TWM608774U - Advanced reverse-treated electrodeposited copper foil and copper clad laminate using the same - Google Patents

Advanced reverse-treated electrodeposited copper foil and copper clad laminate using the same Download PDF

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TWM608774U
TWM608774U TW109207516U TW109207516U TWM608774U TW M608774 U TWM608774 U TW M608774U TW 109207516 U TW109207516 U TW 109207516U TW 109207516 U TW109207516 U TW 109207516U TW M608774 U TWM608774 U TW M608774U
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copper foil
copper
degrees
micro
roughening treatment
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TW109207516U
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宋雲興
李思賢
許紘瑋
高羣祐
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金居開發股份有限公司
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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/0213—Electrical arrangements not otherwise provided for
    • H05K1/0237—High frequency adaptations
    • H05K1/0242—Structural details of individual signal conductors, e.g. related to the skin effect
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/38—Electroplating: Baths therefor from solutions of copper
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • C25D7/0614—Strips or foils
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/05—Insulated conductive substrates, e.g. insulated metal substrate
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
    • H05K3/384—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal by plating
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/03—Conductive materials
    • H05K2201/0302—Properties and characteristics in general
    • H05K2201/0317—Thin film conductor layer; Thin film passive component

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  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Fixed Capacitors And Capacitor Manufacturing Machines (AREA)

Abstract

本創作公開一種進階反轉電解銅箔及應用其的銅箔基板，其中進階反轉電解銅箔具有一不平整的微粗糙化處理層，且微粗糙化處理層具有由銅結晶所構成的多個生產方向條紋。因此，本創作的進階反轉電解銅箔與樹脂基複合材料之間具有良好的結合力，且能夠提高訊號完整性以及減少訊號的傳輸損耗，從而滿足5G應用的需求。 This creation discloses an advanced reverse electrolytic copper foil and a copper foil substrate using the same. The advanced reverse electrolytic copper foil has an uneven micro-roughening treatment layer, and the micro-roughening treatment layer is composed of copper crystals. Stripes in multiple production directions. Therefore, the advanced reverse electrolytic copper foil and resin-based composite material of this creation have a good bonding force, and can improve signal integrity and reduce signal transmission loss, thereby meeting the needs of 5G applications.

Description

進階反轉電解銅箔及應用其的銅箔基板 Advanced reverse electrolytic copper foil and copper foil substrate using the same

本創作涉及一種電解銅箔，特別是涉及一種進階反轉電解銅箔及應用其的銅箔基板。 This creation relates to an electrolytic copper foil, in particular to an advanced reverse electrolytic copper foil and a copper foil substrate using the same.

隨著資訊和電子產業的發展，高頻高速訊號傳輸已成為現代電路設計和製造的一環。為了符合電子產品對於高頻高速訊號傳輸的需求，銅箔基板(copper clad laminates,CCL)需要防止高頻訊號在傳遞時產生過度的***損耗(insertion loss)，以具有良好的訊號完整性(signal integrity,SI)。其中，銅箔基板中的銅箔的***損耗表現與其表面處理面的粗糙度具有高度關聯；然而，銅箔的剝離強度(peel strength)與訊號完整性是相衝突的，進一步而言，在銅箔的表面形貌越平坦，其訊號完整性越好，而銅箔的表面形貌越粗糙，其剝離強度越好。因此，本技術領域亟待研究出可以同時兼顧訊號完整性以及剝離強度的銅箔基板。 With the development of the information and electronic industries, high-frequency and high-speed signal transmission has become a part of modern circuit design and manufacturing. In order to meet the needs of electronic products for high-frequency and high-speed signal transmission, copper clad laminates (CCL) need to prevent excessive insertion loss during transmission of high-frequency signals in order to have good signal integrity (signal integrity). integrity, SI). Among them, the insertion loss performance of the copper foil in the copper foil substrate is highly correlated with the roughness of the surface treatment surface; however, the peel strength of the copper foil conflicts with the signal integrity. The flatter the surface morphology of the foil, the better the signal integrity, and the rougher the surface morphology of the copper foil, the better the peel strength. Therefore, the technical field urgently needs to develop a copper foil substrate that can simultaneously take into account signal integrity and peel strength.

本創作所要解決的技術問題在於，針對現有技術的不足提供一種進階反轉電解銅箔，其可以應用於高頻高速的5G領域，並且可以保持目標應用所需要的特性，例如保持電解銅箔的剝離強度(peel strength)。本創作還提供一種應用此進階反轉電解銅箔的銅箔基板，其可作為高頻高速基板。 The technical problem to be solved by this creation is to provide an advanced reverse electrolytic copper foil for the shortcomings of the existing technology, which can be applied to the high-frequency and high-speed 5G field, and can maintain the characteristics required by the target application, such as maintaining the electrolytic copper foil The peel strength (peel strength). This creation also provides a copper foil substrate using this advanced reverse electrolytic copper foil, which can be used as a high-frequency and high-speed substrate.

為了解決上述的技術問題，本創作所採用的其中一技術方案是，提供一種進階反轉電解銅箔，其包括一銅箔主體以及一形成於所述銅箔 主體上的不平整的微粗糙化處理層，並且在掃描式電子顯微鏡以35度傾斜角與1,000倍放大倍率的觀察下，所述微粗糙化處理層具有由銅結晶所構成的多個生產方向條紋以及多個細條紋，其中至少五個所述細條紋相對於所述生產方向條紋具有一最小夾角，所述最小夾角大於20度。 In order to solve the above technical problems, one of the technical solutions adopted in this creation is to provide an advanced reverse electrolytic copper foil, which includes a copper foil body and a copper foil formed on the copper foil. The uneven micro-roughening treatment layer on the main body, and under the observation of a scanning electron microscope with an inclination angle of 35 degrees and a magnification of 1,000 times, the micro-roughening treatment layer has multiple production directions composed of copper crystals Stripes and a plurality of thin stripes, wherein at least five of the thin stripes have a minimum included angle with respect to the production direction stripes, and the minimum included angle is greater than 20 degrees.

為了解決上述的技術問題，本創作所採用的另外一技術方案是，提供一種銅箔基板，其包括一基板以及一進階反轉電解銅箔。所述進階反轉電解銅箔設置於所述基板上，其中所述進階反轉電解銅箔包括一銅箔主體以及一形成於所述銅箔主體上的不平整的微粗糙化處理層，其中所述微粗糙化處理層接合於所述基板的一表面，並且在掃描式電子顯微鏡以35度傾斜角與1,000倍放大倍率的觀察下，所述微粗糙化處理層具有由銅結晶所構成的多個生產方向條紋以及多個細條紋，其中至少五個所述細條紋相對於所述生產方向條紋具有一最小夾角，所述最小夾角大於20度。 In order to solve the above technical problem, another technical solution adopted in this creation is to provide a copper foil substrate, which includes a substrate and an advanced reverse electrolytic copper foil. The advanced reverse electrolytic copper foil is disposed on the substrate, wherein the advanced reverse electrolytic copper foil includes a copper foil body and an uneven micro-roughening treatment layer formed on the copper foil body , Wherein the micro-roughening treatment layer is bonded to a surface of the substrate, and under the observation of a scanning electron microscope with an inclination angle of 35 degrees and a magnification of 1,000 times, the micro-roughening treatment layer has a surface formed by copper crystals. A plurality of production direction stripes and a plurality of thin stripes are formed, wherein at least five of the thin stripes have a minimum included angle with respect to the production direction stripes, and the minimum included angle is greater than 20 degrees.

在本創作的一實施例中，在掃描式電子顯微鏡以35度傾斜角與10,000倍放大倍率的觀察下，所述細條紋的長度和寬度滿足以下關係：50nm≦寬度≦1000nm；1.0μm≦長度≦10μm。 In an embodiment of this creation, under observation with a scanning electron microscope at an inclination angle of 35 degrees and a magnification of 10,000 times, the length and width of the thin stripes satisfy the following relationship: 50nm≦width≦1000nm; 1.0μm≦length ≦10μm.

在本創作的一實施例中，在掃描式電子顯微鏡以35度傾斜角與10,000倍放大倍率的觀察下，所述微粗糙化處理層具有至少十個長為250nm且寬為250nm的第一平滑區域以及至少一個長為500nm且寬為500nm的第二平滑區域，所述第一平滑區域與所述第二平滑區域不存在銅結晶。 In an embodiment of the present creation, under the observation of a scanning electron microscope with an inclination angle of 35 degrees and a magnification of 10,000 times, the micro-roughening treatment layer has at least ten first smooth layers with a length of 250 nm and a width of 250 nm. Area and at least one second smooth area with a length of 500 nm and a width of 500 nm, where copper crystals do not exist in the first smooth area and the second smooth area.

在本創作的一實施例中，不同數量的所述銅結晶堆疊在一起以形成各自的銅晶鬚，且不同數量的所述銅晶鬚團聚在一起以形成各自的銅結晶團；在掃描式電子顯微鏡以35度傾斜角與10,000倍放大倍率的觀察下，所述銅結晶、所述銅晶鬚或所述銅結晶團的最大直徑中值小於550nm。 In an embodiment of this creation, different numbers of the copper crystals are stacked together to form respective copper whiskers, and different numbers of the copper whiskers are agglomerated together to form respective copper crystal clusters; Observed by an electron microscope with an inclination angle of 35 degrees and a magnification of 10,000 times, the median maximum diameter of the copper crystals, the copper whiskers, or the copper crystal clusters is less than 550 nm.

在本創作的一實施例中，每一個所述銅晶鬚具有一呈錐狀、棒 狀或球狀的頂部銅結晶。 In an embodiment of this creation, each of the copper whiskers has a cone-shaped, rod-shaped Shaped or spherical copper crystals on the top.

在本創作的一實施例中，所述微粗糙化處理層定義出一表面粗糙度(Rz JIS B 0601-1994)小於2.3μm。 In an embodiment of the present invention, the micro-roughening treatment layer defines a surface roughness (Rz JIS B 0601-1994) of less than 2.3 μm.

在本創作的一實施例中，在掃描式電子顯微鏡以35度傾斜角與10,000倍放大倍率的觀察下，所述細條紋的數量為3個以上。 In an embodiment of the present creation, under observation of a scanning electron microscope with an inclination angle of 35 degrees and a magnification of 10,000 times, the number of the thin stripes is 3 or more.

本創作的其中一有益效果在於，本創作所提供的銅箔基板及其進階反轉電解銅箔，其能通過“所述微粗糙化處理層具有由銅結晶所構成的多個生產方向條紋以及多個細條紋，其中至少五個所述細條紋相對於所述生產方向條紋具有一最小夾角，且最小夾角大於20度”的技術特徵，以提高訊號完整性並抑制***損耗(insertion loss)，同時維持良好的剝離強度，以適應訊號傳輸的高頻、高速化，滿足5G應用的需求。 One of the beneficial effects of this creation is that the copper foil substrate and its advanced reversed electrolytic copper foil provided by this creation can pass "the micro-roughening treatment layer has multiple production direction stripes made of copper crystals" And a plurality of thin stripes, wherein at least five of the thin stripes have a minimum included angle with respect to the production direction stripe, and the minimum included angle is greater than 20 degrees" to improve the signal integrity and suppress insertion loss (insertion loss) , While maintaining good peel strength to adapt to the high frequency and high speed of signal transmission, and to meet the needs of 5G applications.

為使能更進一步瞭解本創作的特徵及技術內容，請參閱以下有關本創作的詳細說明與圖式，然而所提供的圖式僅用於提供參考與說明，並非用來對本創作加以限制。 In order to further understand the features and technical content of this creation, please refer to the following detailed descriptions and drawings about this creation. However, the drawings provided are only for reference and explanation, and are not used to limit this creation.

C:銅箔基板 C: Copper foil substrate

1:基板 1: substrate

2:進階反轉電解銅箔 2: Advanced reverse electrolytic copper foil

B:銅箔主體 B: Copper foil body

20:微粗糙化處理層 20: Micro-roughening treatment layer

20a:生產方向條紋 20a: Production direction stripes

20b:細條紋 20b: pinstripe

20c:第一平滑區域 20c: the first smooth area

20d:第二平滑區域 20d: second smooth area

21:銅結晶 21: Copper Crystal

211:頂部銅結晶 211: Top Copper Crystal

W:銅晶鬚 W: Copper whisker

G:銅結晶團 G: Copper crystal group

22:凸峰 22: convex peak

23:凹槽 23: Groove

3:連續式電解設備 3: Continuous electrolysis equipment

31:送料輥 31: Feeding roller

32:收料輥 32: Receiving roller

33:電解槽 33: Electrolyzer

331:電極 331: Electrode

34:電解輥組 34: Electrolytic roller set

35:輔助輥組 35: auxiliary roller group

HL:水平線 HL: horizontal line

EL1-EL10:延伸線 EL1-EL10: extension cord

RL:基準線 RL: Baseline

α1-α10:傾斜角 α1-α10: Tilt angle

β1-β9:最小夾角 β1-β9: Minimum included angle

P1、P2:表面形貌 P1, P2: surface topography

圖1為本創作的銅箔基板的結構示意圖。 Figure 1 is a schematic diagram of the structure of the copper foil substrate created.

圖2為圖1中II部分的局部放大圖。 Fig. 2 is a partial enlarged view of part II in Fig. 1.

圖3為圖2中III部分的局部放大圖。 Fig. 3 is a partial enlarged view of part III in Fig. 2.

圖4為用於生產本創作的進階反轉電解銅箔的連續式電解設備的示意圖。 Fig. 4 is a schematic diagram of a continuous electrolysis equipment used to produce the advanced reverse electrolytic copper foil of this creation.

圖5為以35度傾斜角與1,000倍放大倍率觀察得到的掃描式電子顯微鏡影像，其顯示本創作的進階反轉電解銅箔的表面形貌。 Figure 5 is a scanning electron microscope image observed with an inclination angle of 35 degrees and a magnification of 1,000 times, which shows the surface morphology of the advanced inverted electrolytic copper foil of this creation.

圖6為以35度傾斜角與3,000倍放大倍率觀察得到的掃描式電 子顯微鏡影像，其顯示本創作的進階反轉電解銅箔的表面形貌。 Figure 6 is a scanning electronic device observed at an inclination angle of 35 degrees and a magnification of 3,000 times. The sub-microscope image, which shows the surface morphology of the advanced reverse electrolytic copper foil created by this invention.

圖7為以35度傾斜角與10,000倍放大倍率觀察得到的掃描式電子顯微鏡影像，其顯示本創作的進階反轉電解銅箔的表面形貌。 Figure 7 is a scanning electron microscope image observed with a 35 degree inclination angle and 10,000 times magnification, which shows the surface morphology of the advanced reverse electrolytic copper foil of this creation.

圖8為以35度傾斜角與3,000倍放大倍率觀察得到的掃描式電子顯微鏡影像，其顯示現有的RTF-3銅箔的表面形貌，其中不存在細條紋。 Fig. 8 is a scanning electron microscope image observed at an oblique angle of 35 degrees and a magnification of 3,000 times, which shows the surface morphology of the existing RTF-3 copper foil without fine streaks.

圖9為以35度傾斜角與3,000倍放大倍率觀察得到的掃描式電子顯微鏡影像，其顯示現有的HS1-M2-VSP銅箔的表面形貌，其中不存在生產方向條紋及細條紋。 Fig. 9 is a scanning electron microscope image observed at an inclination angle of 35 degrees and a magnification of 3,000 times, which shows the surface morphology of the existing HS1-M2-VSP copper foil, in which there are no production direction stripes and thin stripes.

以下是通過特定的具體實施例來說明本創作所公開有關“進階反轉電解銅箔及應用其的銅箔基板”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創作的優點與效果。本創作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，在不悖離本創作的構思下進行各種修改與變更。另外，本創作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創作的相關技術內容，但所公開的內容並非用以限制本創作的保護範圍。 The following is a specific embodiment to illustrate the implementation of the "advanced reverse electrolytic copper foil and copper foil substrate using the same" disclosed in this creation. Those skilled in the art can understand the content of this creation from the content disclosed in this specification. Advantages and effects. This creation can be implemented or applied through other different specific embodiments, and various details in this specification can also be based on different viewpoints and applications, and various modifications and changes can be made without departing from the concept of this creation. In addition, the drawings of this creation are merely schematic illustrations, and are not depicted in actual size, and are stated in advance. The following implementations will further describe the related technical content of this creation in detail, but the disclosed content is not intended to limit the protection scope of this creation.

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.

值得一提的是，本創作在某種程度上採用因「技術偏見」而被 捨棄的技術手段，即使銅箔表面的具有一定的不平整度，且此技術手段直接產生了在維持良好剝離強度的前提下進一步優化電氣特性的有益技術效果。 It’s worth mentioning that, to some extent, this creation has been used because of "technical bias". Abandoned technical means, even if the surface of the copper foil has a certain degree of unevenness, and this technical means directly produces the beneficial technical effect of further optimizing the electrical characteristics on the premise of maintaining a good peel strength.

參閱圖1至圖3所示，本創作提供一種銅箔基板C，其包括一基板1以及至少一設置於基板1上的進階反轉電解銅箔2。在本實施例中，進階反轉電解銅箔2的數量為兩個，其各包括一銅箔主體B及一形成於上銅箔主體B的不平整的微粗糙化處理層20，其中微粗糙化處理層20與基板1的一表面接合，但本創作並不限制於此。在其他實施例中，銅箔基板C可以只包括一個進階反轉電解銅箔2。 Referring to FIGS. 1 to 3, the present invention provides a copper foil substrate C, which includes a substrate 1 and at least one advanced reverse electrolytic copper foil 2 disposed on the substrate 1. In this embodiment, the number of advanced reverse electrolytic copper foils 2 is two, each of which includes a copper foil body B and an uneven micro-roughening treatment layer 20 formed on the upper copper foil body B. The roughening treatment layer 20 is bonded to a surface of the substrate 1, but the present invention is not limited to this. In other embodiments, the copper foil substrate C may only include one advanced reverse electrolytic copper foil 2.

為了降低***損耗(insertion loss)，基板1可採用低損耗因子(dissipation factor,Df)的材料形成；基板1在10GHz頻率的Df可為小於或等於0.015，優選為小於或等於0.010，且更優選為小於或等於0.005。 In order to reduce the insertion loss (insertion loss), the substrate 1 may be formed of a material with a low dissipation factor (Df); the Df of the substrate 1 at a frequency of 10 GHz may be less than or equal to 0.015, preferably less than or equal to 0.010, and more preferably Is less than or equal to 0.005.

進一步而言，基板1是以一樹脂基複合材料(即預浸材料，prepreg)形成，其是將一基材含浸於一合成樹脂後再固化而成的複合材料。基材的具體例包括酚醛棉紙、棉紙、樹脂製纖維布、樹脂製纖維不織布、玻璃板、玻璃織布、或玻璃不織布；合成樹脂的具體例包括環氧樹脂、聚酯樹脂、聚醯亞胺樹脂、氰酸酯樹脂、雙馬來醯亞胺三嗪樹脂、聚苯醚樹脂、或酚樹脂，且合成樹脂可以形成單層或多層結構。樹脂基複合材料可以使用中損耗、低損耗、極低損耗、或超低損耗材料，以上術語為本領域的技術人員所熟知，具體可舉出以下產品：EM890、EM890(K)、EM891(K)、EM528、EM526、IT170GRA1、IT958G、IT968G、IT150DA、S7040G、S7439G、S6GX、TU863(+)、TU883(A,SP)、MEGTRON 4、MEGTRON 6，MEGTRON 7及MEGTRON 8。然而，上述所舉的例子只是其中一可行的實施例而並非用以限定本創作。 Furthermore, the substrate 1 is formed of a resin-based composite material (ie, prepreg), which is a composite material formed by impregnating a substrate in a synthetic resin and then curing. Specific examples of the substrate include phenolic cotton paper, cotton paper, resin fiber cloth, resin fiber non-woven fabric, glass plate, glass woven fabric, or glass non-woven fabric; specific examples of synthetic resin include epoxy resin, polyester resin, and polyamide Imine resin, cyanate ester resin, bismaleimide triazine resin, polyphenylene ether resin, or phenol resin, and the synthetic resin may form a single-layer or multi-layer structure. Resin-based composite materials can use medium-loss, low-loss, very low-loss, or ultra-low-loss materials. The above terms are well known to those skilled in the art. Specific examples include the following products: EM890, EM890(K), EM891(K) ), EM528, EM526, IT170GRA1, IT958G, IT968G, IT150DA, S7040G, S7439G, S6GX, TU863(+), TU883(A, SP), MEGTRON 4, MEGTRON 6, MEGTRON 7, and MEGTRON 8. However, the above-mentioned example is only one of the feasible embodiments and is not intended to limit the present creation.

參閱圖2及圖3所示，進階反轉電解銅箔2的微粗糙化處理層20 是通過電沉積銅微粗糙化處理而形成；值得一提的是，微粗糙化處理層20具有多個銅結晶21、多個銅晶鬚W及多個銅結晶團G，它們呈非均勻性分佈，即非均勻地沉積於銅箔表面上。每一個銅晶鬚W由兩個或更多的銅結晶21堆疊而成，且不同數量的銅結晶21堆疊在一起以形成各自的銅晶鬚W，其中每一個銅晶鬚W具有一呈錐狀、棒狀或球狀的頂部銅結晶211，優選為球狀。每一個銅結晶團G由兩個或更多的銅晶鬚W團聚而成，且不同數量的銅晶鬚W團聚在一起以形成各自的銅結晶團G。 2 and 3, the micro-roughening treatment layer 20 of the advanced reverse electrolytic copper foil 2 It is formed by electrodepositing copper micro-roughening treatment; it is worth mentioning that the micro-roughening treatment layer 20 has a plurality of copper crystals 21, a plurality of copper whiskers W, and a plurality of copper crystal clusters G, which are non-uniform Distribution, that is, non-uniformly deposited on the surface of the copper foil. Each copper whisker W is formed by stacking two or more copper crystals 21, and different numbers of copper crystals 21 are stacked together to form respective copper whiskers W, wherein each copper whisker W has a cone The top copper crystal 211 in a shape, rod shape, or spherical shape is preferably spherical. Each copper crystal group G is formed by agglomeration of two or more copper whiskers W, and different numbers of copper whiskers W agglomerate together to form respective copper crystal groups G.

參閱圖5及圖6所示，在使用HITACHI S-3400N型掃描式電子顯微鏡以35度傾斜角與3,000倍放大倍率的觀察下，微粗糙化處理層20具有多條生產方向條紋20a及多條細條紋20b，其中由多條生產方向條紋20a可以定義出一條基準線RL，且每一條細條紋20b與基準線RL之間具有一最小夾角β1-β9，最小夾角β1-β9大於20度。 Referring to Figures 5 and 6, under observation with a HITACHI S-3400N scanning electron microscope at an inclination angle of 35 degrees and a magnification of 3,000 times, the micro-roughening treatment layer 20 has multiple production direction stripes 20a and multiple The thin stripes 20b, wherein a reference line RL can be defined by multiple production direction stripes 20a, and each thin stripe 20b has a minimum included angle β1-β9 with the reference line RL, and the minimum included angle β1-β9 is greater than 20 degrees.

關於基準線RL的定義如下：將樣品放置在生產方向(MD)(即生產方向條紋20a的延伸方向)上，使用掃描式電子顯微鏡以傾斜角度35度、放大倍率1,000倍和3,000倍進行拍攝，得到微粗糙化處理層20的影像圖，如圖5及圖6所示；利用圖像處理軟體ImageJ(由美國國家衛生研究院(National Institutes of Health)開發且公眾可在https：//imagej.nih.gov/ij上獲取)在放大倍率為1,000倍的影像圖的最底部先畫上一條水平線HL，再畫上不同位置的十條生產方向條紋20a的延伸線EL1-EL10，然後取得十條生產方向條紋20a相對於水平線HL的傾斜角α1-α10並計算平均值，最後根據傾斜角α1-α10的平均值以水平線HL為基準畫出一條基準線RL。如圖5所示，生產方向條紋20a的傾斜角α1-α10分別為92.79度、88.13度、89.51度、86.49度、85.74度、91.45度、85.88度、88.27度、79.62度及87.71度，其平均值為87.56度。 The definition of the reference line RL is as follows: the sample is placed in the production direction (MD) (that is, the direction in which the production direction stripe 20a extends), and the scanning electron microscope is used to shoot at an inclination angle of 35 degrees and a magnification of 1,000 times and 3,000 times. Obtain the image map of the micro-roughening treatment layer 20, as shown in Figures 5 and 6; using image processing software ImageJ (developed by the National Institutes of Health (National Institutes of Health) and available to the public at https://imagej. (Acquired from nih.gov/ij) At the bottom of the image with a magnification of 1,000 times, first draw a horizontal line HL, and then draw ten production direction stripe 20a extension lines EL1-EL10 at different positions, and then obtain ten production directions The inclination angles α1-α10 of the stripe 20a relative to the horizontal line HL are calculated and the average value is calculated. Finally, a reference line RL is drawn based on the average value of the inclination angles α1-α10 with the horizontal line HL as a reference. As shown in Figure 5, the inclination angles α1-α10 of the stripes 20a in the production direction are 92.79 degrees, 88.13 degrees, 89.51 degrees, 86.49 degrees, 85.74 degrees, 91.45 degrees, 85.88 degrees, 88.27 degrees, 79.62 degrees, and 87.71 degrees, respectively. The value is 87.56 degrees.

細條紋的傾斜角量測方式如下：同樣利用圖像處理軟體ImageJ 先在放大倍率為3,000倍的影像圖中畫上一條水平線HL，再以水平線HL為基準畫出一條多條互相平行的基準線RL，然後取得多條細條紋20b與基準線RL之間的最小夾角β1、β2、β3、β4、β5、β6、β7、β8、β9；如圖6所示，最小夾角β1、β2、β3、β4、β5、β6、β7、β8、β9大於20度的細條紋20b的數量大於五個。本文中術語“細條紋”，是指一條紋其長度和寬度滿足以下關係：50nm≦寬度≦1000nm；1.0μm≦長度≦10μm。 The method of measuring the tilt angle of the thin stripes is as follows: also using the image processing software ImageJ First draw a horizontal line HL in the image with a magnification of 3,000 times, and then draw a number of parallel reference lines RL based on the horizontal line HL, and then obtain the minimum between the multiple thin stripes 20b and the reference line RL The included angle β1, β2, β3, β4, β5, β6, β7, β8, β9; as shown in Figure 6, the smallest included angle β1, β2, β3, β4, β5, β6, β7, β8, β9 thin stripes greater than 20 degrees The number of 20b is greater than five. The term "fine stripes" in this text refers to a stripe whose length and width satisfy the following relationship: 50nm≦width≦1000nm; 1.0μm≦length≦10μm.

參閱圖7所示，在使用HITACHI S-3400N型掃描式電子顯微鏡以35度傾斜角與10,000倍放大倍率的觀察下，微粗糙化處理層20還具有至少十個長為250奈米且寬為250奈米的第一平滑區域20c及至少一個長為500奈米且寬為500奈米的第二平滑區域20d，其位於多條生產方向條紋20a與多條細條紋20b之間。 Referring to Fig. 7, under observation using a HITACHI S-3400N scanning electron microscope at an inclination angle of 35 degrees and a magnification of 10,000 times, the micro-roughening treatment layer 20 also has at least ten lengths of 250 nanometers and widths of The 250nm first smooth region 20c and at least one second smooth region 20d 500nm long and 500nm wide are located between the multiple production direction stripes 20a and the multiple thin stripes 20b.

值得一提的是，不同於既有的電解銅箔，進階反轉電解銅箔2的微粗糙化處理層20具有由銅結晶21所構成的多條生產方向條紋20a與多條細條紋20b，其中最小夾角β1、β2、β3、β4、β5、β6、β7、β8、β9大於20度的細條紋20b的數量大於五個，並且存在有至少十個長為250奈米且寬為250奈米的第一平滑區域20c與至少一個長為500奈米且寬為500奈米的第二平滑區域20d。藉此，本創作的進階反轉電解銅箔2能夠在維持良好剝離強度的前提下，提高訊號完整性並抑制***損耗(insertion loss)，以適應訊號傳輸的高頻、高速化。此外，微粗糙化處理層20的表面粗糙度(Rz JIS B 0601-1994)小於等於2.3微米，此對線寬和線距的微縮有所貢獻。 It is worth mentioning that, unlike the existing electrolytic copper foil, the micro-roughening treatment layer 20 of the advanced reverse electrolytic copper foil 2 has multiple production direction stripes 20a and multiple thin stripes 20b composed of copper crystals 21. , Among which the smallest included angle β1, β2, β3, β4, β5, β6, β7, β8, β9 is greater than 20 degrees, the number of fine stripes 20b is greater than five, and there are at least ten with a length of 250 nanometers and a width of 250 nanometers The first smooth area 20c of meters and at least one second smooth area 20d having a length of 500 nanometers and a width of 500 nanometers. In this way, the advanced reverse electrolytic copper foil 2 of the present invention can improve signal integrity and suppress insertion loss while maintaining good peel strength, so as to adapt to the high frequency and high speed of signal transmission. In addition, the surface roughness (Rz JIS B 0601-1994) of the micro-roughening treatment layer 20 is less than or equal to 2.3 microns, which contributes to the reduction of line width and line spacing.

複參閱圖3所示，微粗糙化處理層20還包括多個凸峰22及多個位於凸峰22之間的凹槽23，且多個銅結晶21、多個銅晶鬚W與多個銅結晶團G對應形成於多個凸峰22上。其中，每一個凹槽23具有U形或V形的剖面形貌。在將本創作的進階反轉電解銅箔2壓合於一樹脂基複合材料時，微粗糙化處理 層20可以接收更多個樹脂材料，以增加銅箔與基材之間的結合力。 3, the micro-roughening treatment layer 20 also includes a plurality of peaks 22 and a plurality of grooves 23 located between the peaks 22, and a plurality of copper crystals 21, a plurality of copper whiskers W and a plurality of Copper crystal clusters G are correspondingly formed on the plurality of convex peaks 22. Wherein, each groove 23 has a U-shaped or V-shaped cross-sectional profile. When pressing the advanced reverse electrolytic copper foil 2 of this creation on a resin-based composite material, micro-roughening treatment The layer 20 can receive more resin materials to increase the bonding force between the copper foil and the substrate.

[製備例] [Preparation example]

複參閱圖2，並配合圖4所示，本創作的進階反轉電解銅箔2的製備方法可以是對一生箔(raw foil)(銅箔主體)的暗面(matte side)進行電鍍銅微粗糙化處理而獲得，其中經過處理的暗面即形成微粗糙化處理層20。電鍍銅微粗糙化處理可以採用習知設備進行，例如：連續式電解設備或批次式電解設備，並以5m/min至20m/min的生產速度、20℃至60℃的生產溫度與預定的電流密度來實現。值得一提的是，也可以預先使用鋼刷將生箔的暗面刻出刮痕，藉以形成不定向且為線條圖案的凹槽，但不以此為限。在一些實施例中，可以對生箔的亮面(shiny side)進行電鍍銅微粗糙化處理，使其形成微粗糙化處理層20。 Refer to Figure 2 again, and in conjunction with Figure 4, the preparation method of the advanced reversal electrolytic copper foil 2 of this creation can be to electroplate the dark side of the raw foil (the main body of the copper foil). It is obtained by micro-roughening treatment, in which the processed dark surface forms the micro-roughening treatment layer 20. Electroplating copper micro-roughening treatment can be carried out with conventional equipment, such as continuous electrolysis equipment or batch electrolysis equipment, with a production speed of 5m/min to 20m/min, a production temperature of 20°C to 60°C and a predetermined Current density to achieve. It is worth mentioning that a steel brush can also be used in advance to carve scratches on the dark surface of the raw foil, so as to form grooves that are not oriented and have a line pattern, but it is not limited to this. In some embodiments, the shiny side of the green foil may be subjected to copper electroplating micro-roughening treatment to form the micro-roughening treatment layer 20.

參閱圖4所示，在本製備例中，所使用的處理設備為連續式電解設備3，其包括一送料輥31、一收料輥32、多個電解槽33、多個電解輥組34及多個輔助輥組35；多個電解槽33設置於送料輥31與收料輥32之間，用以盛裝相同或不同配方的含銅鍍液，且每一個電解槽33內設有一組電極331(如白金電極)；多個電解輥組34分別設置於多個電解槽33上方，多個輔助輥組35分別設置於多個電解槽33內，多個電解輥組34與多個輔助輥組35能帶動生箔以一定的速度依序經過多個電解槽33內的鍍液；每一個電解槽33內的電極331與相對應的電解輥組34共同電性連接一外部電源(圖未示出)，用以對相對應的鍍液進行電解，而於銅箔上附加所需功效。 Referring to Figure 4, in this preparation example, the processing equipment used is a continuous electrolysis equipment 3, which includes a feed roller 31, a take-up roller 32, a plurality of electrolytic tanks 33, a plurality of electrolytic roller groups 34 and A plurality of auxiliary roller groups 35; a plurality of electrolytic tanks 33 are arranged between the feeding roller 31 and the receiving roller 32 to contain copper-containing plating solutions of the same or different formulations, and each electrolytic tank 33 is provided with a set of electrodes 331 (Such as platinum electrodes); a plurality of electrolytic roller groups 34 are respectively arranged above the plurality of electrolytic tanks 33, a plurality of auxiliary roller groups 35 are respectively arranged in a plurality of electrolytic tanks 33, a plurality of electrolytic roller groups 34 and a plurality of auxiliary roller groups 35 can drive the raw foil to pass through the plating solution in multiple electrolytic tanks 33 in sequence at a certain speed; the electrode 331 in each electrolytic tank 33 and the corresponding electrolytic roller set 34 are electrically connected to an external power source (not shown in the figure) Out), used to electrolyze the corresponding plating solution, and add required effects to the copper foil.

實際應用時，含銅電鍍液內含有銅離子、酸，以及金屬添加劑。銅離子的來源可以是硫酸銅、硝酸銅或其組合。酸的具體例包括硫酸、硝酸或其組合。金屬添加劑的具體例包括鈷、鐵、鋅或其組合。此外，含銅鍍液還可以依照需求進一步添加習知的添加劑，例如：明膠、有機氮化物、羥乙 基纖維素(hydroxyethyl cellulose,HEC)、聚乙二醇(Poly(ethylene glycol),PEG)、3-巰基-1-丙烷磺酸鈉(Sodium 3-mercaptopropanesulphonate,MPS)、聚二硫二丙烷磺酸鈉(Bis-(sodium sulfopropyl)-disulfide,SPS)，或硫脲基化合物。然而，上述所舉的例子只是其中一可行的實施方式，而並非用以限定本創作。 In practical applications, the copper-containing electroplating solution contains copper ions, acid, and metal additives. The source of copper ions may be copper sulfate, copper nitrate or a combination thereof. Specific examples of the acid include sulfuric acid, nitric acid, or a combination thereof. Specific examples of metal additives include cobalt, iron, zinc, or a combination thereof. In addition, the copper-containing plating solution can be further added with conventional additives, such as gelatin, organic nitride, and ethyl acetate. Hydroxyethyl cellulose (HEC), Poly(ethylene glycol) (PEG), Sodium 3-mercaptopropanesulphonate (MPS), Polydithiodipropane sulfonic acid Sodium (Bis-(sodium sulfopropyl)-disulfide, SPS), or thiourea-based compound. However, the above-mentioned example is only one of the feasible implementation manners, and is not intended to limit this creation.

在一些實施例中，電鍍銅微粗糙化處理可以分成兩個階段，所使用含銅鍍液的配方可以相同或不同。電鍍銅微粗糙化處理可以先後使用兩種不同配方的含銅鍍液(即第一和第二含銅鍍液)；第一含銅鍍液中，銅離子濃度可為介於10g/L至30g/L，酸濃度可為介於70g/L至100g/L，金屬添加劑的添加量可為介於150mg/L至300mg/L；第二含銅鍍液中，銅離子濃度可為介於70g/L至100g/L、酸濃度可為介於30g/L至60g/L，金屬添加劑的添加量可為介於15mg/L至100mg/L。 In some embodiments, the copper electroplating micro-roughening treatment can be divided into two stages, and the formula of the copper-containing plating solution used can be the same or different. The copper electroplating micro-roughening treatment can use two different copper-containing plating solutions (ie, the first and second copper-containing plating solutions) successively; in the first copper-containing plating solution, the copper ion concentration can be between 10g/L and 30g/L, the acid concentration can be between 70g/L and 100g/L, and the amount of metal additives can be between 150mg/L and 300mg/L; in the second copper-containing plating solution, the copper ion concentration can be between From 70g/L to 100g/L, the acid concentration can range from 30g/L to 60g/L, and the added amount of metal additives can range from 15mg/L to 100mg/L.

電鍍銅微粗糙化處理可採用定電壓、定電流、脈衝型波形、或鋸型波形的供電形式，但不限於此。電鍍銅微粗糙化處理的條件如表1所示。 The copper electroplating micro-roughening treatment can adopt a constant voltage, constant current, pulse-shaped waveform, or a saw-shaped waveform power supply form, but is not limited to this. The conditions of the electroplated copper micro-roughening treatment are shown in Table 1.

值得一提的是，前述的電鍍銅微粗糙化處理不僅可以用於反轉銅箔的生產，也可以用於高溫延展(High Temperature Elongation,HTE)銅箔或極低粗糙度(Very Low Profile,VLP)銅箔的生產。 It is worth mentioning that the aforementioned electroplated copper micro-roughening treatment can not only be used for the production of inverted copper foil, but also can be used for High Temperature Elongation (HTE) copper foil or Very Low Profile (Very Low Profile, VLP) production of copper foil.

[銅箔性能驗證] [Copper foil performance verification]

對於一通過七個階段的電鍍銅微粗糙化處理而獲得的進階反轉電解銅箔，各階段的製備條件顯示於下表1中，使用Hitachi S-3400N掃描式電子顯微鏡(SEM)以傾斜角度35度進行拍攝，得到銅箔表面形貌的SEM影像圖，即圖5、圖6及圖7；圖5為放大倍率1,000倍的SEM影像圖，圖6為放大倍率3,000倍的SEM影像圖，圖7為放大倍率10,000倍的SEM影像圖。 For an advanced reverse electrolytic copper foil obtained through seven stages of electroplating copper micro-roughening treatment, the preparation conditions of each stage are shown in Table 1 below, using Hitachi S-3400N scanning electron microscope (SEM) to tilt Shoot at an angle of 35 degrees to obtain SEM images of the copper foil surface topography, namely Figure 5, Figure 6 and Figure 7; Figure 5 is an SEM image with a magnification of 1,000 times, and Figure 6 is an SEM image with a magnification of 3,000 times , Figure 7 is a SEM image with a magnification of 10,000 times.

Figure 109207516-A0305-02-0012-1
Figure 109207516-A0305-02-0012-1

從圖5及圖6中可以看出，本創作的進階反轉電解銅箔中，多個銅結晶21、銅晶鬚W與銅結晶團G構成一高低起伏(非均勻分佈)的線條圖案；並且，超過五個細條紋20b與基準線RL的最小夾角β1-β9大於20度，如圖6所示。此外，從圖7中可以看出，本創作的進階反轉電解銅箔的表面輪廓中存在至少十個長為250奈米且寬為250奈米的第一平滑區域20c與至少一個長為500奈米且寬為500奈米的第二平滑區域20d。 It can be seen from Figure 5 and Figure 6 that in the advanced reverse electrolytic copper foil of this creation, a plurality of copper crystals 21, copper whiskers W and copper crystal clusters G form a high and low undulating (non-uniformly distributed) line pattern ; And, the minimum included angle β1-β9 between more than five thin stripes 20b and the reference line RL is greater than 20 degrees, as shown in FIG. 6. In addition, it can be seen from Figure 7 that there are at least ten first smooth regions 20c with a length of 250 nm and a width of 250 nm in the surface profile of the advanced reverse electrolytic copper foil of this creation, and at least one first smooth region 20c with a length of The second smooth area of 500nm and width of 500nm is 20d.

此外，將本創作的進階反轉電解銅箔與不同類型的預浸材製成銅箔基板，並測試其***損耗(insertion loss)值，結果如下表2所示。 In addition, the advanced reverse electrolytic copper foil of this creation and different types of prepregs were made into copper foil substrates, and their insertion loss values were tested. The results are shown in Table 2 below.

Figure 109207516-A0305-02-0013-2
Figure 109207516-A0305-02-0013-2

[試驗例1] [Test Example 1]

將實施例3-1及實施例3-2的進階反轉電解銅箔(皆是利用表1所示實施例1的條件所生產)、根據台灣專利申請號第107133827號的反轉電解銅箔(型號：RG311，以下稱RG311)以及C公司所生產的反轉電解銅箔(型號：RTF-3，以下稱RTF-3)，分別使用I公司生產的中度損耗(Mid-loss)預浸材料(型號：IT170GRA1)貼合固化後，形成各自的單層銅箔基板。其中，RG311的表面粗糙度(Rz JIS B 0601-1994)小於2.3微米。RTF-3在使用掃描式電子顯微 鏡(型號：Hitachi S-3400N)以傾斜角度35度與放大倍率3,000倍觀察得到的表面形貌P1的影像如圖8所示，銅結晶很明顯是均勻地分佈於銅箔表面上。所有的單層銅箔基板的剝離強度皆滿足使用要求，並使用Intel公司提出的Delta L的測試方法，在3 mils Core(1 oz)、10 mils PP及4.5 mils Trace Width進行訊號完整性測試，結果如下表3所示。 The advanced reversal electrolytic copper foil of Example 3-1 and Example 3-2 (all produced under the conditions of Example 1 shown in Table 1), and the reverse electrolytic copper according to Taiwan Patent Application No. 107133827 The foil (model: RG311, hereinafter referred to as RG311) and the reverse electrolytic copper foil (model: RTF-3, hereinafter referred to as RTF-3) produced by Company C, respectively use the Mid-loss pre-cursor produced by Company I. After the immersion material (model: IT170GRA1) is bonded and cured, a single-layer copper foil substrate is formed. Among them, the surface roughness of RG311 (Rz JIS B 0601-1994) is less than 2.3 microns. RTF-3 is using scanning electron microscopy The image of the surface morphology P1 obtained by observing the mirror (model: Hitachi S-3400N) with an inclination angle of 35 degrees and a magnification of 3,000 times is shown in Figure 8. The copper crystals are clearly evenly distributed on the surface of the copper foil. The peel strength of all single-layer copper foil substrates meets the requirements for use, and the Delta L test method proposed by Intel is used for signal integrity testing at 3 mils Core (1 oz), 10 mils PP, and 4.5 mils Trace Width. The results are shown in Table 3 below.

Figure 109207516-A0305-02-0014-4
Figure 109207516-A0305-02-0014-4

由表3的測試結果可知，在8GHz的頻率下，進階反轉電解銅箔的***損耗與RTF-3的***損耗相比降低約17.63%~22.1%，且與RG311的***損耗相比降低約6.2%~10.67%；在16GHz的頻率下，進階反轉電解銅箔的***損耗與RTF-3的***損耗相比降低約21.32%~25.51%，且與RG311的***損耗相比降低約6.01%~10.21%。因此，進階反轉電解銅箔相較於RTF-3與RG311，具有較良好的訊號完整性。 It can be seen from the test results in Table 3 that at 8GHz, the insertion loss of the advanced reverse electrolytic copper foil is reduced by about 17.63%~22.1% compared with the insertion loss of RTF-3, and compared with the insertion loss of RG311. About 6.2%~10.67%; at the frequency of 16GHz, the insertion loss of advanced reverse electrolytic copper foil is reduced by about 21.32%~25.51% compared with the insertion loss of RTF-3, and it is reduced by about 21.32%~25.51% compared with the insertion loss of RG311. 6.01%~10.21%. Therefore, the advanced reverse electrolytic copper foil has better signal integrity than RTF-3 and RG311.

[試驗例2] [Test Example 2]

將實施例4-1及實施例4-2的進階反轉電解銅箔(皆是利用表1所示實施例1的條件所生產)、根據台灣專利申請號第107133827號的反轉電解銅箔(型號：RG311，以下稱RG311)以及C公司所生產的反轉電解銅箔(型號：RTF-3，以下稱RTF-3)，分別使用I公司生產的中度損耗(Low-loss)預浸材料(型號：IT958G)貼合固化後，形成各自的單層銅箔基板。其中，RG311的表面粗糙度(Rz JIS B 0601-1994)小於2.3微米。RTF-3在使用掃描式電子顯微鏡(型號：Hitachi S-3400N)以傾斜角度35度與放大倍率3,000倍觀察得到的表 面形貌P1的影像如圖8所示，銅結晶很明顯是均勻地分佈於銅箔表面上。所有的單層銅箔基板的剝離強度皆滿足使用要求，並使用Intel公司提出的Delta L測試方法，在3 mils Core(1 oz)及10 mils PP及4.5 mils Trace Width的條件下進行訊號完整性測試，結果如下表4所示。 The advanced reverse electrolytic copper foil of Example 4-1 and Example 4-2 (all produced under the conditions of Example 1 shown in Table 1), and the reverse electrolytic copper according to Taiwan Patent Application No. 107133827 The foil (model: RG311, hereinafter referred to as RG311) and the reverse electrolytic copper foil (model: RTF-3, hereinafter referred to as RTF-3) produced by C company, respectively use the low-loss pre-cursor produced by I company. After the immersion material (model: IT958G) is bonded and solidified, the respective single-layer copper foil substrates are formed. Among them, the surface roughness of RG311 (Rz JIS B 0601-1994) is less than 2.3 microns. RTF-3 is using a scanning electron microscope (model: Hitachi S-3400N) to observe the table with an inclination angle of 35 degrees and a magnification of 3,000 times. The image of the surface morphology P1 is shown in Figure 8. The copper crystals are obviously evenly distributed on the surface of the copper foil. The peel strength of all single-layer copper foil substrates meets the requirements for use, and the Delta L test method proposed by Intel is used for signal integrity under the conditions of 3 mils Core (1 oz), 10 mils PP, and 4.5 mils Trace Width The test results are shown in Table 4 below.

Figure 109207516-A0305-02-0015-5
Figure 109207516-A0305-02-0015-5

由表4的測試結果可知，在8GHz的頻率下，進階反轉電解銅箔的***損耗與RTF-3的***損耗相比降低約18.33%~23.06%，且與RG311的***損耗相比降低約18.33%；在16GHz的頻率下，進階反轉電解銅箔的***損耗與RTF-3的***損耗相比降低約21.07%。因此，進階反轉電解銅箔相較於RTF-3與RG311，具有較良好的訊號完整性。 It can be seen from the test results in Table 4 that at 8GHz, the insertion loss of the advanced reverse electrolytic copper foil is reduced by about 18.33%~23.06% compared with the insertion loss of RTF-3, and compared with the insertion loss of RG311. About 18.33%; At a frequency of 16GHz, the insertion loss of the advanced reverse electrolytic copper foil is reduced by about 21.07% compared with the insertion loss of RTF-3. Therefore, the advanced reverse electrolytic copper foil has better signal integrity than RTF-3 and RG311.

[試驗例3] [Test Example 3]

將實施例5-1及實施例5-2的進階反轉電解銅箔(皆是利用表1所示實施例1的條件所生產)、根據台灣專利申請號第107133827號的反轉電解銅箔(型號：RG311，以下稱RG311)以及M公司所生產的電解銅箔(型號：HS1-M2-VSP，以下稱HS1-M2-VSP，其表面形貌P2如圖9所示)，分別使用I公司生產的中度損耗(Ultra Low-loss)預浸材料(型號：IT968)貼合固化後，形成各自單層銅箔基板。其中，RG311的表面粗糙度(Rz JIS B 0601-1994)小於2.3微米。所有的單層銅箔基板的剝離強度皆滿足使用要求，並使用Intel公司提出的Delta L測試方法，在3 mils Core(1 oz)、10 mils PP及4.5 mils Trace Width的條件下進行訊號完整性測試，結果如下表5所示。 The advanced reverse electrolytic copper foils of Example 5-1 and Example 5-2 (all produced under the conditions of Example 1 shown in Table 1), according to Taiwan Patent Application No. 107133827 Foil (model: RG311, hereinafter referred to as RG311) and electrolytic copper foil produced by M Company (model: HS1-M2-VSP, hereinafter referred to as HS1-M2-VSP, and its surface morphology P2 is shown in Figure 9), used respectively The Ultra Low-loss prepreg material (model: IT968) produced by I company is laminated and cured to form a single-layer copper foil substrate. Among them, the surface roughness of RG311 (Rz JIS B 0601-1994) is less than 2.3 microns. The peel strength of all single-layer copper foil substrates meets the requirements for use, and uses the Delta L test method proposed by Intel. The test method is 3 mils Core (1 oz), 10 mils PP and 4.5 The signal integrity test is performed under the condition of mils Trace Width, and the results are shown in Table 5 below.

Figure 109207516-A0305-02-0016-6
Figure 109207516-A0305-02-0016-6

由表5的測試結果可知，在8GHz的頻率下，進階反轉電解銅箔的***損耗與HS1-M2-VSP的***損耗相比降低約16.04%~19.73%，且與RG311的***損耗相比降低約7.31%~11.00%；在16GHz的頻率下，進階反轉電解銅箔的***損耗與HS1-M2-VSP的***損耗相比降低約18.62%~23.09%，且與RG311的***損耗相比降低約7.12%~11.59%。因此，進階反轉電解銅箔相較於HS1-M2-VSP與RG311，具有較良好的訊號完整性。 It can be seen from the test results in Table 5 that at 8GHz, the insertion loss of the advanced reverse electrolytic copper foil is reduced by about 16.04%~19.73% compared with the insertion loss of HS1-M2-VSP, and is comparable to the insertion loss of RG311. The ratio is reduced by about 7.31%~11.00%; at the frequency of 16GHz, the insertion loss of the advanced reverse electrolytic copper foil is reduced by about 18.62%~23.09% compared with the insertion loss of HS1-M2-VSP, and the insertion loss of RG311 Compared with the decrease of about 7.12%~11.59%. Therefore, compared with HS1-M2-VSP and RG311, advanced reverse electrolytic copper foil has better signal integrity.

[實施例的有益效果] [Beneficial effects of the embodiment]

本創作的其中一有益效果在於，本創作所提供的銅箔基板及其進階反轉電解銅箔，其能通過“所述微粗糙化處理層具有由銅結晶所構成的多個生產方向條紋以及多個細條紋，其中至少五個所述細條紋相對於所述生產方向條紋具有一最小夾角，且最小夾角大於20度”的技術特徵，以提高訊號完整性並抑制***損耗(insertion loss)，同時維持良好的剝離強度，以適應訊號傳輸的高頻、高速化，滿足5G應用的需求。 One of the beneficial effects of this creation is that the copper foil substrate and its advanced reversed electrolytic copper foil provided by this creation can pass "the micro-roughening treatment layer has multiple production direction stripes made of copper crystals" And a plurality of thin stripes, wherein at least five of the thin stripes have a minimum included angle with respect to the production direction stripe, and the minimum included angle is greater than 20 degrees" to improve the signal integrity and suppress insertion loss (insertion loss) , While maintaining good peel strength to adapt to the high frequency and high speed of signal transmission, and to meet the needs of 5G applications.

更進一步來說，有別於現有技術的電解銅箔是將銅結晶均勻分布於處理面上，本創作的進階反轉電解銅箔的銅結晶呈非均勻分布在處理面上，且銅結晶可以堆疊或排列形成各式不同的銅晶鬚以及銅結晶團，以掃描式電子顯微鏡以傾斜角度35度與放大倍率10,000倍觀察所述微粗糙化處理層時，銅晶鬚以及銅結晶團並無特殊的方向性；而在放大倍率1000倍觀察 所述微粗糙化處理層時，則可以觀察到多個所述銅結晶構成一線條圖案且大於20度的直條紋數量大於5。經過測試可證明本創作的進階反轉電解銅箔具有較高的訊號完整性。 Furthermore, different from the prior art electrolytic copper foil, the copper crystals are uniformly distributed on the processing surface. The copper crystals of the advanced reverse electrolytic copper foil of this creation are non-uniformly distributed on the processing surface, and the copper crystals are unevenly distributed on the processing surface. Various types of copper whiskers and copper crystal clusters can be stacked or arranged. When the micro-roughening treatment layer is observed with a scanning electron microscope at an inclination angle of 35 degrees and a magnification of 10,000 times, the copper whiskers and copper crystal clusters are No special directionality; but observed at 1000 times magnification When the micro-roughening treatment layer is used, it can be observed that a plurality of the copper crystals form a line pattern and the number of straight stripes greater than 20 degrees is greater than 5. After testing, it can be proved that the advanced reverse electrolytic copper foil of this creation has high signal integrity.

以上所公開的內容僅為本創作的優選可行實施例，並非因此侷限本創作的申請專利範圍，所以凡是運用本創作說明書及圖式內容所做的等效技術變化，均包含於本創作的申請專利範圍內。 The content disclosed above is only a preferred and feasible embodiment of this creation, and does not limit the scope of patent application for this creation. Therefore, all equivalent technical changes made using this creation specification and schematic content are included in the application for this creation. Within the scope of the patent.

21:銅結晶 21: Copper Crystal

211:頂部銅結晶 211: Top Copper Crystal

W:銅晶鬚 W: Copper whisker

G:銅結晶團 G: Copper crystal group

22:凸峰 22: convex peak

23:凹槽 23: Groove

Claims (14)

一種進階反轉電解銅箔，包括一銅箔主體以及一形成於所述銅箔主體上的不平整的微粗糙化處理層，其特徵在於，在掃描式電子顯微鏡以35度傾斜角與1,000倍放大倍率的觀察下，所述微粗糙化處理層具有由銅結晶所構成的多個生產方向條紋以及多個細條紋，其中至少五個所述細條紋相對於所述生產方向條紋具有一最小夾角，所述最小夾角大於20度。 An advanced reversal electrolytic copper foil, comprising a copper foil body and an uneven micro-roughening treatment layer formed on the copper foil body, characterized in that the scanning electron microscope has an inclination angle of 35 degrees and 1,000 Under the observation of multiple magnification, the micro-roughening treatment layer has multiple production direction stripes and multiple thin stripes composed of copper crystals, wherein at least five of the thin stripes have a minimum value relative to the production direction stripes. The included angle, the minimum included angle is greater than 20 degrees. 如請求項1所述的進階反轉電解銅箔，其中，在掃描式電子顯微鏡以35度傾斜角與10,000倍放大倍率的觀察下，所述細條紋的長度和寬度滿足以下關係：50nm≦寬度≦1000nm；1.0μm≦長度≦10μm。 The advanced inverted electrolytic copper foil according to claim 1, wherein, under the observation of a scanning electron microscope at an inclination angle of 35 degrees and a magnification of 10,000 times, the length and width of the thin stripes satisfy the following relationship: 50nm≦ Width≦1000nm; 1.0μm≦length≦10μm. 如請求項1所述的進階反轉電解銅箔，其中，在掃描式電子顯微鏡以35度傾斜角與10,000倍放大倍率的觀察下，所述微粗糙化處理層具有至少十個長為250nm且寬為250nm的第一平滑區域以及至少一個長為500nm且寬為500nm的第二平滑區域，所述第一平滑區域與所述第二平滑區域不存在銅結晶。 The advanced inverted electrolytic copper foil according to claim 1, wherein, under observation of a scanning electron microscope at an inclination angle of 35 degrees and a magnification of 10,000 times, the micro-roughening treatment layer has at least ten lengths of 250 nm And a first smooth area with a width of 250 nm and at least one second smooth area with a length of 500 nm and a width of 500 nm, where copper crystals do not exist in the first smooth area and the second smooth area. 如請求項1所述的進階反轉電解銅箔，其中，不同數量的所述銅結晶堆疊在一起以形成各自的銅晶鬚，且不同數量的所述銅晶鬚團聚在一起以形成各自的銅結晶團；在掃描式電子顯微鏡以35度傾斜角與10,000倍放大倍率的觀察下，所述銅結晶、所述銅晶鬚或所述銅結晶團的最大直徑中值小於550nm。 The advanced reverse electrolytic copper foil according to claim 1, wherein different numbers of the copper crystals are stacked together to form respective copper whiskers, and different numbers of the copper whiskers are agglomerated together to form respective Under the observation of a scanning electron microscope with an inclination angle of 35 degrees and a magnification of 10,000 times, the median maximum diameter of the copper crystals, the copper whiskers or the copper crystal clusters is less than 550nm. 如請求項4所述的進階反轉電解銅箔，其中，每一個所述銅 晶鬚具有一呈錐狀、棒狀或球狀的頂部銅結晶。 The advanced reverse electrolytic copper foil according to claim 4, wherein each of the copper The whisker has a cone, rod, or spherical top copper crystal. 如請求項1所述的進階反轉電解銅箔，其中，所述微粗糙化處理層定義出一表面粗糙度(Rz JIS B 0601-1994)小於2.3μm。 The advanced reverse electrolytic copper foil according to claim 1, wherein the micro-roughening treatment layer defines a surface roughness (Rz JIS B 0601-1994) of less than 2.3 μm. 如請求項1所述的進階反轉電解銅箔，其中，在掃描式電子顯微鏡以35度傾斜角與10,000倍放大倍率的觀察下，所述細條紋的數量為3個以上。 The advanced inverted electrolytic copper foil according to claim 1, wherein, under observation with a scanning electron microscope at an inclination angle of 35 degrees and a magnification of 10,000 times, the number of the thin stripes is 3 or more. 一種銅箔基板，其包括：一基板；一進階反轉電解銅箔，設置於所述基板上，其中所述進階反轉電解銅箔包括一銅箔主體以及一形成於所述銅箔主體上的不平整的微粗糙化處理層，其中所述微粗糙化處理層接合於所述基板的一表面，且在掃描式電子顯微鏡以35度傾斜角與1,000倍放大倍率的觀察下，所述微粗糙化處理層具有由銅結晶所構成的多個生產方向條紋以及多個細條紋，其中至少五個所述細條紋相對於所述生產方向條紋具有一最小夾角，所述最小夾角大於20度。 A copper foil substrate, comprising: a substrate; an advanced reverse electrolytic copper foil disposed on the substrate, wherein the advanced reverse electrolytic copper foil includes a copper foil body and a copper foil formed on the copper foil The uneven micro-roughening treatment layer on the main body, wherein the micro-roughening treatment layer is bonded to a surface of the substrate, and under the observation of a scanning electron microscope with an inclination angle of 35 degrees and a magnification of 1,000 times, The micro-roughening treatment layer has multiple production direction stripes and multiple thin stripes formed by copper crystals, wherein at least five of the thin stripes have a minimum included angle with respect to the production direction stripes, and the minimum included angle is greater than 20. degree. 如請求項8所述的銅箔基板，其中，在掃描式電子顯微鏡以35度傾斜角與10,000倍放大倍率的觀察下，所述細條紋的長度和寬度滿足以下關係：50nm≦寬度≦1000nm；1.0μm≦長度≦10μm。 The copper foil substrate according to claim 8, wherein, under observation with a scanning electron microscope at an inclination angle of 35 degrees and a magnification of 10,000 times, the length and width of the thin stripes satisfy the following relationship: 50nm≦width≦1000nm; 1.0μm≦length≦10μm. 如請求項8所述的銅箔基板，其中，在掃描式電子顯微鏡以 35度傾斜角與10,000倍放大倍率的觀察下，所述微粗糙化處理層具有至少十個長為250nm且寬為250nm的第一平滑區域以及至少一個長為500nm且寬為500nm的第二平滑區域，所述第一平滑區域與所述第二平滑區域不存在銅結晶。 The copper foil substrate according to claim 8, wherein the scanning electron microscope Under the observation of an inclination angle of 35 degrees and a magnification of 10,000 times, the micro-roughening treatment layer has at least ten first smooth areas with a length of 250 nm and a width of 250 nm and at least one second smooth area with a length of 500 nm and a width of 500 nm. Area, there is no copper crystal in the first smooth area and the second smooth area. 如請求項8所述的銅箔基板，其中，不同數量的所述銅結晶堆疊在一起以形成各自的銅晶鬚，且不同數量的所述銅晶鬚團聚在一起以形成各自的銅結晶團；在掃描式電子顯微鏡以35度傾斜角與10,000倍放大倍率的觀察下，所述銅結晶、所述銅晶鬚或所述銅結晶團的最大直徑中值小於550nm。 The copper foil substrate according to claim 8, wherein different numbers of the copper crystals are stacked together to form respective copper whiskers, and different numbers of the copper whiskers are agglomerated together to form respective copper crystal clusters Under the observation of a scanning electron microscope with an inclination angle of 35 degrees and a magnification of 10,000 times, the median maximum diameter of the copper crystals, the copper whiskers or the copper crystal clusters is less than 550 nm. 如請求項11所述的銅箔基板，其中，每一個所述銅晶鬚具有一呈錐狀、棒狀或球狀的頂部銅結晶。 The copper foil substrate according to claim 11, wherein each of the copper whiskers has a top copper crystal in a cone, rod, or spherical shape. 如請求項8所述的銅箔基板，其中，所述微粗糙化處理層定義出一表面粗糙度(Rz JIS B 0601-1994)小於2.3μm。 The copper foil substrate according to claim 8, wherein the micro-roughening treatment layer defines a surface roughness (Rz JIS B 0601-1994) of less than 2.3 μm. 如請求項8所述的銅箔基板，其中，在掃描式電子顯微鏡以35度傾斜角與10,000倍放大倍率的觀察下，所述細條紋的數量為3個以上。 The copper foil substrate according to claim 8, wherein, under observation with a scanning electron microscope at an inclination angle of 35 degrees and a magnification of 10,000 times, the number of the thin stripes is 3 or more.
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