201038766 六、發明說明： 【發明所屬之技術領域】 -種無钱金方法，尤其是—轉別適麟在微小尺 線路上鍍上一厚度均勻的金屬層之方法。 【先前技術】 由於積體電路製造技術的進步’製造〇25微来以下尺 〇 之線路為目前金屬化製程的主流。隨著線路尺寸日益縮小， 如何有效率地達成將導電物質形成於具有微小尺寸線路之 基板則為一個發展的重要關鍵。 電鍍製程即為-财效率地料騎質填充於具有微小 尺寸線路之技術，電鍍乃是將待鍍1件浸沒於含有電鑛金屬 的離子溶液中，使電源與電鐘槽内之陰極及陽極（消耗性或 非消耗性）電性連接，同時將電鍍金屬置放於陽極，而待鑛 工件置放於陰極’通以直魏後便會在待獻件的表面沉積 0 —金屬薄膜層。 ★鑛層之厚度均自性向來為評估魏效能的重要指標。參 閱2-圖所示，習知技術之未使用隔離層之基材鑛金方式之 =意圖，其中基材A上佈設有底材B，當底材B在置入鍍金 洛，進行鍍金作業時’若在底材B外侧未^有隔離層Μ (參 f第二圖）’則金離子瞒在底材B上，會目沒有適當的依 靠，則底材B上的鍍金層c會形成不穩的半圓隆起狀。 參閱第二圖，習知技術之使用隔離層之基材鍍金方式 之示意圖’傳統峨金浴為在紐A上佈設有底材B，且底 材B為金屬材質，在傳統的鍵金方式中，都會在基材a上的 201038766 &材g外侧邊，糊氧化!g、二氧僻或光阻構成隔離層 Aj ’並可在底材b的上方形成鍍金空間M卜而在鑛金的過 程中才會使金離子游離而填入鍍金空間ΑΠ内，堆疊成方正 _金形狀’之後再利用化學藥劑將隔離層A1從基材a上 除去，即完成底材β上的鍍金作業。 然而習知技術之缺點為通電鍍金的方式極易形成厚度不 均勻的鍍金層’其制於電鍍會有高低電流_影響而造成 厚度不均勾，另外鍍金浴在鍍金作業時，須事先預置隔離 〇 | ’而事後再移除隔離層，除了造賴金作業的麻煩與不 便，亦增加材料成本及延長整個製程之處理時間，因此需要 -種憑藉化學成分之相互個，即可祕材之微小尺寸線路 上形成厚度均勻之鍍金層之方法。 【發明内容】 本發明之主要目的在於一種於基材之微小尺寸線路上之 無電鍍金方法，其包含提供一待鍍基板，該待鍍基板具有至 少一待鍍面，該至少一待鍍面上具有一圖案化之待鍍金屬線 路，以一清洗方式對該待鑛基板之該至少一待鍍面進行清潔 處理，以去除該至少一待鍍面上所殘留的有機物質，該清洗 方式可以疋一電漿清洗方式或一清洗液清洗方式，其中該清 洗液可以是至少不超過二十個碳的水溶性界面活性劑或一 含有水溶性有機溶劑之溶液之至少其中之一；將該待鍍基板 浸入於一純水、一含水至少85%以上之界面活性劑或一鹽類 水溶液之至少之一中，以使該待鍍基板的該至少一待鍍面之 表面潤濕度增加；以及將該待鍍基板浸入於一鐘金浴中，其 中該鍍金浴係至少包含一水溶性金化合物、至少一種金錯合 .201038766 劑、至少一種羧基化合物或其鹽類，其中該至少一種羧基化 合物或其鹽類可以是草酸、丙二酸、丁二酸、丁烯二酸、戊 一酸、乳酸、甘醇酉夂、葡萄糖酸、檸檬酸、蘋果酸、酒石酸、 及其鹽類之至少其中之一。 因此本發明可解決習用技術之缺點，於不需通電及隔離 層之條件下，達成一種憑藉化學成分之相互作用而於微小尺 寸線路上形成厚度均勻之鍍金層之方法，如此可有效節省製 造成本及製造時間。 【實施方式】 以下配合圖式及元件符號對本發明之實施方式做更詳細 的說明，俾使熟習該項技藝者在研讀本說明書後能據以實 施。 參閱第二圖，本發明之於基材之微小尺寸線路上之無電 鑛金方法之流程示意圖，並配合第四圖，本發明之於基材之 微小尺寸線路上之無電鍍金方法之基材示意圖。 本發明係有關一種以化學鑛金方式在微小尺寸線路上鍍 上一厚度均勻的金屬層之方法，如第三圖的步驟S10所示， 並配合第四圖，首先提供一待鍍基板1，該待鍍基板1具有 至少一待鍍面11，該待鍍面11上具有一圖案化之待鍍金屬 線路3，其中該待鏡基板1可以是一銅箔基板、一矽基板、 一砷化鎵基板、一氮化鎵基板、一陶瓷基板、一玻璃基板或 其他適當的基板，而該待鍍金屬線路3表面上之金屬可以是 金(gold)、翻（platinum)、把（palladium)、銀（silver)、 錦（nickel)、銅（copper)、一金合金、一鉑合金、一把合 金、一銀合金、一鎳合金、一銅合金或其他適當的合金。 201038766 接著= 步驟S20所示，對該待錢基^的待鑛面 進仃μ處理，以去除待鍍面u 續化學鑛金處理，其中以-適當清洗方： 待鑛基板1的待鍍面11進行_處理，該適當清洗方式 =是:電料洗方式、—清洗液清洗方式或其他適^ 、;月洗方式，財該清洗液包含有至少不超過二十個碳的 水溶性界面雜贼—含妹雜有機賴之溶液或其 他適當溶液。201038766 VI. Description of the invention: [Technical field to which the invention pertains] - A method of moneyless gold, in particular, a method of plating a uniform thickness of a metal layer on a micro-scale line. [Prior Art] Due to advances in the manufacturing technology of integrated circuits, the manufacturing of the 〇25 micro 以下 以下 line is the mainstream of the current metallization process. As the size of the line is shrinking, how to efficiently form a substrate for forming a conductive material on a substrate having a minute size is an important key to development. The electroplating process is a technology that is filled with a small-sized circuit, and the electroplating is to immerse one piece of the object to be plated in an ionic solution containing electric ore metal to make the cathode and anode in the power supply and the electric clock slot. (Consumable or non-consumptive) Electrical connection, at the same time, the electroplated metal is placed on the anode, and the workpiece to be placed on the cathode is filled with a 0-metal thin film layer on the surface of the object to be deposited. ★ The thickness of the ore layer is always an important indicator for evaluating Wei performance. Referring to Figure 2, the prior art does not use the substrate mineralization method of the isolation layer, wherein the substrate A is provided with a substrate B, and when the substrate B is placed in the gold plating, the gold plating operation is performed. 'If there is no barrier layer on the outside of the substrate B (see the second figure of f), then the gold ion is on the substrate B, and the gold-plated layer c on the substrate B will not form. Stable semicircular bulge. Referring to the second figure, the schematic diagram of the gold plating method of the substrate using the isolation layer of the prior art 'the traditional sheet metal bath is provided with the substrate B on the button A, and the substrate B is made of metal, in the traditional key gold method. , will be on the substrate a on the outer side of 201038766 & g, paste oxidation! g, dioxin or photoresist to form a barrier layer Aj ' and can form a gold-plated space above the substrate b and in the gold During the process, the gold ions are freed and filled into the gold-plated space crucible, and stacked into a square-gold shape, and then the chemical layer is used to remove the separator A1 from the substrate a, that is, the gold plating operation on the substrate β is completed. However, the shortcoming of the prior art is that the method of electroplating gold is easy to form a gold-plated layer with uneven thickness. The plating has high and low currents, which may cause uneven thickness. In addition, the gold-plated bath must be preset before gold plating. Isolation 〇 | 'And then remove the isolation layer, in addition to the trouble and inconvenience of the reliance on gold, also increase the cost of materials and extend the processing time of the entire process, so it is necessary to rely on each other A method of forming a gold plating layer of uniform thickness on a minute-sized line. SUMMARY OF THE INVENTION The main object of the present invention is an electroless gold plating method on a micro-sized circuit of a substrate, comprising: providing a substrate to be plated, the substrate to be plated having at least one surface to be plated, the at least one surface to be plated Having a patterned metal line to be plated, the at least one surface to be plated of the substrate to be mined is cleaned in a cleaning manner to remove the organic substance remaining on the at least one surface to be plated, and the cleaning method can be a plasma cleaning method or a cleaning liquid cleaning method, wherein the cleaning liquid may be at least one of a water-soluble surfactant of at least twenty carbons or a solution containing a water-soluble organic solvent; The plated substrate is immersed in at least one of pure water, at least 85% aqueous surfactant or a salt aqueous solution to increase the surface wettability of the at least one surface to be plated of the substrate to be plated; The substrate to be plated is immersed in a gold bath, wherein the gold plating bath comprises at least one water-soluble gold compound, at least one gold mismatch, 201038766 agent, at least one carboxyl compound a salt thereof, wherein the at least one carboxyl compound or a salt thereof may be oxalic acid, malonic acid, succinic acid, butenedioic acid, valeric acid, lactic acid, glycolic acid, gluconic acid, citric acid, malic acid At least one of tartaric acid and its salts. Therefore, the present invention can solve the shortcomings of the conventional technology, and achieve a method of forming a gold-plated layer having a uniform thickness on a minute-sized line by virtue of the interaction of chemical components without requiring electrification and isolation layers, thereby effectively saving manufacturing costs. And manufacturing time. [Embodiment] The embodiments of the present invention will be described in more detail below with reference to the drawings and the reference numerals, which can be implemented by those skilled in the art after studying this specification. Referring to the second figure, the schematic diagram of the electroless gold plating method on the micro-sized circuit of the substrate of the present invention, together with the fourth figure, the substrate of the electroless gold method on the micro-sized circuit of the substrate of the present invention. schematic diagram. The present invention relates to a method for plating a uniform thickness metal layer on a micro-sized line by chemical gold, as shown in step S10 of the third figure, and in conjunction with the fourth figure, first providing a substrate 1 to be plated, The substrate to be plated 1 has at least one surface 11 to be plated, and the surface to be plated 11 has a patterned metal line 3 to be plated, wherein the substrate 1 to be mirrored may be a copper foil substrate, a substrate, and a arsenic. a gallium substrate, a gallium nitride substrate, a ceramic substrate, a glass substrate or other suitable substrate, and the metal on the surface of the metal to be plated 3 may be gold, platinum, palladium, Silver, nickel, copper, a gold alloy, a platinum alloy, a handful of alloys, a silver alloy, a nickel alloy, a copper alloy or other suitable alloy. 201038766 Next, as shown in step S20, the surface of the to-be-poor surface to be treated is subjected to 仃μ treatment to remove the surface to be plated, and the chemical ore treatment is continued, wherein - the appropriate cleaning side: the surface to be plated of the substrate 1 to be mined 11 _ treatment, the appropriate cleaning method = is: electric material washing method, - cleaning liquid cleaning method or other suitable, monthly washing method, the cleaning liquid contains at least no more than twenty carbon water-soluble interface Thieves - solutions containing sisters or other suitable solutions.
該清洗液清洗方式可岐將待雜板丨送至一清洗 機台（圖面未顯示）進行清洗，該清洗機台可以是水平 ，清洗機台、浸洗式機台、沖洗式機卜紐式機台或 單片式清洗機，而水洗溫度可為範圍為6〇卞至2〇〇卞。 參閱第五圖’本發明之於基材之微小尺寸線路上之無 電鑛金方法之浸潤示意圖。接著進入步驟S3〇所示，對 該待鍍基板1進行預浸潤濕處理，以使該待鍍基板丄的 待鍍面11之表面潤濕度增加，據以提升後續化學鍍金的 質其係將待鑛基板1浸入於一純水、—含水至少85% 以上之界面活性劑、一鹽類水溶液或其他適當溶液中， 如第五圖所示，可將待鍍基板1浸入於具有上述溶液之 至少其中之一的槽體4内。 其中該含水至少85%以上之界面活性劑中的界面活 性劑可以是聚乙烯基吡咯烷酮（poly(vinyl pyrrolidone))、聚乙二醇（polyethylene glycol)、 聚丙二醇（P〇ly(propylene glycol))或其共聚合物之 至少其中之一’且該含水至少85%以上之界面活性劑中的 界面活性劑其含量為〇. 1 — 30克/升。 .201038766 其中δ亥鹽類水溶液可以是一氯化納（s〇di um chloride)、一 氯化鉀（potassium chloride)、一磷酸 氫鈉（Sodium phosphate)、一磷酸二氫鈉（船加如以咖 phosphate) 一填酸氫卸（Potassium phosphate)、一 罐酸二氫鉀（monopotassium phosphate)之至少其中之 —咱 〇 參閱第六圖，本發明之於基材之微小尺寸線路上之無電 鍍金方法之化學鍍金浴示意圖。接著進入步驟34〇所示，將 Ο 該待鍵基板1浸入於一鍍金浴5中，並令該鍍金浴5係加熱 至溫度範圍為110°F至175T之間，要注意的是，本發明之 鍍金浴5並不需通電’而是透過該待鍍金屬線路3表面之元 素與該鍍金浴的組成成分之間的化學還原變化，促使鍍金浴 5中的金離子穩定、快速的正向沉積於待鍍金屬線路3的表 面上，以形成一厚度均勻的鍍金層31。 其中該化學鍍金浴5係至少包含一水溶性金化合物、至 少一種金錯合劑以及至少一種羧基化合物或至少一種羧基 ◎ 化合物的鹽類之至少其中一，其中該水溶性金化合物可以是 一氯化金、一亞硫酸金或一硫代硫酸金之至少其中一，該水 溶性金化合物的金含量為2. 0〜4. 5克/升。 而該至少一種缓基化合物可以是草酸（oxalic acid)、 丙二酸（propanedionic acid)、丁二酸（butanedionic acid)、丁浠二酸、戊二酸(pentanedionic acid)、乳酸 (lactic acid)、甘醇酸(glycolic acid)、葡萄糖酸 (gluconic acid)、檸檬酸(citric acid)、蘋果酸 (hydroxybutanedioic acid)、酒石酸(tartaric acid)、及 其鹽類之至少其中之一。 201038766 、該鑛金浴5内可進一步設置一循環過遽器（圖面未顯 不）’該她碱Hx使觀鍍麵5之濃度鋪均句 化’另相待鍍基板1麟鍍金浴5之娜搖擺量為4 -12公尺/分鐘，如此可驅使金離子均自分佈於待鍍金屬 線路3的表面上，使鍍金層31厚度更加均勻。 綜上所述，透過清潔將有殘留的有機物質去除，而基 板浸潤後待錄金屬線路3可增加其表面濕潤度，如此當 频餘1置人_金斜時，_溫度财度的調整， 〇 而激化鍍金浴5中的金離子，使金離子正向沉積鍍金層 於待鑛金屬線路3絲上，因此不f衫加_道設置隔 絕層之步驟，即能透過化學反應形成厚度均勻之鍍金 f ’尤其鍍金浴5中不添加氰化物，因此鍍金浴5為低 毋14 ’並利用其中之竣基化合物及叛基化合物的鹽類， $鑛金浴5的沉麵定劑，使金離子具有高安定性、 …儿積速率及向附著性，因此特別適用於具微小尺寸線 路之基板上。 〇 以上所述者僅為用以解釋本發明之較佳實施例，並非企 1據以對本發明做任何形式上之限制，是以，凡有在相同之 I明精神下所作有關本發明之任何修飾鎌更，皆仍應包括 在本發明意圖保護之範疇。 201038766 【圖式簡單說明】 ^圖圖為習知技術之未使用隔_之基材鍍金方式之干 示意 第二圖為習知技術之使用隔離層之基材鍍金方式 圖。 之 尺寸線路上之無電鍍金 第三圖為本發明之於基材之微小 方法之流程示意圖。 第四圖為本發明之於基材之微小尺寸線路上之無電鍍金方 法之基材示意圖。 “The cleaning liquid cleaning method can send the waiting board to a washing machine (not shown) for cleaning, the cleaning machine can be horizontal, washing machine, dipping machine, flushing machine A machine or a one-piece washer, and the water wash temperature can range from 6 〇卞 to 2 〇〇卞. Referring to Figure 5, a schematic view of the wetting of the electroless gold method on the micro-sized lines of the substrate of the present invention. And proceeding to step S3, the pre-dip wetting treatment is performed on the substrate 1 to be plated to increase the surface wettability of the surface 11 to be plated of the substrate to be plated, thereby improving the quality of the subsequent electroless gold plating. The substrate 1 to be immersed is immersed in a pure water, a surfactant containing at least 85% of water, a salt solution or other suitable solution. As shown in FIG. 5, the substrate 1 to be plated may be immersed in the solution having the above solution. At least one of the tanks 4 is inside. The surfactant in the surfactant containing at least 85% by water may be poly(vinyl pyrrolidone), polyethylene glycol, or polypropylene glycol (P〇ly (propylene glycol)). The surfactant in at least one of the copolymers thereof and at least 85% or more of the surfactant is present in an amount of from 0.1 to 30 g/l. .201038766 wherein the δ hai salt aqueous solution may be sodium sulphate, potassium chloride, sodium phosphate, sodium dihydrogen phosphate (such as ship plus Phosphate) at least one of Potassium phosphate and one pot of monopotassium phosphate - see Figure 6 for electroless gold on the micro-sized lines of the substrate of the present invention. A schematic diagram of an electroless gold bath of the method. Next, proceeding to step 34, the immersion substrate 1 is immersed in a gold plating bath 5, and the gold plating bath 5 is heated to a temperature ranging from 110 °F to 175T. It is noted that the present invention The gold plating bath 5 does not need to be energized, but the chemical reduction between the elements on the surface of the metal line 3 to be plated and the composition of the gold plating bath promotes stable, rapid forward deposition of gold ions in the gold plating bath 5. On the surface of the metal line 3 to be plated, a gold plating layer 31 having a uniform thickness is formed. Wherein the electroless gold plating bath 5 comprises at least one of a water soluble gold compound, at least one gold complexing agent and at least one carboxyl compound or at least one salt of a carboxyl group compound, wherein the water soluble gold compound may be monochlorinated. 5克/升。 The gold, the content of the water-soluble gold compound is 2. 0~4. 5 g / liter. The at least one slow-acting compound may be oxalic acid, propanedionic acid, butaned ionic acid, butyric acid, pentaned ionic acid, lactic acid, At least one of a glycolic acid, a gluconic acid, a citric acid, a hydroxybutanedioic acid, a tartaric acid, and a salt thereof. 201038766, the gold bath 5 in the mine can be further set up a loop through the device (the surface is not shown) 'the base Hx makes the concentration of the plating surface 5 shop evenly. Another phase to be plated substrate 1 Lin gold bath 5 The amount of rock shake is 4 -12 meters / minute, which can drive the gold ions to self-distribute on the surface of the metal line 3 to be plated, so that the thickness of the gold plating layer 31 is more uniform. In summary, the residual organic matter is removed by cleaning, and the metal line 3 to be recorded after the substrate is infiltrated can increase the surface wetness, so when the frequency is set to 1 _ gold oblique, _ temperature financial adjustment, The gold ions in the gold plating bath 5 are intensified, so that the gold ions are positively deposited on the gold wire of the metal wire to be mined, so that the step of providing the insulating layer is not to form a uniform thickness through chemical reaction. Gold-plated f 'especially gold-plated bath 5 does not contain cyanide, so gold-plated bath 5 is low 毋 14 ' and uses the sulfhydryl compound and the salts of the ruthenium compound, the gold surface of the gold bath 5 to make gold Ions have high stability, aglow rate and adhesion, so they are especially suitable for substrates with tiny size lines. The above is only a preferred embodiment for explaining the present invention, and is not intended to limit the present invention in any way, so that any of the inventions in the spirit of the same invention can be used. Modifications should still be included in the scope of the invention as intended. 201038766 [Simple description of the drawing] ^The figure is a dry plating method of the substrate which is not used in the prior art. The second figure shows the gold plating method of the substrate using the isolation layer of the prior art. Electroless gold plating on the size line The third figure is a schematic flow chart of the minute method of the present invention for the substrate. The fourth figure is a schematic view of the substrate of the electroless gold plating method on the micro-sized line of the substrate of the present invention. "
第五圖為本發明之於基材之微小尺寸線路上之無電鑛金 方法之浸潤示意圖。 "V 第六圖為本發明之於基材之微小尺寸線路上之無電鍛金 方法之化學鍍金浴示意圖。 201038766 【主要元件符號說明】 S10、S20、S30、S40 步驟 1待鍍基板 11待鑛面 3待鍍金屬線路 31鍍金層 4槽體 5鍍金浴 A基材 B底材 C鑛金層 A1隔離層 All鍍金空間The fifth figure is a schematic diagram of the wetting of the electroless gold method on the micro-sized line of the substrate of the present invention. "V The sixth figure is a schematic diagram of the electroless gold plating bath of the electroless gold forging method on the micro-sized line of the substrate of the present invention. 201038766 [Description of main components] S10, S20, S30, S40 Step 1 Substrate to be plated 11 To be mined 3 Metal to be plated 31 Gold plated 4 Slot 5 Gold plated bath A Substrate B Substrate C Mineral gold layer A1 Isolation layer All gold-plated space