，型號：NTS Nano Indenter G200)進行測定。使用探針壓痕，當深度達1000nm時量測其壓痕，獲得其Hv值。其中，1000Hv=回授壓力GPa/9.8。經測試後，該試片上的銅層之Hv值為208。The copper-plated test piece was taken and measured by a nanoimprint test system (Nano Indenter, purchased from National Instruments Co., Ltd., model: NTS Nano Indenter G200). Using the probe indentation, the indentation was measured when the depth reached 1000 nm, and its Hv value was obtained. Among them, 1000Hv = feedback pressure GPa / 9.8. After testing, the copper layer on the test piece had an Hv value of 208.

[[ 實施例Example 22 至to 8]8]

本系列實施例的鍍液製備、樣品製備及樣品測試皆與實施例1相似，差異僅在於所採用的試劑種類略有不同。本系列實施例所採用的增硬劑皆為鉈離子，而整平劑是選自咪唑/環氧氯丙烷共聚物、分子量1400之聚乙烯亞胺，及分子量200之聚乙烯亞胺。其等之詳細配方及操作溫度已列於表1。The bath preparation, sample preparation and sample testing of the examples of this series are similar to those of Example 1, except that the types of reagents used are slightly different. The hardening agents used in the examples of this series are all cerium ions, and the leveling agent is selected from the group consisting of an imidazole/epichlorohydrin copolymer, a polyethyleneimine having a molecular weight of 1,400, and a polyethyleneimine having a molecular weight of 200. The detailed formulation and operating temperatures are listed in Table 1.

本系列實施例皆採用鉈離子做為增硬劑，調整鉈離子之濃度並各自輔以不同的整平劑，所製得的銅鍍層Hv值分別為202、198、203、200、204、204、212，皆高於170。In this series of examples, strontium ions are used as hardening agents, and the concentration of cerium ions is adjusted and supplemented with different leveling agents. The Hv values of the copper plating layers are 202, 198, 203, 200, 204, 204, respectively. 212 is higher than 170.

[[ 比較例Comparative example 1]1]

參閱表1，本比較例與實施例1大致相同，差異僅在於未添加整平劑及增硬劑。所獲得的銅鍍層硬度Hv值為108。Referring to Table 1, this comparative example is substantially the same as Example 1, except that the leveling agent and the hardening agent are not added. The obtained copper plating layer had a hardness Hv value of 108.

[[ 比較例Comparative example 2]2]

參閱表1，本比較例與實施例1大致相同，差異僅在於未添加增硬劑，而整平劑是採用IZE，濃度為0.2g/L。所獲得的銅鍍層硬度Hv值為113。Referring to Table 1, this comparative example is substantially the same as Example 1, except that no hardening agent is added, and the leveling agent is IZE at a concentration of 0.2 g/L. The obtained copper plating layer had a hardness Hv value of 113.

[[ 比較例Comparative example 3]3]

參閱表1，本比較例與實施例1大致相同，差異僅在於未添加整平劑，且鉈離子之濃度為0.02g/L。所獲得的銅鍍層硬度Hv值為142。Referring to Table 1, this comparative example is substantially the same as Example 1, except that the leveling agent is not added, and the concentration of barium ions is 0.02 g/L. The obtained copper plating layer had a hardness Hv value of 142.

由比較例1至3可知，沒有添加整平劑及增硬劑的鍍液，所製得的鍍層Hv值僅有108，添加整平劑之後可增至113，而僅有添加鉈離子者，Hv值能增至142。實施例1至8係同時添加鉈離子及整平劑，Hv值皆大於170，由此可知，透過選用特定的整平劑以及增硬劑，能有效改善鍍層的硬度。It can be seen from Comparative Examples 1 to 3 that the plating solution without the addition of the leveling agent and the hardening agent has a Hv value of only 108, and can be increased to 113 after the addition of the leveling agent, and only the addition of strontium ions, The Hv value can be increased to 142. In Examples 1 to 8, the cerium ions and the leveling agent were simultaneously added, and the Hv values were all greater than 170. From this, it was found that the hardness of the plating layer can be effectively improved by selecting a specific leveling agent and a hardening agent.

表1 註：錯合劑C1為乙二胺四乙酸四鈉鹽；錯合劑C2為N,N,N',N'-四(2-羥基丙基)乙烯二胺，購自BASF，品名為Lutropur® Q-75；錯合劑C3為酒石酸鉀鈉；還原劑R1為甲醛(Formalin，重量百分濃度：24wt%)；還原劑R2為乙醛酸(Glyoxylic acid，重量百分濃度：40wt%)；潤濕劑W1為聚壬基酚聚氧乙烯醚磷酸酯(Polyoxyethylene nonylphenyl ether branched phosphate，購自RHODIA，品名為RHODAFAC® RE-610)；潤濕劑W2為聚乙二醇(polyethylene glycol，分子量為6000，購自Dow，品名為CARBOWAX™ PEG 6000)；安定劑S1為2,2'-聯吡啶(2,2'-bipyridine，購自Merck)；安定劑S2為亞鐵氰化鉀(Potassium ferrocyanide，購自Merck)；IZE為咪唑/環氧氯丙烷共聚物(購自BASF，品名為Lugavan® IZE)；G-20為分子量1400的聚乙烯亞胺(購自BASF，品名為Lugalvan® G 20；G-35為分子量200的聚乙烯亞胺(購自BASF，品名為Lugalvan® G 35)。Table 1 Note: The wrong agent C1 is ethylenediaminetetraacetic acid tetrasodium salt; the wrong agent C2 is N, N, N', N'-tetrakis (2-hydroxypropyl) ethylene diamine, purchased from BASF, the product name is Lutropur® Q -75; the wrong agent C3 is sodium potassium tartrate; the reducing agent R1 is formaldehyde (Formalin, weight percent concentration: 24% by weight); the reducing agent R2 is Glyoxylic acid (weight percent concentration: 40% by weight); The agent W1 is polyoxyethylene nonylphenyl ether branched phosphate (purchased from RHODIA, the product name is RHODAFAC® RE-610); the wetting agent W2 is polyethylene glycol (polyethylene glycol, molecular weight 6000, Available from Dow under the trade name CARBOWAXTM PEG 6000); stabilizer S1 is 2,2'-bipyridine (2,2'-bipyridine, available from Merck); stabilizer S2 is potassium ferrocyanide (Potassium ferrocyanide) From Merck); IZE is an imidazole/epichlorohydrin copolymer (available from BASF under the trade name Lugavan® IZE); G-20 is a polyethyleneimine with a molecular weight of 1400 (available from BASF under the trade name Lugalvan® G 20; G -35 is a polyethyleneimine having a molecular weight of 200 (available from BASF under the trade name Lugalvan® G 35).

[[ 實施例Example 99 至to 11]11]

本系列實施例的鍍液製備、樣品製備及樣品測試皆與實施例1相似，差異僅在於所採用的試劑種類略有不同。本系列實施例所採用的增硬劑皆為碲離子，是透過添加二氧化碲而獲得，碲離子之濃度分別為0.02、0.015及0.01g/L。整平劑是選自咪唑/環氧氯丙烷共聚物、分子量140之聚乙烯亞胺，及分子量200之聚乙烯亞胺。經樣品測試後，鍍層的Hv值分別為206、205、209。其等之詳細配方及操作溫度已列於表2。The bath preparation, sample preparation and sample testing of the examples of this series are similar to those of Example 1, except that the types of reagents used are slightly different. The hardening agents used in the examples of this series are all cerium ions, which are obtained by adding cerium oxide, and the concentrations of cerium ions are 0.02, 0.015 and 0.01 g/L, respectively. The leveling agent is selected from the group consisting of an imidazole/epichlorohydrin copolymer, a polyethyleneimine having a molecular weight of 140, and a polyethyleneimine having a molecular weight of 200. After the sample was tested, the Hv values of the coatings were 206, 205, and 209, respectively. The detailed formulation and operating temperatures are listed in Table 2.

[[ 實施例Example 1212 至to 14]14]

本系列實施例的鍍液製備、樣品製備及樣品測試皆與實施例1相似，差異僅在於所採用的試劑種類略有不同。本系列實施例所採用的增硬劑皆為硒離子，是透過添加硒氰酸鉀而獲得，碲離子之濃度分別為0.012、0.01g/L。整平劑是選自咪唑/環氧氯丙烷共聚物及分子量200之聚乙烯亞胺。經樣品測試後，鍍層的Hv值分別為203、195、208。其等之詳細配方及操作溫度已列於表2。The bath preparation, sample preparation and sample testing of the examples of this series are similar to those of Example 1, except that the types of reagents used are slightly different. The hardening agents used in the examples of this series are all selenium ions, which are obtained by adding potassium selenocyanate, and the concentrations of barium ions are 0.012 and 0.01 g/L, respectively. The leveling agent is selected from the group consisting of an imidazole/epichlorohydrin copolymer and a polyethyleneimine having a molecular weight of 200. After the sample was tested, the Hv values of the coatings were 203, 195, and 208, respectively. The detailed formulation and operating temperatures are listed in Table 2.

[[ 比較例Comparative example 4]4]

參閱表2，本比較例與實施例1大致相同，差異僅在於未添加整平劑，而增硬劑是濃度為0.015g/L的碲離子(源自二氧化碲)，所獲得的銅鍍層硬度Hv值為154。Referring to Table 2, this comparative example is substantially the same as Example 1, except that the leveling agent is not added, and the hardening agent is a cerium ion (derived from cerium oxide) having a concentration of 0.015 g/L, and the obtained copper plating layer is obtained. The hardness Hv value was 154.

[[ 比較例Comparative example 5]5]

參閱表2，本比較例與實施例1大致相同，差異僅在於未添加整平劑，而增硬劑是濃度為0.012g/L的硒離子(源自硒氰酸鉀)，所獲得的銅鍍層硬度Hv值為158。Referring to Table 2, this comparative example is substantially the same as Example 1, except that the leveling agent is not added, and the hardening agent is a selenium ion (derived from potassium selenocyanate) having a concentration of 0.012 g/L, and the obtained copper is obtained. The coating hardness Hv value was 158.

表2 註：錯合劑C1為乙二胺四乙酸四鈉鹽；錯合劑C2為N,N,N',N'-四(2-羥基丙基)乙烯二胺，購自BASF，品名為Lutropur® Q-75；錯合劑C3為酒石酸鉀鈉；還原劑R1為甲醛(Formalin，重量百分濃度：24wt%)；還原劑R2為乙醛酸(Glyoxylic acid，重量百分濃度：40wt%)；潤濕劑W1為聚壬基酚聚氧乙烯醚磷酸酯(Polyoxyethylene nonylphenyl ether branched phosphate，購自RHODIA，品名為RHODAFAC® RE-610)；潤濕劑W2為聚乙二醇(polyethylene glycol，分子量為6000，購自Dow，品名為CARBOWAX™ PEG 6000)；安定劑S1為2,2'-聯吡啶(2,2'-bipyridine，購自Merck)；安定劑S2為亞鐵氰化鉀(Potassium ferrocyanide，購自Merck)；IZE為咪唑/環氧氯丙烷共聚物(購自BASF，品名為Lugavan® IZE)；G-20為分子量1400的聚乙烯亞胺(購自BASF，品名為Lugalvan® G 20；G-35為分子量200的聚乙烯亞胺(購自BASF，品名為Lugalvan® G 35)。Table 2 Note: The wrong agent C1 is ethylenediaminetetraacetic acid tetrasodium salt; the wrong agent C2 is N, N, N', N'-tetrakis (2-hydroxypropyl) ethylene diamine, purchased from BASF, the product name is Lutropur® Q -75; the wrong agent C3 is sodium potassium tartrate; the reducing agent R1 is formaldehyde (Formalin, weight percent concentration: 24% by weight); the reducing agent R2 is Glyoxylic acid (weight percent concentration: 40% by weight); The agent W1 is polyoxyethylene nonylphenyl ether branched phosphate (purchased from RHODIA, the product name is RHODAFAC® RE-610); the wetting agent W2 is polyethylene glycol (polyethylene glycol, molecular weight 6000, Available from Dow under the trade name CARBOWAXTM PEG 6000); stabilizer S1 is 2,2'-bipyridine (2,2'-bipyridine, available from Merck); stabilizer S2 is potassium ferrocyanide (Potassium ferrocyanide) From Merck); IZE is an imidazole/epichlorohydrin copolymer (available from BASF under the trade name Lugavan® IZE); G-20 is a polyethyleneimine with a molecular weight of 1400 (available from BASF under the trade name Lugalvan® G 20; G -35 is a polyethyleneimine having a molecular weight of 200 (available from BASF under the trade name Lugalvan® G 35).

實施例9至11皆是採用碲離子作為增硬劑，而實施例12至14是採用硒離子作為增硬劑，前述實施例皆輔以添加整平劑，所獲得的Hv值範圍介於195至209，大於170。而比較例4是僅添加碲離子但不含整平劑之鍍液，Hv值為154，比較例5是僅添加硒離子但不含整平劑之鍍液，Hv值為158。由此可知添加聚亞胺、咪唑系季銨鹽材料作為整平劑後，更能進一步地提高鍍層的硬度。In Examples 9 to 11, all of the ions were used as the hardening agent, and in Examples 12 to 14, the selenium ions were used as the hardening agent, and the foregoing examples were supplemented with the addition of the leveling agent, and the obtained Hv value ranged from 195. To 209, greater than 170. Comparative Example 4 is a plating solution in which only cerium ions are added but no leveling agent is added, and the Hv value is 154. In Comparative Example 5, a plating solution containing only selenium ions but no leveling agent is added, and the Hv value is 158. From this, it is understood that the addition of the polyimide and the imidazole-based quaternary ammonium salt material as a leveling agent can further improve the hardness of the plating layer.

綜上所述，本發明透過添加增硬劑以提高鍍層硬度，並再選用特定的整平劑，迫使銅離子有較為一致的排列，讓所添加的增硬劑均勻地分佈於銅晶粒的周圍，讓鍍層的硬度更為提升，故確實能達成本發明之目的。In summary, the present invention increases the hardness of the coating by adding a hardening agent, and then selects a specific leveling agent to force the copper ions to have a relatively uniform arrangement, so that the added hardening agent is uniformly distributed on the copper crystal grains. Around the circumference, the hardness of the plating layer is further increased, so that the object of the present invention can be achieved.

惟以上所述者，僅為本發明之實施例而已，當不能以此限定本發明實施之範圍，凡是依本發明申請專利範圍及專利說明書內容所作之簡單的等效變化與修飾，皆仍屬本發明專利涵蓋之範圍內。 However, the above is only the embodiment of the present invention, and the scope of the invention is not limited thereto, and all the equivalent equivalent changes and modifications according to the scope of the patent application and the patent specification of the present invention are still The scope of the invention is covered.

Claims (10)

一種無電鍍銅鍍液，含有溶劑、銅離子、錯合劑、還原劑、整平劑，及增硬劑，其中，整平劑選自聚亞胺、咪唑系季銨鹽材料或其等的組合，增硬劑選自鉈離子、碲離子、硒離子，或上述任意組合，該整平劑的分子量介於100至3000，該增硬劑的濃度為0.001至0.1g/L。 An electroless copper plating solution containing a solvent, a copper ion, a binder, a reducing agent, a leveling agent, and a hardening agent, wherein the leveling agent is selected from the group consisting of a polyimide, an imidazole quaternary ammonium salt material, or the like The hardening agent is selected from the group consisting of cerium ions, cerium ions, selenium ions, or any combination thereof, the leveling agent having a molecular weight of 100 to 3000, and the hardening agent having a concentration of 0.001 to 0.1 g/L. 如請求項1所述的無電鍍銅鍍液，其中，該整平劑的聚亞胺為聚乙烯亞胺，咪唑系季銨鹽材料為咪唑/環氧氯丙烷共聚物。 The electroless copper plating solution according to claim 1, wherein the leveling agent has a polyimine of polyethyleneimine and the imidazole-based quaternary ammonium salt material is an imidazole/epichlorohydrin copolymer. 如請求項1所述的無電鍍銅鍍液，其中，鉈離子是源自甲酸鉈，碲離子是源自二氧化碲，硒離子是源自硒氰酸鉀。 The electroless copper plating solution according to claim 1, wherein the cerium ion is derived from cerium formate, the cerium ion is derived from cerium oxide, and the selenium ion is derived from potassium selenate. 如請求項1至3中任一項所述的無電鍍銅鍍液，其中，增硬劑的濃度為0.002至0.05g/L。 The electroless copper plating solution according to any one of claims 1 to 3, wherein the concentration of the hardening agent is from 0.002 to 0.05 g/L. 如請求項1至3中任一項所述的無電鍍銅鍍液，其中，該整平劑的濃度為0.01至0.8g/L。 The electroless copper plating solution according to any one of claims 1 to 3, wherein the leveling agent has a concentration of 0.01 to 0.8 g/L. 如請求項5所述的無電鍍銅鍍液，其中，該整平劑的濃度為0.02至0.3g/L。 The electroless copper plating solution according to claim 5, wherein the leveling agent has a concentration of 0.02 to 0.3 g/L. 如請求項5所述的無電鍍銅鍍液，其中，當整平劑為聚亞胺時，其濃度為0.01至0.2g/L，當整平劑為咪唑系季銨鹽材料時，其濃度為0.02至0.8g/L。 The electroless copper plating solution according to claim 5, wherein when the leveling agent is a polyimine, the concentration is 0.01 to 0.2 g/L, and when the leveling agent is an imidazole-based quaternary ammonium salt material, the concentration thereof is It is 0.02 to 0.8 g/L. 如請求項5所述的無電鍍銅鍍液，其中，當整平劑為聚亞胺時，其濃度為0.02至0.15g/L，當整平劑為咪唑系季銨鹽材料時，其濃度為0.05至0.3g/L。 The electroless copper plating solution according to claim 5, wherein when the leveling agent is a polyimine, the concentration is 0.02 to 0.15 g/L, and when the leveling agent is an imidazole-based quaternary ammonium salt material, the concentration thereof is It is 0.05 to 0.3 g/L. 一種增加銅鍍層硬度的無電鍍銅方法，包含以下步驟：取一試片經前處理後，再浸入如請求項1所述之無電鍍銅鍍液，以成長銅鍍層。 An electroless copper plating method for increasing the hardness of a copper plating layer comprises the steps of: immersing a test piece after pretreatment, and then immersing the electroless copper plating solution as described in claim 1 to grow a copper plating layer. 如請求項9所述的增加銅鍍層硬度的無電鍍銅方法，其中，該無電鍍銅鍍液的溫度控制在40至60℃。 An electroless copper plating method for increasing the hardness of a copper plating layer according to claim 9, wherein the temperature of the electroless copper plating plating solution is controlled at 40 to 60 °C.
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