TWI573687B - Laminated substrate and manufacturing method thereof - Google Patents
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本發明是有關於一種基材及其製作方法，且特別是有關於一種積層板及其製作方法。 The present invention relates to a substrate and a method of fabricating the same, and more particularly to a laminate and a method of making the same.
軟性印刷電路板具可撓、可立體配線以縮減體積以及質輕的特性。其中，聚亞醯胺軟性基材因具有厚度可調、優異之耐熱性、電絕緣性與機械性質，其應用與需求與日俱增。當電子產品需求朝向多功能、高效能、薄形化與輕量化，高密度構裝材料與製程技術關鍵性地影響製程良率、產品的可靠度與使用者的信賴度。 Flexible printed circuit boards are flexible, three-dimensionally spliced to reduce volume and light weight. Among them, the soft polyamide substrate has an adjustable thickness, excellent heat resistance, electrical insulation and mechanical properties, and its application and demand are increasing day by day. When the demand for electronic products is multi-functional, high-performance, thin and lightweight, high-density packaging materials and process technology critically affect process yield, product reliability and user reliability.
伴隨高密度構裝設計，對於窄線寬間距製程的需求逐漸增加。舉例來說，當線寬間距達20μm以下，諸如銅膜的金屬層厚度必須達5μm以下，三層軟板基材(3L-FCCL)已無法應付需求，因而二層軟板基材(2L-FCCL)成為主流。然而，現今高密度構裝用的2L-FCCL是以濺鍍法生產，其價格較高，且相較於塗佈法 或壓合法，以濺鍍法所形成之金屬層與基材之間的附著力較差。因此，在構裝製程中，二層軟板基材易因其他高溫步驟而影響製程良率與產品可靠度。此外，採用2L-FCCL在製作細線路時僅能使用減去法，導致細線化能力受限。 With the high-density package design, the demand for narrow line width spacing processes is increasing. For example, when the line width is less than 20 μm, the thickness of the metal layer such as the copper film must be less than 5 μm, and the three-layer soft board substrate (3L-FCCL) can no longer meet the demand, so the two-layer soft board substrate (2L- FCCL) has become mainstream. However, today's 2L-FCCL for high-density construction is produced by sputtering, which is expensive and compared to the coating method. Or pressing, the adhesion between the metal layer formed by the sputtering method and the substrate is poor. Therefore, in the fabrication process, the two-layer soft board substrate is susceptible to process yield and product reliability due to other high temperature steps. In addition, the use of 2L-FCCL can only use the subtraction method when making fine lines, resulting in limited thinning capability.
本發明提供一種積層板，其中基材與金屬層之間具有良好的附著。 The present invention provides a laminate in which the substrate and the metal layer have good adhesion.
本發明另提供一種積層板的製作方法，使得基材與金屬層之間具有良好的附著。 The invention further provides a method for manufacturing a laminate, which has good adhesion between the substrate and the metal layer.
本發明的積層板包括一基材、一第一金屬層以及一第二金屬層。基材的材料為聚亞醯胺或聚醯胺。第一金屬層配置於基材的表面處，第一金屬層包括選自Pd、Ni、Pt及其組合中的金屬與矽烷化合物，金屬粒子的平均粒徑分佈小於15nm。第二金屬層配置於第一金屬層上。 The laminate of the present invention comprises a substrate, a first metal layer and a second metal layer. The material of the substrate is polyamidamine or polyamine. The first metal layer is disposed at a surface of the substrate, and the first metal layer includes a metal and a decane compound selected from the group consisting of Pd, Ni, Pt, and combinations thereof, and the metal particles have an average particle size distribution of less than 15 nm. The second metal layer is disposed on the first metal layer.
本發明的積層板的製作方法，包括以下步驟。首先，提供一基材，基材的材料為聚亞醯胺或聚醯胺。接著，對基材進行一鹼改質處理。然後，使用一第一金屬前驅物溶液浸漬基材，以於基材的表面處形成一第一金屬前驅物層，其中第一金屬前驅物溶液包括一金屬離子與矽烷化合物，金屬離子的標準還原電位為-0.3~2V。而後，還原第一金屬前驅物層，以於基材的表面處形成一第一金屬層，第一金屬層中的金屬粒子的平均粒徑分佈小於 15nm。繼之，於第一金屬層上形成一第二金屬層。 The method for producing a laminate of the present invention comprises the following steps. First, a substrate is provided, the material of which is polyamidamine or polyamine. Next, the substrate is subjected to an alkali modification treatment. Then, the substrate is impregnated with a first metal precursor solution to form a first metal precursor layer at the surface of the substrate, wherein the first metal precursor solution comprises a metal ion and a decane compound, and the metal ion is reduced. The potential is -0.3~2V. Then, the first metal precursor layer is reduced to form a first metal layer at the surface of the substrate, and the average particle size distribution of the metal particles in the first metal layer is less than 15nm. Then, a second metal layer is formed on the first metal layer.
為讓本發明的上述特徵和優點能更明顯易懂，下文特舉實施例，並配合所附圖式作詳細說明如下。 The above described features and advantages of the invention will be apparent from the following description.
100‧‧‧積層板 100‧‧‧ laminate
102‧‧‧基材 102‧‧‧Substrate
102a‧‧‧表面 102a‧‧‧ surface
104‧‧‧第一金屬前驅物層 104‧‧‧First metal precursor layer
106‧‧‧第一金屬層 106‧‧‧First metal layer
106a‧‧‧金屬粒子 106a‧‧‧ metal particles
108‧‧‧第二金屬層 108‧‧‧Second metal layer
110‧‧‧第三金屬線路層 110‧‧‧ Third metal circuit layer
圖1A至圖1E是依照本發明的一實施例的一種積層板的製作方法的流程剖面示意圖。 1A-1E are schematic cross-sectional views showing a method of fabricating a laminate according to an embodiment of the invention.
圖2A至圖2C是本發明的實施例及參考例1與2的樣品的穿透式電子顯微圖。 2A to 2C are transmission electron micrographs of the examples of the present invention and the samples of Reference Examples 1 and 2.
圖3A至圖3C是本發明的實施例及參考例1與2的樣品的穿透式電子顯微圖。 3A to 3C are transmission electron micrographs of the examples of the present invention and the samples of Reference Examples 1 and 2.
圖1A至圖1E是依照本發明的一實施例的一種積層板的製作方法的流程剖面示意圖。請參照圖1A，首先，提供一基材102。在本實施例中，基材102可為聚亞醯胺基材或聚醯胺基材。 1A-1E are schematic cross-sectional views showing a method of fabricating a laminate according to an embodiment of the invention. Referring to FIG. 1A, first, a substrate 102 is provided. In this embodiment, the substrate 102 can be a polyimide substrate or a polyamide substrate.
接著，對基材102進行一鹼改質處理。在本實施例中，鹼改質處理例如是對基材102中的聚亞醯胺或聚醯胺進行開環活化。鹼改質處理例如是使用以氫氧化鉀、氫氧化鈉等無機氫氧化物鹽或以氫氧化四甲基銨等有機氫氧化物鹽為有效成分的溶液。其中，所使用的鹼化合物的濃度例如是0.1至10mol/L，其溫度例 如是室溫至100℃。再者，鹼改質處理的時間例如是5秒至30分鐘。若前述鹼改質處理的時間過長，則基材表面過度活化，將使基材強度減弱，且金屬層沈積過於深入基材表面，容易造成蝕刻殘留。若前述鹼改質處理的時間過短，則使基材親水性不足，金屬不易沈積。在一實施例中，金屬層沈積深入基材表面的厚度例如是約小於50nm。在一實施例中，為了提高鹼改質處理的效率，可以在所使用的鹼溶液中添加諸如甲醇、乙醇、丙醇等醇類或單乙醇胺等胺類。 Next, the substrate 102 is subjected to an alkali modification treatment. In the present embodiment, the alkali reforming treatment is, for example, ring-opening activation of polyammonium or polyamine in the substrate 102. The alkali reforming treatment is, for example, a solution using an inorganic hydroxide salt such as potassium hydroxide or sodium hydroxide or an organic hydroxide salt such as tetramethylammonium hydroxide as an active ingredient. Wherein the concentration of the alkali compound used is, for example, 0.1 to 10 mol/L, and the temperature is as an example Such as room temperature to 100 ° C. Further, the time of the alkali reforming treatment is, for example, 5 seconds to 30 minutes. If the time of the alkali reforming treatment is too long, the surface of the substrate is excessively activated, the strength of the substrate is weakened, and the deposition of the metal layer is too deep into the surface of the substrate, which tends to cause etching residue. If the time of the alkali reforming treatment is too short, the hydrophilicity of the substrate is insufficient and the metal is not easily deposited. In one embodiment, the thickness of the metal layer deposited deep into the surface of the substrate is, for example, less than about 50 nm. In one embodiment, in order to increase the efficiency of the alkali reforming treatment, an alcohol such as methanol, ethanol, or propanol or an amine such as monoethanolamine may be added to the alkali solution to be used.
請參照圖1B，然後，使用一第一金屬前驅物溶液浸漬基材102，以於基材102的表面102a處形成一第一金屬前驅物層104，其中第一金屬前驅物溶液包括一金屬離子與矽烷化合物，金屬離子的標準還原電位為-0.3~2V。由於金屬離子是作為觸媒金屬離子，因此此步驟實質上為賦與催化金屬離子步驟。在本實施例中，金屬離子例如是選自Pd2+、Ni2+、Pt2+及其組合。第一金屬前驅物溶液例如是包括金屬鹽類溶液與矽烷化合物，其中金屬鹽類可為PdCl2、NiSO4、PtCl4，矽烷化合物例如是環氧烴矽烷化合物、鏈烷烴矽烷化合物，又例如是不含胺基的矽烷化合物，且存在於第一金屬前驅物溶液中的矽烷化合物可以是單一種矽烷化合物或包含至少二種矽烷化合物的混合物。第一金屬前驅物溶液中的矽烷化合物的濃度例如是介於0.1至1v/v%。矽烷化合物的濃度若太高，則對於進一步提升附著力的能力有限，如此一來反而造成成本的不必要增加。相反地，矽烷化合物的濃度若太低，則無法達 到提升附著力的目的。在此步驟中，將基材102浸漬於第一金屬前驅物溶液中，使得諸如Pd2+等金屬離子吸附於基材102的表面上。特別說明的是，實際上部分的第一金屬前驅物溶液會滲入至基材102中，因此有部分的第一金屬前驅物層104會位於基材102中，也就是部分的第一金屬前驅物層104位於基材102的表面102a。 Referring to FIG. 1B, the substrate 102 is then impregnated with a first metal precursor solution to form a first metal precursor layer 104 at the surface 102a of the substrate 102, wherein the first metal precursor solution includes a metal ion. With decane compounds, the standard reduction potential of metal ions is -0.3~2V. Since the metal ion acts as a catalytic metal ion, this step is essentially a step of imparting a catalytic metal ion. In the present embodiment, the metal ion is, for example, selected from the group consisting of Pd 2+ , Ni 2+ , Pt 2+ , and combinations thereof. The first metal precursor solution includes, for example, a metal salt solution and a decane compound, wherein the metal salt may be PdCl 2 , NiSO 4 , PtCl 4 , and the decane compound is, for example, an epoxy sulfonate compound or a paraffin decane compound, for example, The amine-free decane compound, and the decane compound present in the first metal precursor solution may be a single decane compound or a mixture comprising at least two decane compounds. The concentration of the decane compound in the first metal precursor solution is, for example, from 0.1 to 1 v/v%. If the concentration of the decane compound is too high, the ability to further improve the adhesion is limited, which in turn causes an unnecessary increase in cost. Conversely, if the concentration of the decane compound is too low, the adhesion can not be achieved. In this step, the substrate 102 is immersed in the first metal precursor solution such that metal ions such as Pd 2+ are adsorbed on the surface of the substrate 102. In particular, a portion of the first metal precursor solution will penetrate into the substrate 102, so that a portion of the first metal precursor layer 104 will be located in the substrate 102, that is, a portion of the first metal precursor. Layer 104 is located on surface 102a of substrate 102.
請參照圖1C，而後，還原第一金屬前驅物層104，以於基材102表面處形成一第一金屬層106，第一金屬層106中的金屬粒子106a的平均粒徑分佈小於15nm。此步驟為還原步驟，使得第一金屬前驅物層104中的觸媒金屬離子被還原成金屬。在本實施例中，還原第一金屬前驅物層104的方法例如是將基材102浸漬於還原溶液中，使得第一金屬前驅物層104中的金屬離子被還原成金屬。還原溶液例如是二甲基胺硼烷、氫硼化鈉、次磷酸鈉等溶液，金屬例如是Pd金屬。其中，矽烷化合物使得金屬離子在還原後更緊密地結合於基材的有機碳鏈上，進而大幅提升第一金屬層106與基材102之間的附著力。第一金屬層106在基材102的表面102a上的厚度例如是小於100nm，又例如是小於50nm。在基材102中，矽烷化合物例如是僅位於鄰近基材102的表面102a處。 Referring to FIG. 1C, the first metal precursor layer 104 is reduced to form a first metal layer 106 at the surface of the substrate 102. The average particle size distribution of the metal particles 106a in the first metal layer 106 is less than 15 nm. This step is a reduction step such that the catalytic metal ions in the first metal precursor layer 104 are reduced to metal. In the present embodiment, the method of reducing the first metal precursor layer 104 is, for example, immersing the substrate 102 in a reducing solution such that metal ions in the first metal precursor layer 104 are reduced to metal. The reducing solution is, for example, a solution of dimethylamine borane, sodium borohydride or sodium hypophosphite, and the metal is, for example, a Pd metal. Among them, the decane compound causes the metal ions to more closely bond to the organic carbon chain of the substrate after reduction, thereby greatly enhancing the adhesion between the first metal layer 106 and the substrate 102. The thickness of the first metal layer 106 on the surface 102a of the substrate 102 is, for example, less than 100 nm, and is, for example, less than 50 nm. In the substrate 102, the decane compound is, for example, located only adjacent to the surface 102a of the substrate 102.
請參照圖1D，繼之，於第一金屬層106上形成一第二金屬層108。在本實施例中，第二金屬層108的形成方法例如是無電鍍製程，諸如化學鍍製程。第二金屬層108的材料例如是選自Ni、 Cu、Co及其組合。 Referring to FIG. 1D, a second metal layer 108 is formed on the first metal layer 106. In the present embodiment, the method of forming the second metal layer 108 is, for example, an electroless plating process such as an electroless plating process. The material of the second metal layer 108 is, for example, selected from the group consisting of Ni, Cu, Co and combinations thereof.
在本實施例中，在形成第二金屬層108後，可更包括對第二金屬層108進行一熱處理。熱處理的溫度例如是介於150至200℃，以及處理時間例如是10至60分鐘。 In this embodiment, after the second metal layer 108 is formed, the second metal layer 108 may be further subjected to a heat treatment. The temperature of the heat treatment is, for example, 150 to 200 ° C, and the treatment time is, for example, 10 to 60 minutes.
請參照圖1E，在本實施例中，接著，更包括於第二金屬層108上形成一第三金屬線路層110。在本實施例中，第三金屬線路層110的形成方法例如是直接在第二金屬層108上以電鍍製程等濕式製程形成整面的金屬層，再利用減去法製作線路。在另一實施例中，第三金屬線路層110也可以是利用加成法或半加成法直接於第二金屬層108上製作線寬間距較小的線路。第三金屬線路層110的材料例如是包括Cu或其他適合的金屬。在一實施例中，在形第三金屬線路層110後，可更包括對第三金屬線路層110進行一熱處理。熱處理的溫度例如是介於150至200℃，以及處理時間例如是10至60分鐘。前述熱處理的溫度若太高，則銅容易氧化。熱處理的溫度若太低，則對附著力增加無幫助。前述熱處理的時間若太長，則使銅容易氧化，且晶相結構發生變化。熱處理的時間若太短，則對附著力增加無幫助。在本實施例中，第一金屬層106與第二金屬層108及第三金屬線路層110對基材102之間的界面結合力例如是大於0.8Kgf/cm。 Referring to FIG. 1E, in the embodiment, a third metal wiring layer 110 is further formed on the second metal layer 108. In the present embodiment, the third metal wiring layer 110 is formed by, for example, directly forming a metal layer on the second metal layer 108 by a wet process such as an electroplating process, and then using a subtractive method to form a wiring. In another embodiment, the third metal wiring layer 110 may also be formed on the second metal layer 108 by an additive method or a semi-additive method to form a line having a small line width. The material of the third metal wiring layer 110 is, for example, Cu or other suitable metal. In an embodiment, after the third metal circuit layer 110 is formed, the third metal circuit layer 110 may be further subjected to a heat treatment. The temperature of the heat treatment is, for example, 150 to 200 ° C, and the treatment time is, for example, 10 to 60 minutes. If the temperature of the aforementioned heat treatment is too high, copper is easily oxidized. If the temperature of the heat treatment is too low, it does not contribute to the increase in adhesion. If the time of the aforementioned heat treatment is too long, copper is easily oxidized and the crystal phase structure changes. If the heat treatment time is too short, it will not help the adhesion increase. In the present embodiment, the interface bonding force between the first metal layer 106 and the second metal layer 108 and the third metal wiring layer 110 to the substrate 102 is, for example, greater than 0.8 Kgf/cm.
在本實施例中，如圖1E所示，積層板100包括基材102、第一金屬層106以及第二金屬層108。基材102的材料為聚亞醯胺或聚醯胺。第一金屬層106配置於基材102表面處。在本實施例 中，第一金屬層106包括選自Pd、Ni、Pt及其組合中的金屬與矽烷化合物，金屬粒子106a-的平均粒徑分佈小於15nm。第二金屬層108配置於第一金屬層106上。在本實施例中，積層板100更包括第三金屬線路層110，配置於第二金屬層108上。特別說明的是，雖然在本實施例中，是以前述的流程來製作圖1D或圖1E所示的積層板100，但本發明不以此為限。換言之，在其他實施例中，也可以其他製程來製作如圖1D或圖1E所示的積層板100。 In the present embodiment, as shown in FIG. 1E, the laminate 100 includes a substrate 102, a first metal layer 106, and a second metal layer 108. The material of the substrate 102 is polyamidamine or polyamine. The first metal layer 106 is disposed at the surface of the substrate 102. In this embodiment The first metal layer 106 includes a metal and a decane compound selected from the group consisting of Pd, Ni, Pt, and combinations thereof, and the metal particle 106a- has an average particle size distribution of less than 15 nm. The second metal layer 108 is disposed on the first metal layer 106. In the embodiment, the laminated board 100 further includes a third metal circuit layer 110 disposed on the second metal layer 108. In particular, in the present embodiment, the laminated board 100 shown in FIG. 1D or FIG. 1E is produced by the above-described flow, but the present invention is not limited thereto. In other words, in other embodiments, the laminate 100 as shown in FIG. 1D or FIG. 1E may be fabricated by other processes.
在本實施例中，在形成第二金屬層108之前，使用第一金屬前驅物溶液對基材102進行前處理，以在基材102表面處形成作為觸媒金屬層的第一金屬層106。其中，第一金屬前驅物溶液中的矽烷化合物使得金屬離子在還原後緊密地結合於基材的有機碳鏈上，且形成平均粒徑分佈小於15nm的金屬粒子106a。因此，第一金屬層106與基材102之間具有良好的附著力，進而提升第二金屬層108與基材102之間的附著。如此一來，積層板100具有較佳的製程良率與可靠度。 In the present embodiment, the substrate 102 is pretreated with a first metal precursor solution to form a first metal layer 106 as a catalytic metal layer at the surface of the substrate 102 prior to forming the second metal layer 108. Wherein the decane compound in the first metal precursor solution causes the metal ions to closely bond to the organic carbon chain of the substrate after reduction, and forms metal particles 106a having an average particle size distribution of less than 15 nm. Therefore, the first metal layer 106 and the substrate 102 have good adhesion, thereby enhancing the adhesion between the second metal layer 108 and the substrate 102. As a result, the laminated board 100 has better process yield and reliability.
另一方面，第一金屬層106使得第二金屬層108與基材102之間具有良好的結合力，因此形成於第二金屬層108上的第三金屬線路層110與基材102之間亦具有良好的結合力。如此一來，第三金屬線路層110可具有良好的細線化能力與細線化良率。舉例來說，可以應用成本較濺鍍法低的濕式製程來製作第三金屬線路層110。此外，可輕易地調整第三金屬線路層110的厚度以達到客製化目的，以及可製作高密度堆疊的積層板100。因此，採用積 層板100的軟性電路基板具有較佳的良率與可靠度以及較低的製作成本。 On the other hand, the first metal layer 106 has a good bonding force between the second metal layer 108 and the substrate 102, so that the third metal wiring layer 110 formed on the second metal layer 108 and the substrate 102 are also Has a good combination of strength. As a result, the third metal wiring layer 110 can have good thinning ability and fine line yield. For example, the third metal wiring layer 110 can be fabricated using a wet process having a lower cost than the sputtering method. Further, the thickness of the third metal wiring layer 110 can be easily adjusted for customization, and the high-density stacked laminate 100 can be fabricated. Therefore, using the product The flexible circuit substrate of the laminate 100 has better yield and reliability and lower manufacturing cost.
為了讓本發明之上述和其他目的、特徵、和優點能更明顯易懂，下文特舉數實施例作詳細說明如下：實施例與參考例中之鹼改質、催化劑附與、催化劑還原及無電鍍鎳所使用之溶液及其條件如下所述。 The above and other objects, features, and advantages of the present invention will become more apparent and understood. The solution used for nickel plating and its conditions are as follows.
<鹼改質處理> <alkali modification treatment>
使用溶液：1mol/L氫氧化鉀 Use solution: 1mol/L potassium hydroxide
處理溫度：40℃ Processing temperature: 40 ° C
處理時間：5分鐘 Processing time: 5 minutes
<催化劑附與> <catalyst attached>
使用溶液：0.4g/L氯化鈀 Use solution: 0.4g / L palladium chloride
處理溫度：室溫 Processing temperature: room temperature
處理時間：2分鐘 Processing time: 2 minutes
<催化劑還原> <catalyst reduction>
使用溶液：0.2mol/L次亞磷酸鈉 Use solution: 0.2mol/L sodium hypophosphite
處理溫度：室溫 Processing temperature: room temperature
處理時間：2分鐘 Processing time: 2 minutes
<無電鍍鎳> <electroless nickel plating>
使用溶液：SlotoNIP-30 Use solution: SlottoNIP-30
處理溫度：80℃ Processing temperature: 80 ° C
處理時間：0.5分鐘 Processing time: 0.5 minutes
實施例 Example
提供市售的杜邦聚亞醯胺基材(Kapton PI film)。接著，使用KOH溶液對聚亞醯胺基材進行鹼改質處理。然後，將基材浸漬於包括濃度為0.5v/v%的矽烷化合物的PdCl2水溶液中，以進行催化劑附與。而後，對基材進行催化劑還原處理，以於基材的表面處形成Pd層。之後，於Pd層上形成Ni金屬層。 A commercially available DuPont polyamine substrate (Kapton PI film) is provided. Next, the polyiminamide substrate was subjected to an alkali modification treatment using a KOH solution. Then, the substrate was immersed in an aqueous PdCl 2 solution containing a decane compound having a concentration of 0.5 v/v% to carry out catalyst attachment. Then, the substrate is subjected to a catalyst reduction treatment to form a Pd layer at the surface of the substrate. Thereafter, a Ni metal layer is formed on the Pd layer.
參考例1 Reference example 1
提供經二氧化矽(silica)改質之混成聚亞醯胺基材。接著，使用KOH溶液對混成聚亞醯胺基材進行鹼改質處理。然後，將基材浸漬於不含矽烷化合物的PdCl2水溶液中，以進行催化劑附與。而後，對基材進行催化劑還原處理，以於基材的表面處形成Pd層。之後，於Pd層上形成Ni金屬層。 A mixed polyamidene substrate modified with silica is provided. Next, the mixed polyamidamide substrate was subjected to alkali reforming treatment using a KOH solution. Then, the substrate was immersed in an aqueous solution of PdCl 2 containing no decane compound to carry out catalyst attachment. Then, the substrate is subjected to a catalyst reduction treatment to form a Pd layer at the surface of the substrate. Thereafter, a Ni metal layer is formed on the Pd layer.
參考例2 Reference example 2
在參考例2中，對基材的處理方式與實施例相同，其不同處僅在於PdCl2水溶液中不包含矽烷化合物。 In Reference Example 2, the substrate was treated in the same manner as in the examples except that the PdCl 2 aqueous solution contained no decane compound.
在依照實施例及參考例1與2所述步驟處理基材以獲得樣品後，使用穿透式電子顯微鏡觀察實施例及參考例1與2的各樣品，以及觀察Pd金屬粒子在各樣品中的分布情形，結果分別如圖2A至圖2C以及圖3A至圖3C所示。 After the substrate was treated in accordance with the procedures described in the Examples and Reference Examples 1 and 2 to obtain a sample, each sample of the Examples and Reference Examples 1 and 2 was observed using a transmission electron microscope, and Pd metal particles were observed in each sample. Distribution results, the results are shown in Figures 2A to 2C and Figures 3A to 3C, respectively.
請同時參照圖2A至圖2C及圖3A至圖3C，在參考例1(圖2A)中，在PI基材的表面上的Ni金屬層的厚度約為60nm，而滲入基材內的Ni金屬層的厚度約為435nm。在參考例2(圖2B)中， 在PI基材的表面上的Ni金屬層的厚度約為70nm，而滲入基材內的Ni金屬層的厚度約為35nm。在實施例(圖2C)中，在PI基材的表面上的Ni金屬層的厚度約為65nm，而滲入基材內的Ni金屬層的厚度約為40nm。由上述結果可知，參考例1的Pd金屬粒子滲入PI基材中的深度受鹼處理的影響較大，而參考例2與實施例的Pd金屬粒子滲入PI基材中的深度受鹼處理的影響較小。 Referring to FIG. 2A to FIG. 2C and FIG. 3A to FIG. 3C simultaneously, in Reference Example 1 (FIG. 2A), the thickness of the Ni metal layer on the surface of the PI substrate is about 60 nm, and the Ni metal infiltrated into the substrate. The thickness of the layer is approximately 435 nm. In Reference Example 2 (Fig. 2B), The thickness of the Ni metal layer on the surface of the PI substrate was about 70 nm, and the thickness of the Ni metal layer penetrating into the substrate was about 35 nm. In the embodiment (Fig. 2C), the thickness of the Ni metal layer on the surface of the PI substrate was about 65 nm, and the thickness of the Ni metal layer penetrating into the substrate was about 40 nm. From the above results, the depth of penetration of the Pd metal particles of Reference Example 1 into the PI substrate was greatly affected by the alkali treatment, and the depth of the Pd metal particles of Reference Example 2 and the Example penetrated into the PI substrate was affected by the alkali treatment. Smaller.
此外，在參考例1(圖3A)與參考例2(圖3B)中，Pd金屬粒子會團聚而形成較大顆粒。然而，在實施例(圖3C)中，Pd金屬粒子幾乎不會團聚且均勻分布於基材表面處，其中Pd金屬粒子的平均顆粒粒徑小於15nm。因此，可減少鈀的使用量，降低成本。另一方面，參考例1滲入基材內的Ni金屬層的厚度很深，將使Pd/Ni易殘留於PI基板中，影響積層板的電性。而實施例的Pd/Ni因則滲入基材內的Ni金屬層的厚度淺，將不易殘留於PI基板中。由此可知，在金屬前驅物溶液中添加矽烷化合物可以使得金屬離子在還原後能均勻地分布於基材上且具有較小的平均顆粒粒徑，且金屬粒子較不易殘留於基材中。 Further, in Reference Example 1 (Fig. 3A) and Reference Example 2 (Fig. 3B), Pd metal particles agglomerated to form larger particles. However, in the embodiment (Fig. 3C), the Pd metal particles hardly agglomerate and are uniformly distributed at the surface of the substrate, wherein the Pd metal particles have an average particle diameter of less than 15 nm. Therefore, the amount of palladium used can be reduced and the cost can be reduced. On the other hand, in the reference example 1, the thickness of the Ni metal layer which penetrated into the substrate was so deep that Pd/Ni easily remained in the PI substrate, and the electrical properties of the laminated plate were affected. On the other hand, in the Pd/Ni of the examples, the thickness of the Ni metal layer which penetrated into the substrate was shallow, and it would not easily remain in the PI substrate. It can be seen that the addition of the decane compound to the metal precursor solution enables the metal ions to be uniformly distributed on the substrate after reduction and has a small average particle diameter, and the metal particles are less likely to remain in the substrate.
接著，測試實施例與參考例2的樣品中Ni金屬層與PI基材之間的界面結合力。詳細地說，以拉伸試驗機台測試實施例與參考例2的樣品分別在未經處理、經熱處理以及經老化處理條件下的Ni金屬層與PI基材之間的界面結合力。其中，熱處理是在180℃下烘烤1小時。老化處理是在150℃下處理168小時。以下表1顯示在各條件下處理後的樣品中Ni金屬層與PI基材之間 的界面結合力。 Next, the interface bonding force between the Ni metal layer and the PI substrate in the samples of the Example and the Reference Example 2 was tested. In detail, the interfacial adhesion between the Ni metal layer and the PI substrate under the conditions of the untreated, heat-treated, and aged treatments of the samples of the tensile test machine test example and the reference example 2, respectively. Among them, the heat treatment was baked at 180 ° C for 1 hour. The aging treatment was carried out at 150 ° C for 168 hours. Table 1 below shows the Ni metal layer and the PI substrate in the sample treated under each condition. Interface bonding.
由表1可知，相較於未添加矽烷的參考例2，在添加矽烷的實施例中，Ni金屬層與PI基材之間的界面結合力較大。此外，即使經老化處理，添加矽烷的實施例中的Ni金屬層與PI基材之間仍具有均勻的界面結合力。由上述結果可知，在金屬前驅物溶液中添加矽烷可以提升基材與觸媒金屬層之間的界面結合力。 As is clear from Table 1, in the example in which decane was added, the interface bonding force between the Ni metal layer and the PI substrate was large as compared with Reference Example 2 in which decane was not added. Further, even after the aging treatment, the Ni metal layer in the embodiment in which decane is added still has a uniform interfacial bonding force with the PI substrate. From the above results, it is known that the addition of decane to the metal precursor solution can enhance the interfacial bonding force between the substrate and the catalytic metal layer.
綜上所述，本發明使用含有矽烷化合物的金屬前驅物溶液對基材進行前處理，以在基材的表面處形成作為觸媒金屬層的第一金屬層。其中，矽烷化合物使得金屬離子在還原後更緊密地結合於基材的有機碳鏈上，且金屬粒子具有小於15nm的平均粒徑 分佈，因此基材與第一金屬層之間具有良好的結合力，進而提升基材與第二金屬層之間的附著性。 In summary, the present invention pretreats a substrate using a metal precursor solution containing a decane compound to form a first metal layer as a catalytic metal layer at the surface of the substrate. Wherein the decane compound causes the metal ion to more closely bind to the organic carbon chain of the substrate after reduction, and the metal particle has an average particle diameter of less than 15 nm. The distribution, therefore, has a good bonding force between the substrate and the first metal layer, thereby improving the adhesion between the substrate and the second metal layer.
如此一來，當在第二金屬層上製作第三金屬線路層時，基材與金屬導線之間亦有良好的結合力，使得第三金屬線路層可具有良好的細線化能力與細線化良率。此外，積層板中基材與觸媒金屬層之間的界面結合力不易受到高溫影響，因此積層板不易因後續製程中的高溫步驟而受到破壞。因此，積層板具有較佳的製程良率與可靠度以及具有較低的製作成本。 In this way, when the third metal circuit layer is formed on the second metal layer, the substrate and the metal wire also have a good bonding force, so that the third metal circuit layer can have good thinning ability and fine line. rate. In addition, the interface bonding force between the substrate and the catalytic metal layer in the laminate is not easily affected by high temperature, and thus the laminate is not easily damaged by the high temperature step in the subsequent process. Therefore, the laminate has better process yield and reliability and lower manufacturing costs.
雖然本發明已以實施例揭露如上，然其並非用以限定本發明，任何所屬技術領域中具有通常知識者，在不脫離本發明的精神和範圍內，當可作些許的更動與潤飾，故本發明的保護範圍當視後附的申請專利範圍所界定者為準。 Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention, and any one of ordinary skill in the art can make some changes and refinements without departing from the spirit and scope of the present invention. The scope of the invention is defined by the scope of the appended claims.
100‧‧‧積層板 100‧‧‧ laminate
102‧‧‧基材 102‧‧‧Substrate
102a‧‧‧表面 102a‧‧‧ surface
106‧‧‧第一金屬層 106‧‧‧First metal layer
106a‧‧‧金屬粒子 106a‧‧‧ metal particles
108‧‧‧第二金屬層 108‧‧‧Second metal layer
110‧‧‧第三金屬線路層 110‧‧‧ Third metal circuit layer
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