TWI710020B - Manufacturing method of flexible circuit board, electroplating solution and etching solution - Google Patents
Manufacturing method of flexible circuit board, electroplating solution and etching solution Download PDFInfo
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本發明涉及一種電路板的製造方法，特別是涉及一種軟性電路板的製造方法、電鍍藥水及蝕刻藥水。 The invention relates to a method for manufacturing a circuit board, in particular to a method for manufacturing a flexible circuit board, an electroplating solution and an etching solution.
近年來，隨著4G/5G高速傳輸的相關技術愈趨發展成熟，相關電子產品的設計需要趨向輕薄短小，相關電子產品內部所使用的印刷電路板(printed circuit board，PCB/flexible circuit board，FPCB)與電子零件相對也要小型化和輕量化。 In recent years, as the related technologies of 4G/5G high-speed transmission have become more mature, the design of related electronic products needs to be lighter, thinner and shorter. The printed circuit board (PCB/flexible circuit board, FPCB) used in related electronic products ) Compared with electronic parts, miniaturization and weight reduction are also required.
進一步地說，現有的軟性電路板的製造方式上有許多的改良，目的都是為了製造出更適合應用於4G/5G高速傳輸的相關電子產品中的軟性電路板。 Furthermore, there are many improvements in the existing manufacturing methods of flexible circuit boards, and the purpose is to manufacture flexible circuit boards that are more suitable for 4G/5G high-speed transmission related electronic products.
然而，現有的軟性電路板的製造方法已逐漸無法滿足細線寬的要求，並且現有的軟性電路板的製造方法在生產細線路的軟性基板時，容易產生良率不足、電鍍厚度控制不佳、及部份過蝕刻且部分蝕刻不足等問題。 However, the existing flexible circuit board manufacturing methods have gradually failed to meet the requirements of fine line width, and the existing flexible circuit board manufacturing methods are prone to insufficient yield, poor plating thickness control, and poor control of plating thickness when producing thin-circuit flexible substrates. Some problems such as over-etching and under-etching.
於是，本發明人認為上述缺陷可改善，乃特潛心研究並配合科學原理的運用，終於提出一種設計合理且有效改善上述缺陷的本發明。 Therefore, the inventor believes that the above-mentioned shortcomings can be improved, and with great concentration of research and the application of scientific principles, we finally propose an invention with reasonable design and effective improvement of the above-mentioned shortcomings.
本發明所要解決的技術問題在於，針對現有技術的不足提供一種軟性電路板的製造方法、電鍍藥水及蝕刻藥水，能有效改善現有的軟性電路板的製造方法所存在的缺陷。 The technical problem to be solved by the present invention is to provide a method for manufacturing a flexible circuit board, an electroplating solution and an etching solution in view of the shortcomings of the prior art, which can effectively improve the defects of the existing manufacturing method of the flexible circuit board.
為了解決上述的技術問題，本發明所採用的其中一技術方案是，提供一種軟性電路板的製造方法，其包括：提供一軟性基板，其具有位於相反側的兩個表面；形成一金屬晶種層於所述軟性基板的至少其中一個所述表面上；形成一圖案化遮罩於所述金屬晶種層的相反於所述軟性基板的一側表面上；其中，所述圖案化遮罩的內側包圍形成有多個圖案化間隙，並且所述金屬晶種層的至少局部能通過多個所述圖案化間隙而暴露於外界環境；將所述軟性基板置入一電鍍藥水中，以使得所述電鍍藥水能進入多個所述圖案化間隙中、且能接觸於所述金屬晶種層；其中，所述電鍍藥水的表面張力大於所述圖案化遮罩的表面張力，並且所述電鍍藥水的所述表面張力與所述圖案化遮罩的所述表面張力的差值不大於20mN/m；通過電鍍的方式形成多個導電金屬於多個所述圖案化間隙中；其中，多個所述導電金屬是自所述金屬晶種層朝著相反於所述軟性基板的方向延伸地形成、且填充於多個所述圖案化間隙中；移除所述圖案化遮罩；以及使用一蝕刻藥水對所述金屬晶種層進行蝕刻，以將所述金屬晶種層的未被多個所述導電金屬覆蓋的部分移除，從而使得多個所述導電金屬形成為一圖案化線路。 In order to solve the above technical problems, one of the technical solutions adopted in the present invention is to provide a method for manufacturing a flexible circuit board, which includes: providing a flexible substrate with two surfaces on opposite sides; forming a metal seed crystal Layer on at least one of the surfaces of the flexible substrate; forming a patterned mask on the surface of the metal seed layer opposite to the flexible substrate; wherein the patterned mask A plurality of patterned gaps are formed on the inner side, and at least a part of the metal seed layer can be exposed to the external environment through the plurality of patterned gaps; the flexible substrate is placed in an electroplating bath to make the The electroplating solution can enter a plurality of the patterned gaps and can contact the metal seed layer; wherein the surface tension of the electroplating solution is greater than the surface tension of the patterned mask, and the electroplating solution The difference between the surface tension of the patterned mask and the surface tension of the patterned mask is not more than 20mN/m; a plurality of conductive metals are formed in the plurality of patterned gaps by electroplating; wherein, a plurality of The conductive metal is formed to extend from the metal seed layer in a direction opposite to the flexible substrate, and is filled in the plurality of patterned gaps; remove the patterned mask; and use an etching The liquid medicine etches the metal seed layer to remove the part of the metal seed layer not covered by the plurality of conductive metals, so that the plurality of conductive metals form a patterned circuit.
為了解決上述的技術問題，本發明所採用的另外一技術方案是，提供一種電鍍藥水，其適用於軟性電路板的電鍍製程，其特徵在於所述電鍍藥水包括：銅錯合物、表面張力調整劑、硫酸、鹽酸、及助劑；其中，基於所述電鍍藥水的總重為100wt%，所述銅錯合物的濃度範圍是介於3wt%至15wt%之間，並且所述表面張力調整劑的濃度範圍是介於7wt%至30wt%之 間；其中，所述銅錯合物的構型為八面體，所述銅錯合物的中心為銅離子，並且所述銅錯合物的配體分子中包含有：含氮官能基(N-group)及含硫官能基(S-group)的至少其中之一；其中，所述表面張力調整劑為聚醚多元醇(polyether polyol)；其中，所述電鍍藥水的表面張力是介於45mN/m至60mN/m。 In order to solve the above technical problems, another technical solution adopted by the present invention is to provide an electroplating solution, which is suitable for the electroplating process of flexible circuit boards, and is characterized in that the electroplating solution includes: copper complex, surface tension adjustment Agent, sulfuric acid, hydrochloric acid, and auxiliary agent; wherein, based on the total weight of the electroplating solution is 100wt%, the concentration of the copper complex is between 3wt% to 15wt%, and the surface tension is adjusted The concentration range of the agent is between 7wt% to 30wt% Wherein, the configuration of the copper complex is an octahedron, the center of the copper complex is a copper ion, and the ligand molecule of the copper complex contains: a nitrogen-containing functional group ( N-group) and at least one of a sulfur-containing functional group (S-group); wherein, the surface tension modifier is polyether polyol; wherein the surface tension of the electroplating solution is between 45mN/m to 60mN/m.
為了解決上述的技術問題，本發明所採用的另外一技術方案是，提供一種蝕刻藥水，其適用於軟性電路板的蝕刻製程，其特徵在於所述蝕刻藥水包括：蝕刻阻劑、蝕刻主劑、硫酸銅、安定劑、及加速劑；其中，基於所述蝕刻藥水的總重為100wt%，所述蝕刻阻劑的濃度範圍是介於5wt%至20wt%之間；其中，所述蝕刻阻劑為尿唑(CAS號：3232-84-6)，所述蝕刻主劑是由硫酸及雙氧水組成，所述安定劑為磺酸鹽，並且所述加速劑為丁二醇。 In order to solve the above technical problem, another technical solution adopted by the present invention is to provide an etching solution suitable for the etching process of flexible circuit boards, characterized in that the etching solution includes: an etching resist, an etching main agent, Copper sulfate, stabilizer, and accelerator; wherein, based on the total weight of the etching potion is 100wt%, the concentration range of the etching resist is between 5wt% to 20wt%; wherein, the etching resist It is urazole (CAS number: 3232-84-6), the main etching agent is composed of sulfuric acid and hydrogen peroxide, the stabilizer is sulfonate, and the accelerator is butanediol.
本發明的其中一有益效果在於，本發明所提供的所述軟性電路板的製造方法，其能通過“改良電鍍藥水成分”以及“改良蝕刻藥水成分”的技術方案，據以改善現有的軟性電路板的製造方法在生產細線路的軟性基板時，容易產生良率不足、電鍍厚度控制不佳、及部份過蝕刻且部分蝕刻不足等問題。 One of the beneficial effects of the present invention is that the method for manufacturing the flexible circuit board provided by the present invention can improve the existing flexible circuit through the technical solutions of "improving the composition of electroplating solution" and "improving the composition of etching solution" The manufacturing method of the board is prone to problems such as insufficient yield rate, poor plating thickness control, and partial over-etching and partial under-etching when producing thin-circuit flexible substrates.
為使能更進一步瞭解本發明的特徵及技術內容，請參閱以下有關本發明的詳細說明與圖式，然而所提供的圖式僅用於提供參考與說明，並非用來對本發明加以限制。 In order to further understand the features and technical content of the present invention, please refer to the following detailed description and drawings about the present invention. However, the provided drawings are only for reference and description, and are not used to limit the present invention.
1:圖案化線路 1: Patterned circuit
C:軟性基板 C: Flexible substrate
C1:表面 C1: Surface
C2:金屬晶種層 C2: Metal seed layer
C21:側表面 C21: Side surface
M:圖案化遮罩 M: Patterned mask
M1:圖案化間隙 M1: Patterned gap
E:導電金屬 E: conductive metal
L:縱向方向 L: longitudinal direction
W:橫向方向 W: horizontal direction
W1min:最小圖案化間隙 W1min: Minimum patterning gap
W2min:最小線路寬度 W2min: minimum line width
圖1為本發明實施例的軟性電路板的製造方法示意圖(一)。 FIG. 1 is a schematic diagram (1) of a manufacturing method of a flexible circuit board according to an embodiment of the present invention.
圖2為本發明實施例的軟性電路板的製造方法示意圖(二)。 FIG. 2 is a schematic diagram (2) of the manufacturing method of the flexible circuit board according to the embodiment of the present invention.
圖3為本發明實施例的軟性電路板的製造方法示意圖(三)。 FIG. 3 is a schematic diagram (3) of the manufacturing method of the flexible circuit board according to the embodiment of the present invention.
圖4為本發明實施例的軟性電路板的製造方法示意圖(四)。 4 is a schematic diagram (4) of the manufacturing method of the flexible circuit board according to the embodiment of the present invention.
圖5為本發明實施例的軟性電路板的製造方法示意圖(五)。 FIG. 5 is a schematic diagram (5) of the manufacturing method of the flexible circuit board according to the embodiment of the present invention.
圖6為本發明實施例的軟性電路板的製造方法示意圖(六)。 Fig. 6 is a schematic diagram (6) of the manufacturing method of the flexible circuit board according to the embodiment of the present invention.
以下是通過特定的具體實施例來說明本發明所公開的實施方式，本領域技術人員可由本說明書所公開的內容瞭解本發明的優點與效果。本發明可通過其他不同的具體實施例加以施行或應用，本說明書中的各項細節也可基於不同觀點與應用，在不悖離本發明的構思下進行各種修改與變更。另外，本發明的附圖僅為簡單示意說明，並非依實際尺寸的描繪，事先聲明。以下的實施方式將進一步詳細說明本發明的相關技術內容，但所公開的內容並非用以限制本發明的保護範圍。 The following are specific examples to illustrate the disclosed embodiments of the present invention. Those skilled in the art can understand the advantages and effects of the present invention from the content disclosed in this specification. The present invention can be implemented or applied through other different specific embodiments, and various details in this specification can also be modified and changed based on different viewpoints and applications without departing from the concept of the present invention. In addition, the drawings of the present invention are merely schematic illustrations, and are not drawn according to actual dimensions, and are stated in advance. The following embodiments will further describe the related technical content of the present invention in detail, but the disclosed content is not intended to limit the protection scope of the present invention.
應當可以理解的是，雖然本文中可能會使用到“第一”、“第二”、“第三”等術語來描述各種元件或者信號，但這些元件或者信號不應受這些術語的限制。這些術語主要是用以區分一元件與另一元件，或者一信號與另一信號。另外，本文中所使用的術語“或”，應視實際情況可能包括相關聯的列出項目中的任一個或者多個的組合。 It should be understood that although terms such as “first”, “second”, and “third” may be used herein to describe various elements or signals, these elements or signals should not be limited by these terms. These terms are mainly used to distinguish one element from another, or one signal from another signal. In addition, the term "or" used in this document may include any one or a combination of more of the associated listed items depending on the actual situation.
請參閱圖1至圖6所示，本發明實施例提供一種軟性電路板的製造方法。所述軟性電路板的製造方法包含步驟S110至S170，據以於一軟性基板C上形成有一圖案化線路1。必須說明的是，本實施例所載的各步驟的順序與實際的操作方式可視需求而調整，並不限於本實施例所載。 Referring to FIG. 1 to FIG. 6, an embodiment of the present invention provides a method for manufacturing a flexible circuit board. The manufacturing method of the flexible circuit board includes steps S110 to S170, according to which a patterned circuit 1 is formed on a flexible substrate C. It must be noted that the order of the steps and the actual operation mode contained in this embodiment can be adjusted according to requirements and are not limited to those contained in this embodiment.
如圖1所示，所述步驟S110包含：提供所述軟性基板C，其具有位於相反側的兩個表面C1。所述軟性基板C本身呈片狀，並且所述軟性 基板C的一橫截面於圖1中大致呈矩形。上述矩形的長邊大致平行於一橫向方向W，上述矩形的短邊大致平行於一縱向方向L，並且所述橫向方向W是垂直於所述縱向方向L。 As shown in FIG. 1, the step S110 includes: providing the flexible substrate C, which has two surfaces C1 on opposite sides. The flexible substrate C itself is sheet-like, and the soft A cross section of the substrate C is substantially rectangular in FIG. 1. The long sides of the rectangle are substantially parallel to a transverse direction W, the short sides of the rectangle are substantially parallel to a longitudinal direction L, and the transverse direction W is perpendicular to the longitudinal direction L.
在本實施例中，所述軟性基板C主要用來提供如下述的一金屬晶種層C2、一圖案化遮罩M、多個導電金屬E、及所述圖案化線路1等形成於所述軟性基板C的至少其中一個所述表面C1上。所述軟性基板C的材質可以例如是聚醯亞胺(polyimide，PI)、聚碳酸酯(polycarbonate，PC)、聚對苯二甲酸乙二酯(polyethylene terephthalate，PET)、及聚四氟乙烯(polytetrafluoroethylene，PTFE)的至少其中之一。在本實施例中，所述軟性基板C的材質優選為聚醯亞胺。 In this embodiment, the flexible substrate C is mainly used to provide a metal seed layer C2, a patterned mask M, a plurality of conductive metals E, and the patterned circuit 1 formed on the On at least one of the surfaces C1 of the flexible substrate C. The material of the flexible substrate C can be, for example, polyimide (PI), polycarbonate (PC), polyethylene terephthalate (PET), and polytetrafluoroethylene ( at least one of polytetrafluoroethylene, PTFE). In this embodiment, the material of the flexible substrate C is preferably polyimide.
如圖2所示，所述步驟S120包含：形成所述金屬晶種層C2於所述軟性基板C的至少其中一個所述表面C1上。在本實施例中，所述金屬晶種層C2是形成於所述軟性基板C朝向圖2中上方的所述表面C1，但本發明不受限於此。舉例來說，於本發明未繪示的其他實施例中，於所述軟性基板C的兩個所述表面C1也可以皆形成有所述金屬晶種層C2。此外，所述金屬晶種層C2可以例如是通過無電鍍(electroless plating)或濺鍍(sputtering)的方式所形成，並且所述金屬晶種層C2的材質可以例如是銅金屬，但本發明不受限於此。 As shown in FIG. 2, the step S120 includes: forming the metal seed layer C2 on at least one of the surfaces C1 of the flexible substrate C. In this embodiment, the metal seed layer C2 is formed on the surface C1 of the flexible substrate C facing the upper side in FIG. 2, but the present invention is not limited to this. For example, in other embodiments not shown in the present invention, the metal seed layer C2 may also be formed on the two surfaces C1 of the flexible substrate C. In addition, the metal seed layer C2 can be formed, for example, by electroless plating or sputtering, and the material of the metal seed layer C2 can be, for example, copper metal, but the present invention does not Limited by this.
如圖3所示，所述步驟S130包含：形成所述圖案化遮罩M於所述金屬晶種層C2的相反於所述軟性基板C的一側表面C21上。更具體地說，所述圖案化遮罩M是直接地形成於金屬晶種層C2上、且位於所述軟性基板C的所述表面C1上方。所述圖案化遮罩M的內側包圍形成有多個圖案化間隙M1，並且所述金屬晶種層C2的至少局部(如：金屬晶種層C2的未被圖案化遮罩M遮蔽的部分)能通過多個所述圖案化間隙M1而暴露於外界環境。 As shown in FIG. 3, the step S130 includes: forming the patterned mask M on the surface C21 of the metal seed layer C2 opposite to the flexible substrate C. More specifically, the patterned mask M is formed directly on the metal seed layer C2 and located above the surface C1 of the flexible substrate C. A plurality of patterned gaps M1 are formed on the inner side of the patterned mask M, and at least a part of the metal seed layer C2 (for example, the portion of the metal seed layer C2 that is not covered by the patterned mask M) It can be exposed to the external environment through a plurality of the patterned gaps M1.
於本實施例中，所述圖案化遮罩M的材料可以為一乾膜光阻， 並且所述圖案化遮罩M的材料優選為壓克力乾膜光阻。所述圖案化遮罩M的表面張力是介於33mN/m至43mN/m之間，並且所述圖案化遮罩M的所述表面張力優選為介於36mN/m至40mN/m之間。需要說明的是，如圖3所示，於本實施例中的所述圖案化遮罩M的外形是以三個矩形來說明，但所述圖案化遮罩M的數量、外形、材質、尺寸、形成位置、及其他相關性質等皆可依據需求變化，本發明不受限於此。 In this embodiment, the material of the patterned mask M may be a dry film photoresist, Moreover, the material of the patterned mask M is preferably an acrylic dry film photoresist. The surface tension of the patterned mask M is between 33 mN/m and 43 mN/m, and the surface tension of the patterned mask M is preferably between 36 mN/m and 40 mN/m. It should be noted that, as shown in FIG. 3, the shape of the patterned mask M in this embodiment is illustrated by three rectangles, but the number, shape, material, and size of the patterned mask M , Formation location, and other related properties can be changed according to requirements, and the present invention is not limited to this.
於本實施例中，是以兩個尺寸相等的所述圖案化間隙M1來說明，但多個所述圖案化間隙M1的尺寸不限制為相等，並且多個所述圖案化間隙M1的數量、形成位置等也可依據需求變化，本發明不受限於此。在本發明未繪示的其他實施例中，所述圖案化間隙M1的數量也可以是一個。此外，於所述橫向方向W上，多個所述圖案化間隙M1中的一最小圖案化間隙W1min不大於25微米，並且所述最小圖案化間隙W1min優選為不大於20微米。 In the present embodiment, two patterned gaps M1 of equal size are used for illustration, but the size of a plurality of patterned gaps M1 is not limited to be equal, and the number of patterned gaps M1 is The forming position and the like can also be changed according to requirements, and the present invention is not limited to this. In other embodiments not shown in the present invention, the number of the patterned gap M1 may also be one. In addition, in the lateral direction W, a minimum patterning gap W1min of the plurality of patterning gaps M1 is not greater than 25 microns, and the minimum patterning gap W1min is preferably not greater than 20 microns.
所述步驟S140包含：將所述軟性基板C置入一電鍍藥水中(如：將所述軟性基板C浸泡於所述電鍍藥水中)，以使得所述電鍍藥水能進入多個所述圖案化間隙M1中、且能接觸於所述金屬晶種層C2(圖未繪示)；其中，所述電鍍藥水的所述表面張力是介於45mN/m至60mN/m，並且所述電鍍藥水的所述表面張力優選為介於50mN/m至55mN/m。此外，所述電鍍藥水的表面張力大於所述圖案化遮罩M的所述表面張力，並且所述電鍍藥水的所述表面張力與所述圖案化遮罩M的所述表面張力的差值不大於20mN/m。 The step S140 includes: immersing the flexible substrate C in an electroplating bath (for example, immersing the flexible substrate C in the electroplating bath), so that the electroplating bath can enter a plurality of the patterning baths. The gap M1 is in contact with the metal seed layer C2 (not shown); wherein, the surface tension of the electroplating solution is between 45mN/m and 60mN/m, and the electroplating solution has The surface tension is preferably between 50 mN/m and 55 mN/m. In addition, the surface tension of the electroplating solution is greater than the surface tension of the patterned mask M, and the difference between the surface tension of the electroplating solution and the surface tension of the patterned mask M is different. More than 20mN/m.
值得一提的是，上述電鍍藥水與圖案化遮罩M之間的表面張力差值能使所述電鍍藥水有效地進入多個所述圖案化間隙M1中，進而避免因所述電鍍藥水難以進入多個所述圖案化間隙M1而造成漏鍍現象。並且，上述差值優選為不大於15mN/m。此外，於所述步驟S140中，還可以對置入於所述電鍍藥水中的所述軟性基板C施加一外力(如：超音波震盪)，據以使所述電鍍 藥水能更有效地進入多個所述圖案化間隙M1中，但本發明不受限於此。 It is worth mentioning that the difference in surface tension between the electroplating solution and the patterned mask M can enable the electroplating solution to effectively enter the patterned gaps M1, thereby preventing the electroplating solution from being difficult to enter. A plurality of the patterned gaps M1 causes a plating leakage phenomenon. Also, the above difference is preferably not more than 15 mN/m. In addition, in the step S140, an external force (such as ultrasonic vibration) may be applied to the flexible substrate C placed in the electroplating bath, so that the electroplating The medicine can enter the patterned gaps M1 more effectively, but the present invention is not limited to this.
一般來說，於所述步驟S140中，多個所述圖案化間隙M1中會有氣泡存在，並且上述氣泡會使所述電鍍藥水不易進入多個所述圖案化間隙M1中，進而造成漏鍍現象。因此，還可以於鄰近於多個所述圖案化間隙M1的位置設置一高流量噴嘴(圖未示)，並且使所述高流量噴嘴帶動鄰近於多個所述圖案化間隙M1的流體，據以使原本位於所述圖案化間隙M1中的氣泡離開所述圖案化間隙M1，進而避免因氣泡存在於所述圖案化間隙M1而產生漏鍍現象。需要說明的是，所述高流量噴嘴的噴壓、外形、噴口大小、數量、設置位置、及其他相關性質等皆可依據需求變化，本發明於此不加以限制。 Generally speaking, in the step S140, there will be bubbles in the plurality of patterned gaps M1, and the above-mentioned bubbles will make it difficult for the electroplating solution to enter the plurality of patterned gaps M1, thereby causing leakage of plating. phenomenon. Therefore, a high-flow nozzle (not shown) can also be arranged at a position adjacent to the plurality of patterned gaps M1, and the high-flow nozzle can drive the fluid adjacent to the plurality of patterned gaps M1, according to This allows the bubbles originally located in the patterned gap M1 to leave the patterned gap M1, thereby avoiding the occurrence of plating leakage due to the presence of the bubbles in the patterned gap M1. It should be noted that the spray pressure, shape, nozzle size, number, setting position, and other related properties of the high-flow nozzle can be changed according to requirements, and the present invention is not limited herein.
進一步地說，所述電鍍藥水的組成至少包含有銅錯合物及表面張力調整劑。其中，基於所述電鍍藥水的總重為100wt%，所述銅錯合物的濃度範圍是介於3wt%至15wt%之間，並且所述表面張力調整劑的濃度範圍是介於7wt%至30wt%之間。優選地，所述銅錯合物的濃度範圍是介於5wt%至8wt%之間，並且所述表面張力調整劑的濃度範圍是介於10wt%至20wt%之間。 Furthermore, the composition of the electroplating solution at least includes a copper complex and a surface tension regulator. Wherein, based on the total weight of the electroplating solution being 100wt%, the concentration range of the copper complex is between 3wt% to 15wt%, and the concentration range of the surface tension modifier is between 7wt% to Between 30wt%. Preferably, the concentration range of the copper complex compound is between 5 wt% and 8 wt%, and the concentration range of the surface tension adjusting agent is between 10 wt% and 20 wt%.
所述銅錯合物的構型為八面體，所述銅錯合物的中心為銅離子，並且所述銅錯合物的配體分子中包含有：含氮官能基(N-group)及含硫官能基(S-group)的至少其中之一。詳細來說，所述銅錯合物是可以通過下述的助劑(如：光澤劑及平整劑)將水性銅離子修改成具有N-group及S-group而形成，使所述銅錯合物有最小體積的分子結構及最低的立體障礙，進而使所述銅錯合物能有效地進入所述圖案化間隙M1並與所述金屬晶種層C2進行銅沉積反應。舉例來說，所述銅錯合物可以例如是四氨合銅離子(Tetraamminecopper(II)ion)，其化學式為[Cu(NH3)4]2+，但本發明不受限於此。 The configuration of the copper complex is an octahedron, the center of the copper complex is a copper ion, and the ligand molecule of the copper complex contains: a nitrogen-containing functional group (N-group) And at least one of the sulfur-containing functional groups (S-group). In detail, the copper complex can be formed by modifying the aqueous copper ions to have N-group and S-group with the following auxiliary agents (such as: a gloss agent and a leveling agent) to make the copper complex The substance has the smallest volume of molecular structure and the lowest steric barrier, so that the copper complex can effectively enter the patterned gap M1 and undergo a copper deposition reaction with the metal seed layer C2. For example, the copper complex may be, for example, tetraammine copper ion (Tetraammine copper (II) ion), the chemical formula of which is [Cu(NH3)4]2+, but the present invention is not limited thereto.
所述表面張力調整劑為長鏈環氧基聚合物(如：聚醚多元醇)， 其可以降低所述電鍍藥水的極性，據以使所述電鍍藥水易於進入具有低極性的所述圖案化遮罩M(於本實施例中，其材質為如上所述的壓克力乾膜光阻)所形成的所述圖案化間隙M1中。並且，所述表面張力調整劑可以螯合所述電鍍藥水中的銅離子，據以形成如下圖中所示的化合物。 The surface tension modifier is a long-chain epoxy polymer (such as polyether polyol), It can reduce the polarity of the electroplating solution, so that the electroplating solution can easily enter the patterned mask M with low polarity (in this embodiment, the material is acrylic dry film light as described above). Resistance) in the patterned gap M1 formed. In addition, the surface tension adjusting agent can chelate copper ions in the electroplating bath to form a compound as shown in the following figure.
於上圖中，R、R1、及R2可以是碳數為1個至8個的烷基或是碳數為1個至8個的醇類，並且R3及R4可以是氫基、碳數為1個至8個的烷基或是碳數為1個至8個的醇類。上述聚醚多元醇(polyether polyol)，簡稱聚醚，是由起始劑(含活性氫基團的化合物)與環氧乙烷(EO)、環氧丙烷(PO)、環氧丁烷(BO)等在催化劑存在下經加聚反應製得。 In the above figure, R, R1, and R2 can be alkyl groups with 1 to 8 carbons or alcohols with 1 to 8 carbons, and R3 and R4 can be hydrogen groups with carbon numbers An alkyl group having 1 to 8 or an alcohol having 1 to 8 carbon atoms. The above-mentioned polyether polyol (polyether polyol), referred to as polyether, is composed of an initiator (a compound containing active hydrogen groups) and ethylene oxide (EO), propylene oxide (PO), butylene oxide (BO) ) And so on in the presence of a catalyst through addition polymerization.
所述表面張力調整劑還能有效地降低所述電鍍藥水的所述表面張力，據以使所述電鍍藥水更容易進入多個所述圖案化間隙M1中。並且，所述表面張力調整劑選自分子量較大的聚合物(如上述長鏈環氧基聚合物)，據以避免因所述表面張力調整劑進入多個所述圖案化間隙M1中而影響電鍍效果(如：造成漏鍍現象或降低電鍍效率)。 The surface tension adjusting agent can also effectively reduce the surface tension of the electroplating solution, so that the electroplating solution can easily enter the plurality of patterned gaps M1. In addition, the surface tension modifier is selected from polymers with larger molecular weights (such as the above-mentioned long-chain epoxy-based polymers), so as to avoid the influence of the surface tension modifier entering the plurality of patterned gaps M1 Electroplating effect (such as: causing leakage or reducing plating efficiency).
更進一步地，所述電鍍藥水的組成含有：硫酸、鹽酸、及所述助劑；其中，所述助劑包含有：所述平整劑(leveler)及所述光澤劑(brightener)；其中，基於所述電鍍藥水的總重為100wt%，硫酸、鹽酸、及助劑的濃度範圍的總和是介於55wt%至90wt%之間。 Furthermore, the composition of the electroplating solution contains: sulfuric acid, hydrochloric acid, and the auxiliary agent; wherein, the auxiliary agent includes: the leveler and the brightener; wherein, based on The total weight of the electroplating solution is 100 wt%, and the sum of the concentration ranges of sulfuric acid, hydrochloric acid, and additives is between 55 wt% and 90 wt%.
如圖4所示，所述步驟S150包含：通過電鍍的方式形成多個所述導電金屬E於多個所述圖案化間隙M1中；其中，多個所述導電金屬E是自所述 金屬晶種層C2朝著相反於所述軟性基板C的方向延伸地形成、且填充於多個所述圖案化間隙M1中。也就是說，多個所述導電金屬E是沿所述縱向方向L朝圖4中的上方延伸地形成，並且於各個所述圖案化間隙M1皆形成有所述導電金屬E。 As shown in FIG. 4, the step S150 includes: forming a plurality of the conductive metals E in the plurality of patterned gaps M1 by electroplating; wherein, the plurality of conductive metals E are from the The metal seed layer C2 is formed to extend in a direction opposite to the flexible substrate C, and is filled in the plurality of patterned gaps M1. That is, a plurality of the conductive metals E are formed to extend upward in FIG. 4 along the longitudinal direction L, and the conductive metals E are formed in each of the patterned gaps M1.
此外，於所述步驟S150中(通過所述電鍍的方式形成多個所述導電金屬E於多個所述圖案化間隙M1中)，所述電鍍的條件為：電鍍藥水溫度介於20℃至25℃、及電流密度介於40ASF至50ASF之間，以使得所述導電金屬E的沉積速率不小於0.2微米/分鐘(也就是，每分鐘沿所述縱向方向L沉積的厚度，並且上述厚度的單位為微米)。 In addition, in the step S150 (a plurality of the conductive metals E are formed in the plurality of patterning gaps M1 by the electroplating method), the electroplating condition is: the electroplating bath temperature is between 20° C. and 25°C and a current density between 40ASF and 50ASF, so that the deposition rate of the conductive metal E is not less than 0.2 microns/minute (that is, the thickness deposited along the longitudinal direction L per minute, and the above thickness The unit is microns).
如圖5所示，所述步驟S160包含：移除所述圖案化遮罩M，據以使部分的所述金屬晶種層C2(如：所述金屬晶種層C2的被所述圖案化遮罩M覆蓋的部分)暴露於所述外界環境。 As shown in FIG. 5, the step S160 includes: removing the patterned mask M, so that a part of the metal seed layer C2 (for example, the metal seed layer C2 is patterned) The part covered by the mask M) is exposed to the external environment.
如圖6所示，所述步驟S170包含：使用一蝕刻藥水對所述金屬晶種層C2進行蝕刻，以將所述金屬晶種層C2的未被多個所述導電金屬E覆蓋的部分移除，從而使得多個所述導電金屬E形成為所述圖案化線路1。也就是說，所述金屬晶種層C2的被移除的部分即是所述金屬晶種層C2的原本被所述圖案化遮罩M覆蓋的部分。於所述步驟S170中，所述蝕刻藥水對於所述金屬晶種層C2的蝕刻速率不小於1微米/分鐘(也就是，每分鐘沿所述縱向方向L蝕刻的厚度，並且上述厚度的單位為微米)。 As shown in FIG. 6, the step S170 includes: using an etching solution to etch the metal seed layer C2, so as to move the part of the metal seed layer C2 that is not covered by the plurality of conductive metals E In this way, a plurality of the conductive metals E are formed as the patterned circuit 1. In other words, the removed part of the metal seed layer C2 is the part of the metal seed layer C2 originally covered by the patterned mask M. In the step S170, the etching rate of the etching solution for the metal seed layer C2 is not less than 1 μm/min (that is, the thickness of the etching along the longitudinal direction L per minute, and the unit of the thickness is Micrometers).
在本實施例中，所述圖案化線路1較佳是通過半加成法(semi-additive process，SAP)的方式形成，但本發明不受限於此。舉例來說，在本發明未繪示的實施例中，所述圖案化線路1也可以例如是通過減成法的方式、或全加成法的方式形成於所述軟性基板C的所述表面C1。 In this embodiment, the patterned circuit 1 is preferably formed by a semi-additive process (SAP), but the present invention is not limited to this. For example, in an embodiment not shown in the present invention, the patterned circuit 1 may also be formed on the surface of the flexible substrate C by a subtractive method or a full additive method. C1.
所述圖案化線路1的平行於所述橫向方向W具有一最小線路寬 度W2min。所述最小線路寬度W2min不大於25微米，並且所述最小線路寬度W2min優選為不大於20微米。 The patterned circuit 1 has a minimum circuit width parallel to the lateral direction W Degree W2min. The minimum line width W2min is not greater than 25 microns, and the minimum line width W2min is preferably not greater than 20 microns.
於所述步驟S170中，所述蝕刻藥水的組成至少包含有蝕刻阻劑。基於所述蝕刻藥水的總重為100wt%，所述蝕刻阻劑的濃度範圍是介於5wt%至20wt%之間，並且所述蝕刻阻劑的濃度範圍優選為介於10wt%至15wt%之間。所述蝕刻阻劑可以選自含N-H官能基的化合物，其可以與銅離子錯合以降低蝕刻效率。舉例來說，於本實施例中的所述蝕刻阻劑可以為尿唑(CAS號：3232-84-6)。 In the step S170, the composition of the etching solution includes at least an etching resist. Based on the total weight of the etching solution being 100wt%, the concentration range of the etching resist is between 5wt% to 20wt%, and the concentration range of the etching resist is preferably between 10wt% to 15wt% between. The etching resist may be selected from compounds containing N-H functional groups, which may be complexed with copper ions to reduce etching efficiency. For example, the etching resist in this embodiment may be urazole (CAS number: 3232-84-6).
於所述步驟S170中，由於所述蝕刻阻劑較不容易通過所述圖案化間隙M1而吸附於所述金屬晶種層C2的所述側表面C21，所以所述導電金屬E的一外表面相較於所述金屬晶種層C2的所述側表面C21吸附有較多的所述蝕刻阻劑。也就是說，所述蝕刻阻劑於所述導電金屬E的所述外表面附近的濃度大於其於所述金屬晶種層C2的所述側表面C21的濃度。通過所述蝕刻阻劑的添加及所述蝕刻阻劑於不同位置的濃度差異，於本實施例中的所述軟性電路板的製造方法能據以有效地改善在生產細線路的軟性電路板時，於所述導電金屬E的外表面過蝕刻且於所述金屬晶種層C2的所述側表面C21蝕刻不足的問題。也就是說，所述蝕刻阻劑能提供差異化蝕刻的效果。 In the step S170, since the etching resist is less likely to be adsorbed on the side surface C21 of the metal seed layer C2 through the patterned gap M1, an outer surface of the conductive metal E is Compared with the side surface C21 of the metal seed layer C2, more etching resist is adsorbed. In other words, the concentration of the etching resist near the outer surface of the conductive metal E is greater than the concentration of the etching resist on the side surface C21 of the metal seed layer C2. Through the addition of the etching resist and the concentration difference of the etching resist at different positions, the method for manufacturing the flexible circuit board in this embodiment can effectively improve the production of flexible circuit boards with fine lines. The problem of over-etching on the outer surface of the conductive metal E and insufficient etching on the side surface C21 of the metal seed layer C2. In other words, the etching resist can provide a differentiated etching effect.
於所述步驟S170中，所述蝕刻藥水的組成還可以包含有蝕刻主劑、硫酸銅、安定劑、及加速劑。基於所述蝕刻藥水的總重為100wt%，蝕刻主劑、硫酸銅、安定劑、及加速劑的濃度範圍總和是介於80wt%至95wt%之間。其中所述蝕刻主劑是由硫酸及雙氧水組成，其具有均勻性佳且安定性高的特性。所述安定劑為鹽類(如：磺酸鹽)。所述安定劑可以抑制雙氧水分解並且避免金屬離子催化氧化水解反應。所述加速劑為醇類(如：丁二醇)。所述加速劑可以催化雙氧水對所述導電金屬E的蝕刻效能。 In the step S170, the composition of the etching solution may further include an etching main agent, copper sulfate, a stabilizer, and an accelerator. Based on the total weight of the etching solution being 100% by weight, the total concentration range of the main etching agent, copper sulfate, stabilizer, and accelerator is between 80% and 95% by weight. The main etching agent is composed of sulfuric acid and hydrogen peroxide, which has the characteristics of good uniformity and high stability. The stabilizer is a salt (such as sulfonate). The stabilizer can inhibit the decomposition of hydrogen peroxide and prevent the oxidative hydrolysis reaction catalyzed by metal ions. The accelerator is alcohol (such as butanediol). The accelerator can catalyze the etching performance of the conductive metal E by hydrogen peroxide.
[實施例的有益效果] [Beneficial effects of the embodiment]
本發明的其中一有益效果在於，本發明所提供的所述軟性電路板的製造方法，其能通過“改良電鍍藥水成分”以及“改良蝕刻藥水成分”的技術方案，據以改善現有的軟性電路板的製造方法在生產細線路的軟性基板時，容易產生良率不足、電鍍厚度控制不佳、部分過蝕刻且部分蝕刻不足的問題。 One of the beneficial effects of the present invention is that the method for manufacturing the flexible circuit board provided by the present invention can improve the existing flexible circuit through the technical solutions of "improving the composition of electroplating solution" and "improving the composition of etching solution" The manufacturing method of the board is prone to problems of insufficient yield, poor plating thickness control, partial over-etching and partial under-etching when producing flexible substrates with thin circuits.
進一步來說，如下的數個方法特別能改善現有的軟性電路板的製造方法在生產細線路的軟性基板時，因電鍍藥水不容易進入所述圖案化間隙進而產生良率不足及電鍍厚度控制不佳的問題：所述電鍍藥水的所述表面張力與所述圖案化遮罩的所述表面張力的差值不大於20m/Nm(優選為不大於15m/Nm)，據以使所述電鍍藥水有效地進入所述圖案化間隙中；所述電鍍藥水至少包含有所述銅錯合物，據以使所述電鍍藥水能有效地進入所述圖案化間隙；所述表面張力調整劑為長鏈環氧基聚合物(如：聚醚多元醇)，其可以降低所述電鍍藥水的極性，據以使所述電鍍藥水易於進入低極性的圖案化遮罩M所形成的圖案化間隙M1中。 Furthermore, the following methods can particularly improve the existing flexible circuit board manufacturing methods. When producing thin-circuit flexible substrates, the electroplating solution does not easily enter the patterning gap, resulting in insufficient yield and poor plating thickness control. Good question: the difference between the surface tension of the electroplating solution and the surface tension of the patterned mask is not more than 20m/Nm (preferably not more than 15m/Nm), so that the electroplating solution Effectively enter the patterning gap; the electroplating solution at least contains the copper complex, so that the electroplating solution can effectively enter the patterning gap; the surface tension adjusting agent is a long chain The epoxy-based polymer (such as polyether polyol) can reduce the polarity of the electroplating solution, so that the electroplating solution can easily enter the patterned gap M1 formed by the patterned mask M with low polarity.
再者，如下的方法特別能改善現有的軟性電路板的製造方法在生產細線路的軟性基板時，部分過蝕刻且部分蝕刻不足的問題：所述蝕刻藥水的組成至少包含有蝕刻阻劑，並且所述蝕刻阻劑於所述導電金屬E的所述外表面附近的濃度大於其於所述金屬晶種層C2的所述側表面C21的濃度。 Furthermore, the following method can particularly improve the existing flexible circuit board manufacturing method when producing thin-circuit flexible substrates, partly over-etched and partly under-etched: the composition of the etching solution includes at least an etching resist, and The concentration of the etching resist near the outer surface of the conductive metal E is greater than the concentration on the side surface C21 of the metal seed layer C2.
需要額外說明的是，所述電鍍藥水及所述蝕刻藥水於本實施例中是搭配所述軟性電路板的製造方法來說明，但本發明不受限於此。舉例來說，在本發明未繪示的其他實施例中，所述電鍍藥水及所述蝕刻藥水皆可以是單獨地被運用(如：販賣)或應用於其他電路板的製造方法中。 It should be additionally noted that the electroplating solution and the etching solution are described in this embodiment in conjunction with the manufacturing method of the flexible circuit board, but the present invention is not limited thereto. For example, in other embodiments not shown in the present invention, both the electroplating solution and the etching solution may be used separately (eg, sold) or applied to other circuit board manufacturing methods.
以上所公開的內容僅為本發明的優選可行實施例，並非因此侷 限本發明的申請專利範圍，所以凡是運用本發明說明書及圖式內容所做的等效技術變化，均包含於本發明的申請專利範圍內。 The content disclosed above is only a preferred and feasible embodiment of the present invention, not for this reason. The scope of the patent application of the present invention is limited, so all equivalent technical changes made by using the description of the present invention and the content of the drawings are included in the scope of the patent application of the present invention.
1:圖案化線路 1: Patterned circuit
C:軟性基板 C: Flexible substrate
C1:表面 C1: Surface
L:縱向方向 L: longitudinal direction
W:橫向方向 W: horizontal direction
W2min:最小線路寬度 W2min: minimum line width
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| TW201228822A (en) * | 2010-10-08 | 2012-07-16 | Fujifilm Corp | Laminate body and fabricating method thereof, print circuit board and circuit |
| TW201522071A (en) * | 2013-09-10 | 2015-06-16 | Dainippon Ink & Chemicals | Laminate body, conductive pattern, electrical circuit, and method for producing laminate body |
| TW201642105A (en) * | 2015-05-19 | 2016-12-01 | 富士軟片股份有限公司 | Touch sensor panel |
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| TW201228822A (en) * | 2010-10-08 | 2012-07-16 | Fujifilm Corp | Laminate body and fabricating method thereof, print circuit board and circuit |
| TW201522071A (en) * | 2013-09-10 | 2015-06-16 | Dainippon Ink & Chemicals | Laminate body, conductive pattern, electrical circuit, and method for producing laminate body |
| TW201642105A (en) * | 2015-05-19 | 2016-12-01 | 富士軟片股份有限公司 | Touch sensor panel |
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