TWI736325B - Advanced reverse-treated electrodeposited copper foil having long and island-shaped structures and copper clad laminate using the same - Google Patents
Advanced reverse-treated electrodeposited copper foil having long and island-shaped structures and copper clad laminate using the same Download PDFInfo
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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
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- 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
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- C25D7/0614—Strips or foils
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- 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
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Abstract
Description
本發明涉及一種電解銅箔,特別是涉及一種具有長島狀微結構的進階反轉電解銅箔,以及應用其的銅箔基板。 The invention relates to an electrolytic copper foil, in particular to an advanced reverse electrolytic copper foil with a long island-like microstructure, 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插入損耗(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插入損耗表現與其表面處理面的粗糙度具有高度關聯,原因在於高頻高速訊號傳輸時將產生集膚效應(Skin effect):導體內部的電流分布不均勻的一種現象。隨著與導體表面的距離逐漸增加,導體內的電流密度呈指數遞減,即導體內的電流會集中在導體的表面,因此導體表面處理面的表面積愈小愈有利於高頻高速訊號傳輸;然而,表面積愈大愈有利於剝離強度,這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,而銅箔的表面積愈大,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. The reason is that the skin effect will occur during high-frequency and high-speed signal transmission: the current distribution inside the conductor is uneven A phenomenon. As the distance from the surface of the conductor gradually increases, the current density in the conductor decreases exponentially, that is, the current in the conductor is concentrated on the surface of the conductor. Therefore, the smaller the surface area of the conductor surface treatment surface, the more conducive to high-frequency and high-speed signal transmission; however, , The larger the surface area, the better the peel strength, which is in conflict with the signal integrity. Furthermore, the flatter the surface of the copper foil, the better the signal integrity, and the larger the surface area 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具有長島狀微結構的進階反轉電解銅箔,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)。本發明還提供一種使用此進階反轉電解銅箔的銅箔基板,可作為高頻高速基板。 The technical problem to be solved by the present invention is to provide an advanced reverse electrolytic copper foil with a long island-like microstructure in view of the deficiencies of the prior art, which can be applied to the high-frequency and high-speed 5G field, and can maintain the characteristics required by the target application , For example, to maintain the peel strength of the electrolytic copper foil (peel strength). The invention also provides a copper foil substrate using the 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,本發明所採用的其中一技術方案是提供一種具有長島狀微結構的進階反轉電解銅箔,其包括一微粗糙化處理面。所述微粗糙化處理面具有多個呈非均勻性分佈的銅結晶,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,所述微粗糙化處理面具有以下結構特徵:(1)至少十個長為250nm且寬為250nm的第一平滑區域;(2)至少一個長為500nm且寬為500nm的第二平滑區域;(3)至少一個長為1,500nm以上的長島狀微結構,且所述長島狀微結構中有至少三個所述銅結晶及/或銅晶鬚;以及(4)至少兩個長為1,000nm以上的線條狀無銅區域。 In order to solve the above technical problems, one of the technical solutions adopted by the present invention is to provide an advanced reverse electrolytic copper foil with a long island-like microstructure, which includes a micro-roughened surface. The micro-roughened surface has a plurality of copper crystals distributed non-uniformly, 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 their respective copper crystal clusters. Observed by a scanning electron microscope with an inclination angle of 35 degrees and a magnification of 10,000 times, the micro-roughened surface has the following structural characteristics: (1) at least ten first smooth regions with a length of 250 nm and a width of 250 nm; (2) At least one second smooth region with a length of 500 nm and a width of 500 nm; (3) At least one long island-like microstructure with a length of 1,500 nm or more, and there are at least three copper crystals in the long island-like microstructure And/or copper whiskers; and (4) at least two linear copper-free regions with a length of 1,000 nm or more.
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,且具有一微粗糙化處理面接合於所述基板的一表面。所述微粗糙化處理面具有多個呈非均勻性分佈的銅結晶,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,所述微粗糙化處理面具有以下結構特徵:(1)至 少十個長為250nm且寬為250nm的第一平滑區域;(2)至少一個長為500nm且寬為500nm的第二平滑區域;(3)至少一個長為1,500nm以上的長島狀微結構,且所述長島狀微結構中有至少三個所述銅結晶及/或銅晶鬚;以及(4)至少兩個長為1,000nm以上的線條狀無銅區域。 In order to solve the above-mentioned technical problems, another technical solution adopted by the present invention is to provide a copper foil substrate, which includes a substrate and an advanced reverse electrolytic copper foil, and the advanced reverse electrolytic copper foil is disposed on the On the substrate, there is a micro-roughening treatment surface bonded to a surface of the substrate. The micro-roughened surface has a plurality of copper crystals distributed non-uniformly, 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 their 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 micro-roughened surface has the following structural characteristics: (1) to At least ten first smooth regions with a length of 250nm and a width of 250nm; (2) at least one second smooth region with a length of 500nm and a width of 500nm; (3) at least one long island-like microstructure with a length of more than 1,500nm, And there are at least three copper crystals and/or copper whiskers in the long island-shaped microstructure; and (4) at least two linear copper-free regions with a length of 1,000 nm or more.
在本發明的一實施例中,所述第一平滑區域與所述第二平滑區域內都不存在所述銅結晶。 In an embodiment of the present invention, the copper crystals do not exist in the first smooth area and the second smooth area.
在本發明的一實施例中,每一個所述銅晶鬚具有一頂部銅結晶。 In an embodiment of the present invention, each of the copper whiskers has a top copper crystal.
在本發明的一實施例中,多個所述頂部銅結晶呈錐狀、棒狀及/或球狀。 In an embodiment of the present invention, a plurality of the top copper crystals are cone-shaped, rod-shaped, and/or spherical.
在本發明的一實施例中,所述微粗糙化處理面的表面粗糙度(Rz jis94)小於2.1微米。 In an embodiment of the present invention, the surface roughness (Rz jis94) of the micro-roughened surface is less than 2.1 microns.
在本發明的一實施例中,所述微粗糙化處理面還包括多個凸峰以及位於多個所述凸峰之間的多個凹槽,且多個所述銅結晶、多個所述銅晶鬚與多個所述銅結晶團對應形成於多個所述凸峰上。 In an embodiment of the present invention, the micro-roughened surface further includes a plurality of convex peaks and a plurality of grooves located between the plurality of convex peaks, and a plurality of the copper crystals and a plurality of the copper Whiskers are formed on the plurality of convex peaks corresponding to the plurality of copper crystal clusters.
在本發明的一實施例中,每一個所述凹槽具有一U形或V形的剖面形貌。 In an embodiment of the present invention, each of the grooves has a U-shaped or V-shaped cross-sectional profile.
本發明的其中一有益效果在於,本發明的進階反轉銅箔,其能通過“微粗糙化處理面具有多個呈非均勻性分佈的銅結晶,而具有至少十個長為250nm且寬為250nm的第一平滑區域、至少一個長為500nm且寬為500nm的第二平滑區域以及至少一個長為1,500nm以上的長島狀微結構,且所述長島狀微結構中有至少三個所述銅結晶及/或銅晶鬚”的技術手段,以在不損害剝離強度的前提下減少插入損耗(insertion loss),提高訊號完整性,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 the present invention is that the advanced inverted copper foil of the present invention can have at least ten copper crystals with a length of 250nm and a width of Is a first smooth region of 250 nm, at least one second smooth region of 500 nm in length and 500 nm in width, and at least one long island-like microstructure with a length of 1,500 nm or more, and at least three of the long island-like microstructures "Copper crystals and/or copper whiskers" are used to reduce insertion loss and improve signal integrity without compromising the peel strength, so as to adapt to the high frequency and high speed of signal transmission and meet the requirements of 5G applications. need.
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 Regarding the detailed description and drawings of the present invention, the provided drawings are only for reference and description, and are not used to limit the present invention.
C:銅箔基板 C: Copper foil substrate
1:基板 1: substrate
2:進階電解銅箔 2: Advanced electrolytic copper foil
20:微粗糙化處理面 20: Micro-roughened surface
20a:第一平滑區域 20a: the first smooth area
20b:第二平滑區域 20b: Second smooth area
20c:長島狀微結構 20c: Long island-like microstructure
20d:線條狀無銅區域 20d: Line-shaped copper-free 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
圖1為本發明的銅箔基板的結構示意圖。 Fig. 1 is a schematic diagram of the structure of the copper foil substrate of the present invention.
圖2為圖1的II部分的放大示意圖。 Fig. 2 is an enlarged schematic diagram of part II of Fig. 1.
圖3為圖2的III部分的放大示意圖。 Fig. 3 is an enlarged schematic diagram of part III of Fig. 2.
圖4為用於生產本發明的具有長島狀微結構的進階反轉電解銅箔的連續式電解設備的結構示意圖。 Fig. 4 is a schematic structural diagram of a continuous electrolysis device for producing the advanced reverse electrolytic copper foil with a long island-like microstructure of the present invention.
圖5為以放大倍率1000倍觀察得到的掃描式電子顯微鏡圖影像,其顯示本發明的具有長島狀微結構的進階反轉電解銅箔的表面形貌。 FIG. 5 is a scanning electron microscope image obtained by observation at a magnification of 1000 times, which shows the surface morphology of the advanced inverted electrolytic copper foil with a long island-like microstructure of the present invention.
圖6為以放大倍率3000倍觀察得到的掃描式電子顯微鏡圖影像,其顯示本發明的具有長島狀微結構的進階反轉電解銅箔的表面形貌。 6 is a scanning electron microscope image obtained by observation at a magnification of 3000 times, which shows the surface morphology of the advanced inverted electrolytic copper foil with a long island-like microstructure of the present invention.
圖7為以放大倍率10000倍觀察得到的掃描式電子顯微鏡圖影像,其顯示本發明的具有長島狀微結構的進階反轉電解銅箔的表面形貌。 FIG. 7 is a scanning electron microscope image obtained by observation at a magnification of 10000 times, which shows the surface morphology of the advanced inverted electrolytic copper foil with a long island-like microstructure of the present invention.
圖8為掃描式電子顯微鏡圖影像,其顯示現有的RTF-3銅箔的表面形貌。 Figure 8 is a scanning electron microscope image showing the surface morphology of the existing RTF-3 copper foil.
圖9為掃描式電子顯微鏡圖影像,其顯示現有的MLS-G銅箔的表面形貌。 FIG. 9 is a scanning electron microscope image, which shows the surface morphology of the existing MLS-G copper foil.
以下是通過特定的具體實施例來說明本發明所公開有關“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,在不背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。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。 The following are specific examples to illustrate the implementation of the "advanced reverse electrolytic copper foil and copper foil substrate using the same" disclosed in the present invention. Those skilled in the art can understand the present invention from the content disclosed in this specification. Advantages and effects. The present invention can be implemented through other different specific implementations. The embodiments are implemented or applied, 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. 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.
參閱圖1至圖3所示,本發明提供一種銅箔基板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,其各具有一不平整的微粗糙化處理面20與基板1的表面接合,但本發明並不限制於此。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
為了降低插入損耗(insertion loss),基板1可以低損耗因子(dissipation factor,Df)的材料形成;基板1在10千兆赫茲(GHz)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 (dissipation factor, Df); the Df of the substrate 1 at a frequency of 10 gigahertz (GHz) may be less than or equal to 0.015, preferably less than or equal to 0.010, and more preferably 0.005 or less.
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,以上術語為本領預的技術人員所熟知,具體可舉出以下市售產品: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發明。
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. Specifically, the following commercially available products can be cited: EM890, EM890(K), EM891 (K), EM528, EM526, IT170GRA1, IT958G, IT968G, IT150DA, S7040G, S7439G, S6GX, TU863(+), TU883(A, SP),
參閱圖2及圖3所示,進階反轉電解銅箔2的微粗糙化處理面20是通過電沉積銅微粗糙化處理而形成;值得一提的是,微粗糙化處理面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
在一些實施例中,多個銅晶鬚W的平均高度可小於3微米,優選為小於1.8微米,且更優選為小於1.0微米;另外,多個銅結晶團G的平均高度可小於3.5微米,優選為小於1.8微米,且更優選為小於1.0微米。在一些實施例中,每一個銅晶鬚W可包括最多25個銅結晶21,優選為最多12個銅結晶21,更優選為最多10個銅結晶21,且特別優選為最多8個銅結晶21。在一些實施例中,多個銅結晶21的平均外徑可小於0.5微米,優選為0.05至0.5微米,且更優選為0.1至0.4微米。
In some embodiments, the average height of the plurality of copper whiskers W may be less than 3 microns, preferably less than 1.8 microns, and more preferably less than 1.0 microns; in addition, the average height of the plurality of copper crystal groups G may be less than 3.5 microns, It is preferably less than 1.8 micrometers, and more preferably less than 1.0 micrometers. In some embodiments, each copper whisker W may include up to 25
值得一提的是,不同於既有的電解銅箔,其中多個銅結晶是均勻地分佈於銅箔表面上,僅有少部分聚集在一起;本發明的進階反轉電解銅箔2的表面上,除了有非均勻性分佈的多個銅結晶21之外,還有不同數量的銅結晶21所分別形成的多個銅晶鬚W以及不同數量的銅晶鬚W所分別形成的銅結晶團G,使得銅箔的表面形貌有明顯的凹凸起伏。藉此,本發明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插入損耗(insertion loss),以適應訊號傳輸的高頻、高速化。此外,微粗糙化處理面
20的表面粗糙度(Rz jis)小於等於2.1微米,此對線寬和線距的微縮有所貢獻。
It is worth mentioning that, different from the existing electrolytic copper foil, a plurality of copper crystals are evenly distributed on the surface of the copper foil, and only a small part are gathered together; the advanced reverse
如圖3所示,微粗糙化處理面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。在將本發明的進階電解銅箔2壓合於一樹脂基複合材料時,微粗糙化處理面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。
As shown in FIG. 3, the
複參閱圖2,並配合圖4所示,本發明的進階反轉電解銅箔2的製備方法可以是對一生箔(raw foil)的暗面(matte side)進行電鍍銅微粗糙化處理而獲得,其中經過處理的亮面即形成微粗糙化處理面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,亦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長島狀圖案的凹槽,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面20。電鍍銅微粗糙化處理的條件如表1所示。
Referring again to FIG. 2 and in conjunction with FIG. 4, the preparation method of the advanced reverse
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
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,而並非用以限定本發明。 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 as required, such as: gelatin, organic nitride, hydroxyethyl cellulose (HEC), polyethylene glycol (Poly(ethylene glycol), PEG) , Sodium 3-mercaptopropanesulphonate (MPS), Bis-(sodium sulfopropyl)-disulfide (SPS), or thiourea-based compounds. However, the above-mentioned example is only one of the feasible implementation manners, and is not intended to limit the present invention.
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.
實施例1為本發明的具有長島狀微結構的進階反轉電解銅箔(為方便說明,下稱“長島狀微結構銅箔”或“ULVLP銅箔”),其是通過前述的電鍍銅微粗糙化處理而獲得,各階段的製備條件顯示於下表1中,銅箔的表面形貌如圖5、圖6及圖7所示。圖5、圖6及圖7都是使用Hitachi S-3400N掃描式電子顯微鏡(SEM)以傾斜角度35度進行拍攝而獲得;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。 Example 1 is the advanced reverse electrolytic copper foil with long island-like microstructures of the present invention (for convenience of description, hereinafter referred to as "long island-like microstructure copper foil" or "ULVLP copper foil"), which is obtained by the aforementioned electroplating copper It is obtained by micro-roughening treatment. The preparation conditions of each stage are shown in Table 1 below. The surface morphology of the copper foil is shown in Figs. 5, 6 and 7. Figure 5, Figure 6 and Figure 7 are all captured using Hitachi S-3400N Scanning Electron Microscope (SEM) at an inclination angle of 35 degrees; Figure 5 is an SEM image with a magnification of 1,000 times, and Figure 6 is a magnification of 3,000. The SEM image of 10,000 times magnification is shown in Fig. 7.
從圖5及圖6中可以看出,實施例1的反轉銅箔中,多個銅結晶21、銅晶鬚W與銅結晶團G構成一高低起伏的長島狀圖案。此外,從圖7中可以看出,實施例1的長島狀微結構銅箔的微粗糙化處理面具有以下結構特徵:(1)至少十個長為250nm且寬為250nm的第一平滑區域20a,第一平滑區域20a的面積相當於250nm×250nm;(2)至少一個長為500nm且寬為500nm的第二平滑區域20b,第二平滑區域20b的面積相當於500nm×500nm;(3)至少一個長為1,500nm以上的長島狀微結構20c,且所述長島狀微結構20c中有至少三個所述銅結晶及/或銅晶鬚;以及(4)至少兩個長為1,000nm以上的線條狀無銅區域20d。結構特徵(1)及(2)有助於降低銅箔表面積。
It can be seen from FIGS. 5 and 6 that in the inverted copper foil of Example 1, a plurality of
需要說明的是,上述結構特徵都是使用掃描式電子顯微鏡(SEM,型號:Hitachi S-3400N),並以傾斜角度35度與適當的放大倍率(若沒有特別註明倍率即指10,000倍)觀察銅箔的表面形貌後得到的結果,其中電子顯微鏡照電所對應的面積尺寸約為12.7μm×9.46μm,接近120μm2;用語“第一平滑區域20a”及“第二平滑區域20b”是指在SEM的觀察下無銅結晶存在的區域;用語“長島狀微結構20c”是指一結構在SEM的觀察下具有接近島狀或半島狀的輪廓形狀,其四周存在許多平滑區;用語“線條狀無銅區域20d”是指一無銅結晶存在且寬度為長度的1/3以下的區域(可為直線狀或非直線狀),例如1/10、1/100或1/1000,其可為直線狀或非直線狀且可具有均一或非均一的寬度。
It should be noted that the above structural features are used to observe the copper with a scanning electron microscope (SEM, model: Hitachi S-3400N), and an oblique angle of 35 degrees and an appropriate magnification (if not specified, the magnification is 10,000 times). The result obtained after the surface morphology of the foil, the area size corresponding to the electron microscope irradiation is about 12.7μm×9.46μm, which is close to 120μm 2 ; the terms "first
使用實施例1的ULVLP銅箔與不同類型的預浸材製成銅箔基板,測試其插入損耗(insertion loss)值,結果如下表2所示。 The ULVLP copper foil of Example 1 and different types of prepregs were used to make a copper foil substrate, and its insertion loss (insertion loss) value was tested. The results are shown in Table 2 below.
將實施例1及實施例2的ULVLP銅箔、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銅箔)以及C公司所生產的反轉電解銅箔(型號:RTF-3,以下稱RTF-3銅箔),分別與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銅箔的表面粗糙度(Rz jis94)小於2.3微米。RTF-3銅箔的表面形貌如圖8所示,其是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10000倍拍攝得到的,其中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3mils Core(1oz)、10mils PP及4.5mils Trace Width對其進行訊號完整性測試,結果如下表3所示。 The ULVLP copper foil of Example 1 and Example 2, the reverse electrolytic copper foil according to Taiwan Patent Application No. 107133827 (model: RG311, hereinafter referred to as RG311 copper foil) and the reverse electrolytic copper foil produced by C company ( Model: RTF-3, hereinafter referred to as RTF-3 copper foil), which are respectively bonded with the Mid-loss prepreg material (model: IT170GRA1) produced by I company and cured to form their own single-layer copper foil substrate . Among them, the surface roughness (Rz jis94) of RG311 copper foil is less than 2.3 microns. The surface morphology of the RTF-3 copper foil is shown in Figure 8. It was taken using a scanning electron microscope (model: Hitachi S-3400N) with an inclination angle of 35 degrees and a magnification of 10000 times. 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 using the Delta L test method proposed by Intel, the signal integrity test is performed on 3mils Core (1oz), 10mils PP and 4.5mils Trace Width. The result is As shown in Table 3 below.
由表3的測試結果可知,在8GHz的頻率下,ULVLP銅箔的插入損耗與RTF-3銅箔的插入損耗相比降低約16%~21%,且與RG311銅箔的插入損耗相比降低約5%~10%;在16GHz的頻率下,ULVLP銅箔的插入損耗與RTF-3 銅箔的插入損耗相比降低約20%~24%,與RG311銅箔的插入損耗相比降低約6%~10%。因此,ULVLP銅箔相較於RTF-3銅箔與RG311銅箔,具有較良好的訊號完整性。 From the test results in Table 3, it can be seen that at 8GHz, the insertion loss of ULVLP copper foil is reduced by about 16%~21% compared with the insertion loss of RTF-3 copper foil, and compared with the insertion loss of RG311 copper foil. About 5%~10%; At 16GHz, the insertion loss of ULVLP copper foil is comparable to RTF-3 The insertion loss of copper foil is reduced by about 20%~24%, and the insertion loss of RG311 copper foil is reduced by about 6%~10%. Therefore, ULVLP copper foil has better signal integrity than RTF-3 copper foil and RG311 copper foil.
將實施例1及實施例2的ULVLP銅箔、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銅箔)以及C公司所生產的反轉電解銅箔(型號:RTF-3,以下稱RTF-3銅箔),分別與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銅箔的表面粗糙度(Rz jis94)小於2.3微米。RTF-3銅箔的表面形貌如圖8所示,其是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10,000倍拍攝得到的,其中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3mils Core(1oz)、10mils PP及4.5mils Trace Width對其進行訊號完整性測試,結果如下表4所示。 The ULVLP copper foil of Example 1 and Example 2, the reverse electrolytic copper foil according to Taiwan Patent Application No. 107133827 (model: RG311, hereinafter referred to as RG311 copper foil) and the reverse electrolytic copper foil produced by C company ( Model: RTF-3, hereinafter referred to as RTF-3 copper foil), respectively and the low-loss prepreg material (model: IT958G) produced by I company after being bonded and solidified to form their respective single-layer copper foil substrates . Among them, the surface roughness (Rz jis94) of RG311 copper foil is less than 2.3 microns. The surface morphology of the RTF-3 copper foil is shown in Figure 8. It was taken using a scanning electron microscope (model: Hitachi S-3400N) with an inclination angle of 35 degrees and a magnification of 10,000 times. 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 using the Delta L test method proposed by Intel, the signal integrity test is performed on 3mils Core (1oz), 10mils PP and 4.5mils Trace Width. The result is As shown in Table 4 below.
由表4的測試結果可知,在8GHz的頻率下,ULVLP銅箔的插入損耗與RTF-3銅箔的插入損耗相比降低約15.80%~20.53%,與RG311銅箔的插入損耗相比降低約3%~9%;在16GHz的頻率下,ULVLP銅箔的插入損耗與RTF-3銅箔的插入損耗相比降低約18%~23%,與RG311銅箔的插入損耗相比降低約??。因此, ULVLP銅箔相較於RTF-3銅箔與RG311銅箔,具有較良好的訊號完整性。 It can be seen from the test results in Table 4 that at a frequency of 8 GHz, the insertion loss of ULVLP copper foil is reduced by approximately 15.80% to 20.53% compared with the insertion loss of RTF-3 copper foil, and is reduced by approximately 15.80% to 20.53% compared with the insertion loss of RG311 copper foil. 3%~9%; at the frequency of 16GHz, the insertion loss of ULVLP copper foil is reduced by about 18%~23% compared with the insertion loss of RTF-3 copper foil, and the insertion loss of RG311 copper foil is reduced by about? ? . therefore, Compared with RTF-3 copper foil and RG311 copper foil, ULVLP copper foil has better signal integrity.
將實施例1及實施例2的ULVLP銅箔、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銅箔),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,形成各自的單層銅箔基板。其中,RG311的表面粗糙度(Rz jis94)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的測試方法,在3mils Core(1oz)、10mils PP及4.5mils Trace Width對其進行訊號完整性測試,結果如下表5所示。 The ULVLP copper foil of Example 1 and Example 2, the reverse electrolytic copper foil (model: RG311, hereinafter referred to as RG311) according to Taiwan Patent Application No. 107133827 and the electrolytic copper foil produced by M company (model: HS1- M2-VSP, hereinafter referred to as HS1-M2-VSP copper foil), respectively use the ultra low-loss prepreg material (model: IT968) produced by I company to form a single-layer copper foil after being laminated and solidified Substrate. Among them, the surface roughness (Rz jis94) of RG311 is less than 2.3 microns. The peel strength of all single-layer copper foil substrates meets the requirements for use, and using the Delta L test method proposed by Intel, the signal integrity test is performed on 3mils Core (1oz), 10mils PP and 4.5mils Trace Width. The result is As shown in Table 5 below.
由表5的測試結果可知,在8GHz的頻率下,ULVLP銅箔的插入損耗與HS1-M2-VSP銅箔的插入損耗相比降低約16.04%~19.73%,與RG311銅箔的插入損耗相比降低約5%~10%;在16GHz的頻率下,ULVLP銅箔的插入損耗與HS1-M2-VSP銅箔的插入損耗相比降低約16%~21%,與RG311的插入損耗相比降低約5%~10%。因此,ULVLP銅箔相較於RG311銅箔與HS1-M2-VSP銅箔,具有較良好的訊號完整性。 From the test results in Table 5, it can be seen that the insertion loss of ULVLP copper foil is about 16.04%~19.73% lower than the insertion loss of HS1-M2-VSP copper foil at the frequency of 8GHz, which is compared with the insertion loss of RG311 copper foil. Reduced by about 5%~10%; at the frequency of 16GHz, the insertion loss of ULVLP copper foil is reduced by about 16%~21% compared with the insertion loss of HS1-M2-VSP copper foil, and the insertion loss of RG311 is reduced by about 5%~10%. Therefore, ULVLP copper foil has better signal integrity than RG311 copper foil and HS1-M2-VSP copper foil.
本發明的其中一有益效果在於,本發明的長島狀微結構的進階反轉銅箔,其能通過“微粗糙化處理面具有多個呈非均勻性分佈的銅結晶,而具有至少十個長為250nm且寬為250nm的第一平滑區域、至少一個長為500 nm且寬為500nm的第二平滑區域以及至少一個長為1,500nm以上的長島狀微結構,且長島狀微結構中有至少三個所述銅結晶及/或銅晶鬚”的技術手段,以在不損害剝離強度的前提下減少插入損耗(insertion loss),提高訊號完整性,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 the present invention is that the advanced inverted copper foil with a long island-like microstructure of the present invention can have at least ten copper crystals with a plurality of non-uniformly distributed copper crystals on the micro-roughened surface. The first smooth area with a length of 250 nm and a width of 250 nm, at least one of which is 500 in length A second smooth region with a width of 500 nm and at least one long island-like microstructure with a length of more than 1,500 nm, and at least three of the copper crystals and/or copper whiskers in the long island-like microstructure, to It reduces insertion loss and improves signal integrity without compromising the peel strength, so as to adapt to the high frequency and high speed of signal transmission and meet the needs of 5G applications.
值得一提的是,本發明在某種程度上採用因「技術偏見」而被捨棄之技術手段,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維持良好剝離強度並進一步優化電氣特性的有益技術效果。 It is worth mentioning that the present invention adopts technical means that have been abandoned due to "technical bias" to some extent, even if the surface of the copper foil has a certain degree of unevenness, and this technical means directly produces good peel strength and maintains good peel strength. The beneficial technical effect of further optimizing the electrical characteristics.
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 the preferred and feasible embodiments of the present invention, and does not limit the scope of the patent application of the present invention. Therefore, all equivalent technical changes made using the description and schematic content of the present invention are included in the application of the present invention. 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
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