1259105 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種鈀金屬奈米粒子，特別是指一種 以高分子為保護劑之纪金屬奈米粒子，這些奈米粒子不 但能長時間穩定懸浮於溶液中，且能廣泛應用於電子線 路製作的無電鍍銅程序，以及各種非導體元件金屬之活 化技術。 【先前技術】 在習用的無電鍍活化程序中，乃是採用錫鈀或離子 鈀為無電鍍活化液。其中錫鈀膠體是以鈀金屬為催化中 心，外層為SnCV等帶負電之離子，利用電荷相斥支援 裡，使|巴金屬微粒懸浮於溶液中（J. Horkans，J.R. White, and J. M. Roldan，/5M J.及以· Deve/o;?· 1988，32，5)，但 是由於外層之亞錫離子（Sn2+)易被空氣所氧化成錫四價 離子（Sn4+)且鍚鈀膠體在操作上需維持一定的錫鈀濃度 比，造成濃度使用上的限制。為了改善錫鈀膠體系統不 穩定的問題，本發明採用抗氧化之高分子為保護劑，在 乙二醇溶劑的環境下合成出奈米尺度之鈀金屬粒子。因 此具有比表面積大、活性高等特點，因此本發明具有低 成本且高催化活性之優點。 在合成技術方面，由於習用之錫鈀膠體需要將氯化 i巴（Palladium Chloride, PdCl2)及氣化亞錫（Stannous 1259105 讹nde，Sncy分別溶於鹽酸水溶液中，再將兩液混 &亚升溫至HKTC ’反應數小時後，方能形成錫把活化 液(如關第4593016號發明專利案中所揭露者）。本私 明係將金屬鹽類及保護劑溶於乙二醇溶财稱為料 :，另外將氫氧化納溶於乙二醇溶劑稱為溶液乙，再於 室溫下加適量溶液乙於溶液甲巾，即完餘奈米粒子的 製備，本發明整體製備時間僅需約3〇 知之習用技術縮短許多。 較已 在粒子大小方面，由於在奈米尺度下，其催化活性 可由其粒子大小影響。習用之錫㈣體，其平均顆粒大 J、、、勺為15.3nm且粒子大小不均，不易控制其粒徑分布。 本發明利用在足夠的促進劑濃度下能夠合成出粒子大小 約為2.4nm，且粒徑分布均勻的鈀奈米粒子，並可藉由 铨制氫氧化鈉濃度之不同控制鈀奈米粒子大小，其粒徑 較習知技術小且均一。 本發明採用高分子為奈米粒子保護劑，目前已經證 明與現有之商業整孔劑（R〇ckw〇〇d伊希特化公司整孔 州i號· ML371)能互相搭配，實驗證明pcj/pvp/EG 奈米粒子與ML371的搭配在印刷電路板的鍍通孔程序 與非導體樹酯表面上的活化效果良好，不需要另外尋找 整孔劑，為本發明的另一優點。 【發明内容】 由於尚为子聚乙烯。比略酮（P〇lyvinylpyrr〇lid〇ne， 1259105 簡稱PVP ) template)，^ 在南分子模;j 4於溶劑中會糾纏行成軟性模板（s禮 由於其尺度在奈米大小，因此，當金屬粒子 在南义子模板的侷限空間還原時，其粒子大小與均勻度 會受到這些模板限制而生成奈米級的粒子。吾人可以^ 由改變氫氧化鈉的濃度來控制粒子的大小。利用此法= 成出來㈣金屬奈米粒子具有高活性、低成本等特性i 有適當的無電鍍整孔劑可與之搭配。 本發明作為無電鍍製程活化液的優點如下： 使用抗氧化的南分子作為粒子保護劑，較習用技術 更能穩定粒子。 2·使用加入氫氧化鈉在乙二醇系統的方法，在室溫下 即旎合成出顆粒均勻且小的鈀奈米粒子，較習用技 術簡單方便且合成時間較短。 3·可以利用不同濃度的Α氧化納來合成出不銅粒徑之 鈀金屬奈米粒子，較習用技術小且均勻。 4. 本發明之奈米粒子，能與現有之商業整孔劑 (Rockwood伊希特化整孔劑型號：ML371)搭被使用， 完全不需要開發新型之整孔劑，具有商業價值。1259105 IX. Description of the Invention: [Technical Field] The present invention relates to a palladium metal nanoparticle, in particular to a metal nanoparticle using a polymer as a protective agent, which is stable not only for a long time. It is suspended in a solution and can be widely used in electroless copper plating processes for electronic circuit fabrication, as well as various non-conductor component metal activation techniques. [Prior Art] In the conventional electroless plating activation procedure, tin-palladium or ionic palladium is used as an electroless plating activation solution. The tin-palladium colloid is a palladium metal-based catalytic center, and the outer layer is a negatively charged ion such as SnCV. The charge is repelled to support the metal particles in the solution (J. Horkans, JR White, and JM Roldan, / 5M J. and Deve/o;?· 1988,32,5), but because the outer layer of stannous ions (Sn2+) is easily oxidized by air into tin tetravalent ions (Sn4+) and the palladium-palladium colloid is required for operation. Maintain a certain ratio of tin to palladium concentration, resulting in restrictions on the use of concentration. In order to improve the instability of the tin-palladium colloidal system, the present invention uses an anti-oxidation polymer as a protective agent to synthesize nanometer-sized palladium metal particles in an ethylene glycol solvent environment. Therefore, the present invention has the characteristics of large specific surface area, high activity, and the like, and therefore has the advantages of low cost and high catalytic activity. In terms of synthesis technology, since the conventional tin-palladium colloid needs to be chlorinated (Palladium Chloride, PdCl2) and vaporized stannous (Stannous 1259105 讹nde, Sncy are respectively dissolved in aqueous hydrochloric acid solution, and then the two liquids are mixed & After heating up to HKTC's reaction for several hours, it can form a tin-activated solution (as disclosed in the invented patent No. 4593016). This private product dissolves metal salts and protective agents in ethylene glycol. For the preparation of the present invention, the preparation time of the present invention is only required to further dissolve the sodium hydroxide in a solvent of ethylene glycol as solution B, and then add an appropriate amount of solution B to the solution at room temperature, that is, the preparation of the remaining nano particles. About 3 knowing the conventional techniques are shortened a lot. Compared with the particle size, the catalytic activity can be affected by the particle size at the nanometer scale. The conventional tin (tetra) body has an average particle size J, and the spoon is 15.3 nm. Moreover, the particle size is not uniform, and it is difficult to control the particle size distribution. The present invention can synthesize palladium nanoparticles having a particle size of about 2.4 nm and a uniform particle size distribution at a sufficient accelerator concentration, and can be made by tanning. Hydrogen The difference in sodium concentration controls the size of the palladium nanoparticle, and its particle size is smaller and uniform than the conventional technique. The present invention uses a polymer as a nanoparticle protectant, and has been proved to be compatible with the existing commercial pore former (R〇ckw〇〇). d Ishitization Co., Ltd., the whole hole state i · ML371) can be matched with each other. Experiments show that the combination of pcj/pvp/EG nano particles and ML371 is activated on the plated through-hole procedure and non-conductive resin surface of printed circuit boards. The effect is good, and there is no need to find a new pore-forming agent, which is another advantage of the present invention. [Summary of the Invention] Since it is still a sub-polyethylene, a ketone (P〇lyvinylpyrr〇lid〇ne, 1259105 for short PVP) template, ^ In the south molecular model; j 4 will entangle into a soft template in the solvent (s because its scale is in nanometer size, therefore, when the metal particle is reduced in the confined space of the southern template, its particle size and uniformity will Restricted by these templates to produce nano-sized particles. We can control the particle size by changing the concentration of sodium hydroxide. Using this method = (4) Metal nanoparticles have high activity, low cost, etc. A suitable electroless plating porogen can be matched with it. The advantages of the present invention as an electroless plating activation solution are as follows: The use of an anti-oxidation south molecule as a particle protectant is more stable than conventional techniques. In the ethylene glycol system method, uniform and small palladium nanoparticles are synthesized at room temperature, which is simpler and more convenient than conventional techniques and has a short synthesis time. 3. It can be synthesized by using different concentrations of ruthenium oxide. The palladium metal nanoparticle having a non-copper particle size is smaller and more uniform than conventional techniques. 4. The nanoparticle of the present invention can be blended with a conventional commercial pore former (Rockwood Ishitization pore former model: ML371) Use, no need to develop new pore-forming agents, has commercial value.
活化反應，不需經過其他純化處理。 本發明之鈀金屬奈米粒子，可以水稀釋至低操作濃 5. 合成出纟的！巴金屬纟米粒子能有效長時間穩定地分 1259105 度（lOppm)作為無電鍍活化液仍保有其催化效果，且 其穩定度較習用技術佳。 8·原料取得簡單，製備方法節省能源，適用於大規模 生產。 本發明所採用的具體實施例，將藉由以下之實施例 及附呈圖式作進一步之說明。 【實施方式】 近年來，人們採用高科技的方法致力於製備均勻、 高純度、顆粒小、球狀、分散性好、粒徑分布窄和比表 面積大的貴重金屬粒子。由於奈米級貴重金屬具有較高 的表面積比及催化活性，因此有極高的潛力應用化學鍍 銅活化液。 本發明利用化學還原法，以高分子為保護劑在室溫 下的純乙二醇系統中加入氫氧化鈉促進乙二醇還原鈀的 速率，此方法成功的改進了過去乙二醇下合成鈀奈米粒 子需要外加還原劑或升溫的方法（如參考文件一：F· Bonet， V· Delmas，S. Grugeon，R· Herrera Urbina*，P-Y. Silvert and K.Tekaia-Elhsissen，NanoStructured Materials, 11，8，1277 (1999);參考文件二：κ· Tekaia-Elhsissen，F.Bonet，S· Grugeon，S. Lambert，and R. Herrera-Urbina，J· Mate. Res·，14，9，3707 (1999)，參考文件三：L.K.Kurihara，NanoStructured Materials，5, 607 (1995);參考文件四：t. Yonezawa，N· Toshima，J· Chem. Soc. Faraday Trans·，91(22)，4111-4119 (1995)與參考文件五：η. P. 1259105The activation reaction does not require additional purification. The palladium metal nano particles of the invention can be diluted with water to a low operating concentration. Ba metal glutinous rice particles can effectively be stably divided into 1259105 degrees (lOppm) for a long time as an electroless plating activator, and its stability is better than conventional techniques. 8. The raw materials are simple, the preparation method saves energy, and is suitable for mass production. The specific embodiments of the present invention will be further described by the following examples and the accompanying drawings. [Embodiment] In recent years, high-tech methods have been used to prepare precious metal particles having uniformity, high purity, small particle size, spherical shape, good dispersibility, narrow particle size distribution, and large specific surface area. Due to the high surface area ratio and catalytic activity of nano-grade precious metals, there is a high potential for the application of electroless copper plating activators. The invention utilizes a chemical reduction method to add sodium hydroxide to a pure ethylene glycol system at room temperature to promote the rate of reduction of palladium by ethylene glycol. This method successfully improves the synthesis of palladium under ethylene glycol. Nanoparticles require the addition of a reducing agent or a method of warming up (eg, Reference 1: F. Bonet, V. Delmas, S. Grugeon, R. Herrera Urbina*, PY. Silvert and K. Tekaia-Elhsissen, NanoStructured Materials, 11, 8,1277 (1999); Reference 2: κ· Tekaia-Elhsissen, F. Bonet, S. Grugeon, S. Lambert, and R. Herrera-Urbina, J. Mate. Res·, 14, 9, 3707 (1999 ), Reference Document 3: LKKurihara, NanoStructured Materials, 5, 607 (1995); Reference Document 4: t. Yonezawa, N. Toshima, J. Chem. Soc. Faraday Trans., 91(22), 4111-4119 ( 1995) and reference document five: η. P. 1259105
Choo, Κ· Y. Liew and Η· R Liu，J. Mater· Chem·，12，934 (2⑻2))。利用TEM與XRD鑑定鈀奈米粒子，得知隨著 氫氧化鈉濃度的增加得到顆粒小均勻、分散性好且粒徑 分布窄的鈀奈米粒子。當氫氧化鈉從〇增加到3.2 X lC^M (莫耳/公升，mole/1)，粒徑則由8.6降低到2.4 nm。吾 人進一步利用FT-IR鑑定氫氧化鈉加入乙二醇的產物， 發現隨著時間的增加，具有還原力的醛化合物亦增加， 證明在乙二醇中加入氫氧化鈉可加速乙二醇的還原力。 將合成出來的鈀金屬奈米粒子不需純化可以用水直 接析釋配活化液，應用於印刷電路板無電鍍銅製程。由 鍍通孔或無電鍍銅的研究發現，此鈀奈米粒子在低濃度 (lOppm)操作亦具有很好的穩定性，且不若市售鈀離子 系統活化液(Atotech阿托公司產品），它需要外加還原劑 的程序，且目前已有適用的商用整孔可以搭配使用，反 應原料簡單並且適合工業大量製造使用，詳細的實施例 說明如下： <實施例一 > 將分子量8000之聚乙烯吡咯酮 （PVP) 0.05g，溶 於10ml純乙二醇溶液中，並將0.05g的氯化把溶於上 述溶液中，並加入少量鹽酸幫助金屬鹽類溶解。並在劇 烈的攪拌下加入事先溶解在乙二醇溶劑中的0.32M氫氧 化鈉3ml。在剛滴入氫氧化鈉時，溶液由暗褐紅色漸漸 變成黑色，約30分鐘後溶液完全呈現黑色，表示反應 1259105 凡成。合成出來的鈀奈米 分析，發《子電:?微鏡(TEM) 現象，如圖一所_ _ 生好，沒有相互聚集之 屬奸大。$ ° ®二顯示的是經由軟體統計其免金 〇4…’所得到的粒子直徑為，標準誤差為 =;改變不同之氣氧化納濃度從。到。.通，亦Ϊ 侍不同粒徑大小之鈀金屬奈米粒子，並粒护分 Umn降低到24 η 苴 ，、二布由 分布如圖三與心所示 U丰錢《化納濃度 〈貫施例二> 班—如實施例一，實施無電鍍程序。將2cm χ 2cm的 環氧樹脂板(FR-4)’先經由商㈣MU71(R〇ckw〇〇d伊 希特化公司產品）’以上述製備之奈米把金屬為活化液， =水稀釋到50Ppm，浸泡5分鐘後，於室溫下進行$分 鐘之無電鍍銅催化反應。其無電鍍銅沉積量（〇.= mg/cm2) ’與濃度為6〇ppm之商用鈀/錫活化液在 之無電鍍銅沉積量相當（0.25 mg/cm2)。而鈀在FR_4板 材上的吸附量為1.56 pg/cm2，其與商用鈀/錫活化液的 1.64 pg/cm2 相當。 〈實施例三> 如實施例一所述之合成方法，將合成出來的奈米把 活化液，用水稀釋到不同濃度，發現隨著鈀操作濃度不 同’在固定操作溫度60°C下，採用整孔劑為 11 1259105 ML371(Rockwood伊希特化公司產品），其鈀吸附量分布 於0.5pg/cm2到2.0pg/cm2，而5分鐘無電鍍銅在FR-4 上的沉積量約為0.2 mg/cm2到0.34mg/cm2，與習用技術 (I巴/錫活化液，其濃度60ppm)之0.25mg/cm2相當。以上 如圖五所示。 <實施例四> 如實施例一所述之合成方法，將合成出來的活化 液，固定操作濃度為50ppm，改變活化液操作溫度為3〇 到70°C，採用整孔劑為ML371(Rockwood伊希特化公司 產品），發現其鈀吸附量分布於1.06到1.69 jug/cm2與 ¥用技術之1 · 6 9 μ g/cm2相當。且5分鐘的無電鍍銅在 FR-4上的沉積量相近，約為〇·23 mg/cm2到〇.25mg/cm2 與習用技術（濃度為60ppm之I巴/錫活化液）〇.25mg/cm2 相當。以上如圖六所示。 <實施例五> 如實施例一所述之合成方法，將合成出來的活化 液，應用於印刷電路板鑛通孔的無電鍍銅製程的活化程 序，進行無電鍍銅程序12分鐘，發現其鍍層性質良好。 如圖七所示，採用整孔劑分別為ML371(Rockwood伊希 特化公司產品）與UX-DK(Atotech阿托公司產品），經由 背光檢測無論50ppm或在低至ι〇ρρηι的無電鍍銅層在 通孔表面的覆蓋率亦可達與習用的鈀/錫活化液相匹敵 1259105 =果。由於本方法合成出來的奈米絲子㈣用技術 =早合成’催化性高，且可在低濃度操作之優勢， 局度商業價值。 〃 藉由上述之本發明實施例可知，本發明確具產業上 =利用仏值。惟以上之實施例說明，僅為本發明之較佳 二施例況明，凡習於此項技術者當可依據本發明之上述 貝知例口兒明而作其它種種之改良及變化。然、❿這些依據 本發明實施例所作的種種改良及變化，當仍屬於本發明 之發明精神及界定之專利範圍内。 【圖式簡單說明】 第一圖係顯示利用0.32M氫氧化鈉合成之鈀奈米膠體粒 子在穿透式電子顯微鏡(TEM)下之影像（放大倍率 45萬倍，比例尺為i〇nm); 第二圖係顯示利用0.32M氫氧化鈉合成之鈀奈米膠體粒 子（0.32M NaOH)之粒徑分布統計圖，其平均粒徑 為2.4nm，標準差為〇.4nm ; 第二圖係顯示加入不濃度的NaOH所合成出之 +子粒徑大小與標準差之對照表； 第四圖係顯示加入不濃度的NaOH所合成出之鈀奈米粒 子粒徑大小與標準差之曲線分布圖； 第五圖係顯示改變鈀活化液的操作濃度（從1〇 8卯^到 13〇ppm)， 經過5分鐘的60°C活化液浸泡與5分 鐘的無電鍍銅程序後，鈀活化液的操作濃度輿^巴 13 1259105 在FR-4上之吸附量之四分位曲線分布圖，以及鈀 活化液的操作濃度與銅沉積量之四分位曲線分布 圖； 第六圖係顯示改變鈀活化液的操作溫度（從30°C到 70°C )，經過5分鐘的50ppm活化液浸泡與‘5分 鐘的無電鍍銅程序後，鈀活化液的操作濃度與鈀 在FR-4上的吸附量以及銅沉積量之四分位曲線分 布圖； 第七圖係顯示新發明之鈀奈米粒子與習用技術活化液在 lOppm與50ppm活化液濃度下，應用於無電鍍銅 通孔製程之背光檢測圖。使用之整孔劑分別為 ML371(Rockwood伊希特化公司產品）與UX-DK(Atotech阿托公司產品）。 【主要元件符號說明】 (無） 14Choo, Κ·Y. Liew and Η·R Liu, J. Mater·Chem., 12, 934 (2(8)2)). The palladium nanoparticles were identified by TEM and XRD, and it was found that palladium nanoparticles having small particles, good dispersibility, and narrow particle size distribution were obtained as the concentration of sodium hydroxide increased. When sodium hydroxide increased from 〇 to 3.2 X lC^M (mole/liter, mole/1), the particle size decreased from 8.6 to 2.4 nm. We further used FT-IR to identify the product of sodium hydroxide added to ethylene glycol. It was found that the aldehyde compound with reducing power increased with time, which proved that the addition of sodium hydroxide to ethylene glycol can accelerate the reduction of ethylene glycol. force. The synthesized palladium metal nanoparticles can be directly applied to the electroless copper plating process on a printed circuit board without purification. Studies of plated through holes or electroless copper have found that the palladium nanoparticles have good stability at low concentrations (10 ppm) and are not commercially available as palladium ion system activation solutions (Atotech products). It requires a procedure for adding a reducing agent, and currently available commercial full holes can be used in combination, and the reaction materials are simple and suitable for industrial mass production. The detailed examples are as follows: <Example 1> Phenylpyrrolidone (PVP) 0.05 g, dissolved in 10 ml of pure ethylene glycol solution, and 0.05 g of chlorinated solution was dissolved in the above solution, and a small amount of hydrochloric acid was added to help dissolve the metal salt. 3 ml of 0.32 M sodium hydroxide previously dissolved in an ethylene glycol solvent was added under vigorous stirring. When the sodium hydroxide was just dripped, the solution gradually turned black from dark brownish red, and the solution completely appeared black after about 30 minutes, indicating that the reaction was 1259105. The synthesized palladium nanometer analysis, issued "sub-electricity: ? micro-mirror (TEM) phenomenon, as shown in Figure _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ $ ° ® II shows the diameter of the particles obtained by software-free 免4...', and the standard error is =; To. Tong, also 钯 钯 钯 不同 钯 钯 钯 钯 钯 钯 钯 钯 钯 钯 钯 钯 钯 钯 钯 钯 钯 钯 钯 钯 钯 钯 钯 钯 钯 钯 钯 钯 钯 钯 钯 钯 钯 钯 钯 钯 钯 钯 钯 钯 钯 钯 钯 钯 钯Example 2 > Class - As in the first embodiment, an electroless plating process was carried out. 2cm χ 2cm epoxy resin sheet (FR-4) was firstly passed through the commercial (four) MU71 (R〇ckw〇〇d Ishitization Co., Ltd. product), and the metal prepared above was used as an activation solution, and water was diluted to After 50 minutes of soaking for 50 minutes, an electroless copper catalyzed reaction of $ minutes was carried out at room temperature. Its electroless copper deposition (〇.= mg/cm2)' is comparable to the commercial palladium/tin activation solution at a concentration of 6 〇ppm (0.25 mg/cm2). The amount of palladium adsorbed on the FR_4 plate was 1.56 pg/cm2, which was equivalent to 1.64 pg/cm2 of the commercial palladium/tin activator. <Example 3> As in the synthesis method described in the first embodiment, the activated liquid was diluted with water to different concentrations, and found to be used at a fixed operating temperature of 60 ° C with different palladium operating concentrations. The pore former is 11 1259105 ML371 (product of Rockwood Ishitization Co., Ltd.), and its palladium adsorption amount is distributed from 0.5 pg/cm 2 to 2.0 pg/cm 2 , and the deposition amount of electroless copper on FR-4 for 5 minutes is about 0.2. From mg/cm2 to 0.34 mg/cm2, it is equivalent to 0.25 mg/cm2 of the conventional technique (I bar/tin activation solution, concentration 60 ppm). The above is shown in Figure 5. <Example 4> The synthesis method according to the first embodiment, the activated activation solution was fixed at a concentration of 50 ppm, the activation liquid was changed to an operating temperature of 3 Torr to 70 ° C, and the pore former was ML371 ( Rockwood Ishitization Co., Ltd. found that its palladium adsorption capacity is between 1.06 and 1.69 jug/cm2, which is equivalent to the technology of 1 · 6 9 μg/cm2. And the deposition of 5 minutes of electroless copper on FR-4 is similar, about 23 mg / cm 2 to 〇 25 mg / cm 2 and the conventional technology (concentration of 60 ppm I bar / tin activation solution) 〇.25mg / Cm2 is equivalent. The above is shown in Figure 6. <Example 5> The synthesis method according to the first embodiment, the activated activation solution is applied to the activation process of the electroless copper plating process of the printed circuit board ore through hole, and the electroless copper plating process is performed for 12 minutes, and it is found Its coating properties are good. As shown in Figure 7, the sizing agents are ML371 (Rockwood Ishitization Co., Ltd.) and UX-DK (Atotech Atotech), and the electroless copper is detected by backlight at 50 ppm or as low as ι〇ρρηι. The coverage of the layer on the surface of the via can also be comparable to the conventional palladium/tin activation liquid 1259105 = fruit. Because of the synthesis of the nanosynthesis (4) by the method of technology = early synthesis 'catalytic high, and can be used in low concentration, the commercial value.可 According to the embodiments of the present invention described above, the present invention does have an industrial use value. However, the above embodiments are merely illustrative of the preferred embodiments of the present invention, and those skilled in the art can make various other modifications and changes in accordance with the present invention. However, various modifications and changes made in accordance with the embodiments of the present invention are still within the scope of the invention and the scope of the invention. BRIEF DESCRIPTION OF THE DRAWINGS The first figure shows an image of a palladium nanoparticle colloidal particle synthesized by using 0.32M sodium hydroxide under a transmission electron microscope (TEM) (magnification: 450,000 times, scale bar is i〇nm); The second graph shows the particle size distribution of palladium nano colloidal particles (0.32 M NaOH) synthesized using 0.32 M sodium hydroxide, the average particle diameter of which is 2.4 nm, and the standard deviation is 〇.4 nm; A comparison table of the size and standard deviation of the + sub-particles synthesized by adding the non-concentrated NaOH; the fourth figure shows the curve distribution of the particle size and the standard deviation of the palladium nanoparticle synthesized by adding the non-concentrated NaOH; The fifth figure shows the operation concentration of the palladium activation solution (from 1〇8卯^ to 13〇ppm). After 5 minutes of 60°C activation solution soaking and 5 minutes of electroless copper plating, the operation of the palladium activation solution Concentration 舆^巴13 1259105 The quartile curve of the adsorption amount on FR-4, and the quartile curve distribution of the operating concentration of palladium activation solution and copper deposition; The sixth figure shows the change of palladium activation solution Operating temperature (from 30 ° C to 70 ° C), after 5 minutes of 50p After pm activation solution immersion and '5 minutes of electroless copper plating procedure, the operating concentration of palladium activation solution and the adsorption amount of palladium on FR-4 and the quartile curve distribution of copper deposition amount; the seventh figure shows the new invention The palladium nanoparticle and the conventional activation solution are applied to the backlight detection pattern of the electroless copper through-hole process at a concentration of 10 ppm and 50 ppm of the activation solution. The pore formers used were ML371 (Rockwood Ishitization Co., Ltd.) and UX-DK (Atotech Ato product). [Main component symbol description] (none) 14