TW200836609A

TW200836609A - Flexible circuit board and process for producing the same

Info

Publication number: TW200836609A
Application number: TW96126820A
Authority: TW
Inventors: Tsunemi Oiwa; Masatoshi Kondou
Original assignee: Metal Finishing System Co Ltd
Priority date: 2007-02-16
Filing date: 2007-07-23
Publication date: 2008-09-01
Also published as: WO2008099527A1

Abstract

A flexible circuit board of high reliability that excels in the adherence of a copper based metal layer, permitting microetching. Resin film (1) on its surface is provided with silicon nitride layer (2) according to sputtering technique wherein nitrogen is contained in an amount of 0.5 to 1.33 in terms of equivalent to silicon, and further provided with copper based metal layer (3). Accordingly, the adherence of the copper based metal layer (3) is high. Further, as the silicon nitride layer (2) is an insulator, etching thereof is not needed with the copper based metal layer only to be etched, so that side etching is less likely to occur, allowing execution of microetching. Still further, even in the event of penetration of moisture or oxygen from the side of resin film (1) at high temperature, it would be blocked by the silicon nitride layer (2), so that any oxidation or adherence deterioration of the copper based metal layer (3) would not occur to thereby provide flexible circuit board (6) of high reliability.

Description

200836609 九、發明說明【發明所屬之技術領域】本發明關於例如聚醯亞胺薄膜等之樹脂薄膜的表面，形成銅系金屬層之可撓性電路基板及其製造方法。 ir _ 【先前技術】近年，伴隨電子機器的小型化、高性能化，成爲元件 φ 或基板等構成部品的介面之安裝技術的高密度化行進，在所對應之可撓性印刷電路基板（FPC )，也被要求高精細化。作爲這種電路基板之一的可撓性印刷電路基板的製作方法，在耐熱性薄膜上形成銅膜，對銅膜進行圖案蝕刻，並將1C等進行晶片焊接，製作可撓性電路板之方法。關於作爲本電路用加以使用之可撓性電路基板，一般採用下述方式，即，層積銅箔與聚醯亞胺薄膜之方式，與 • 形成用來對聚醯亞胺薄膜上賦予密接力之鎳·鉻合金濺鍍膜與用來賦予導電性之銅濺鍍膜，在其上，藉由鍍裝法來一形成銅膜之方式。兩者中之後述的利用濺鍍法所形成者，由於具有可將銅作薄等之特徴，從未來性的觀點來看，今後將被廣泛使用。但，由於銅膜的厚度變薄，並且進行微細圖案化之際 ’用來賦予密接力之鎳-鉻合金濺鍍膜不易蝕刻，故，會有下述問題，即，側蝕刻會進行，無法形成線寬3 5 μηι以下的微細圖案。且，在高溫下的保存試驗，由於受到來自 -4- 200836609 於聚醯亞胺薄膜側的水分或氧之浸透，鎳·鉻合金氧化造成密接力降低，由可靠性的觀點來看，存有問題。爲了解決這些的問題，提案有使用他的金屬例如鎳-銅合金等，來代替鎳-鉻合金（下述的專利文獻1 )。然，而，在專利文獻1的方法，雖然改良了微細圖案的這一點 . ，但在可靠性的這一點上仍存有問題。作爲解決此問題之對策，提案有在與銅濺鍍膜相反側 Φ 之聚醯亞胺面形成氧化物之方法（下述的專利文獻1及2 )。但，在這些的方法，由於成膜程序多，裝置變得複雑，故會造成成本提高。作爲解決此問題之對策，於薄膜與銅濺鍍之界面，形成氧化矽或氧化鉻等的氧化物（下述的專利文獻3 )。但，在此方法，密接力並不充分。因此，提案出，爲了獲得矽、鉻、鎳等的金屬與氮之化合物膜、與銅之密接力，在銅側使用氮少的膜，來提昇 • 密接力且防止水分透過之方法（下述的專利文獻4 )。又’提案有形成銅氧氮化物層來代替氮化物者（下述的·專利文獻5 )。專利文獻1 日本特許第3447070號公報專利文獻2 日本特開2005-219259號公報專利文獻3日本特開平1 - 1 3 3 729號公報 •專利文獻4日本特開2005-347438號公報專利文獻5日本特開2005-54259號公報 200836609 【發明內容】〔發明所欲解決之課題〕但’由於在上述專利文獻4的方法所形成之聚醯亞胺側之與氮的化合物膜，未充分地促進氮化反應，不會成爲 - 化學計量的氮化物，故，會有若不將膜厚作成非常厚的話 • ’則無法獲得充分的密接性之問題。且，在真空蒸鍍，因即使導入氮氣，也無法促進化學反應，所以，矽或鉬等， • 無法成爲氮化物，僅能獲得接近金屬狀態之膜，無法提昇可靠性。且’爲了改善密接力，而加入矽或鎳、鉻等的金屬層’但其結果’會殘留有下述問題，即，使得後程序的蝕刻之蝕刻變得不易進行，在進行微細圖案化之際，側蝕刻行進之問題。另外，在裝置方面，由於標靶數變多，會有裝置變大等之問題產生。又，在上述專利文獻5的方法，在與聚醯亞胺薄膜之密接性的這一點上，並不充分。本發明是有鑑於上述情事而開發完成之發明，其目的 ® 在於提供，具有優良銅系金屬層之密接性，且可進行微細蝕刻，可靠性高的可撓性電路基板及其製造方法。〔用以解決課題之手段〕爲了達到上述目的，本發明的可撓性電路基板，第1 要旨是在樹脂薄膜的表面，形成有對矽在當量含有0.5〜 1·33之氮的利用濺鍍法所形成之氮化矽層，進一步形成有銅系金屬層。爲了達到上述目的，本發明的可撓性電路基板，第2 -6 - 200836609 要旨是在樹脂薄膜的表面，形成有對矽在當量含有0.3〜 1.1之氮的利用濺鍍法所形成之氧氮化矽層，.進一步形成有銅系金屬層。爲了達到上述目的，本發明的可撓性電路基板，第3 ^ 要旨是在樹脂薄膜的表面，形成有利用濺鍍法所形成之氮 . 化矽層或氧氮化矽層，且形成有由矽、鋁、鎳所選擇之厚度0·5〜5 nm的金屬膜，進一步形成有銅系金屬層。 • 爲了達到上述目的，本發明的可撓性電路基板的製造方法，第1要旨是具備：在樹脂薄膜的表面，形成對矽在當量含有0·5〜1·33之氮的利用濺鍍法所形成之氮化矽層的氮化矽濺鍍製程；及進一步形成銅系金屬層之銅系金屬形成製程。又，爲了達到上述目的，本發明的可撓性電路基板的製造方法，第2要旨是具備在樹脂薄膜的表面，形成對矽在當量含有〇·3〜1·1之氮的利用濺鍍法所形成之氧氮化 ® 矽層的製程；及進一步形成銅系金屬層之製程。。又，爲了達到上述目的，本發明的可撓性電路基板的、製造方法，第3要旨是在樹脂薄膜的表面，形成利用濺鍍法所形成之氮化矽層或氧氮化矽層的第1濺鍍製程；形成由矽、鋁、鎳所選擇之厚度0·5〜5 nm的金屬膜之第2濺鍍製程；及進一步形成銅系金屬層之銅系金屬形成製程。〔發明效果〕即，第1的本發明是在樹脂薄膜的表面，形成有對矽 200836609 在當量含有0.5〜1 · 3 3之氮的利用濺鍍法所形成之氮化矽層’進一步形成有銅系金屬層。如此，藉由形成在當量含有0 · 5〜1 · 3 3之氮的氮化矽層作爲中間層，可使銅系金屬層之密接性變得良好。且，由於上述氮化矽層爲絕緣物， • 故’不需要進行蝕刻，僅將銅系金屬層進行蝕刻即可，因 - 此’不太會產生側蝕刻，而能夠進行微細餓刻。並且，即使在高溫下，來自於樹脂薄膜側的水分或氧滲透，受到氮 φ 化矽層所封鎖，不會產生銅系金屬層的氧化或密接力的降低，成爲可靠性優良的可撓性電路基板。即，第2的本發明是在樹脂薄膜的表面，形成有對矽在當量含有0.3〜1.1之氮的利用濺鍍法所形成之氧氮化矽層，進一步形成有銅系金屬層。如此，由形成在當量含有0.3〜1 . 1之氮的氮化矽層作爲中間層，可使得銅系金屬層之密接性變得良好。且，由於上述氧氮化矽層爲絕緣物，故，不需要進行蝕刻，僅將銅系金屬層進行蝕刻即可 • ，因此，不太會產生側飩刻，而可進行微細蝕刻。並且，即使在高溫下，來自於樹脂薄膜側的水分或氧滲透，受到氮化矽層所封鎖，不會產生銅系金屬層的氧化或密接力的降低，成爲可靠性優良的可撓性電路基板。 * 又，第3的本發明是在樹脂薄膜的表面，形成有利用濺鍍法所形成之氮化矽層或氧氮化矽層’且形成有由砂、鋁、鎳所選擇之厚度0· 5〜5nm的金屬膜’進一步形成有銅系金屬層。如此’藉由形成氮化矽層或氧氮化5夕層與由矽、鋁、鎳所選擇的厚度〇·5〜5nm的金屬膜來作爲中間 -8- 200836609 層，可使得銅系金屬層之密接性變得良好。且，由於上述氮化矽層或氧氮化矽層爲絕緣物，故，不需要進行蝕刻，僅將極薄的矽等的金屬膜與銅系金屬層進行蝕刻即可，因此，不太會產生側蝕刻，而可進行微細触刻。並且，即使 • 在高溫下，來自於樹脂薄膜側的水分或氧滲透，氮化矽層 , 或氧受到氮化矽層所封鎖，不會產生銅系金屬層的氧化或密接力的降低，成爲可靠性優良的可撓性電路基板。 • 本發明的第1的可撓性電路基板的製造方法，上述氮化矽濺鍍製程是在對在與標靶相對面的領域輸送樹脂薄膜之電極滾子，一邊施加高頻偏向電壓一邊進行之情況，由於藉由高頻偏向電壓使得樹脂薄膜側之電極滾子對周圍觀看時朝上負電位側轉移，故，不僅可充分確保氮化砂中的氮量，並且可大寬度提昇氮化矽層之密接力。本發明的第2的可撓性電路基板的製造方法，上述氧氮化矽濺鍍製程是在對與標靶相對面的領域輸送樹脂薄膜 β 之電極滾子，一邊施加高頻偏向電壓一邊進行情況，由於藉由高頻偏向電壓使得樹脂薄膜側之電極滾子對周圍觀看、時朝上負電位側轉移，故，不僅可充分確保氮化矽中的氮量，並且可大寬度提昇氮化矽層之密接力。本發明的第3的可撓性電路基板的製造方法，上述第 2濺鍍製程是在對與標靶相對面的領域輸送樹脂薄膜之電極滾子，一邊施加高頻偏向電壓一邊進行情況，由於藉由局頻偏向電壓使得樹脂薄膜側之電極滾子對周圍觀看時朝上負電位側轉移，故，金屬膜的密接力也大寬度提昇。冬 200836609 【實施方式】其次，說明用來實施本發明之理想形態。圖1式顯示本發明的第1實施形態的可撓性電路基板 - 之斷面圖。 . 此可撓性電路基板6是在樹脂薄膜1的表面，形成對矽在當量含有0.5〜1.33之氮的利用濺鍍法所形成之氮化 Φ 矽層2a，進一步形成有銅系金屬層3。在這個例子，上述銅系金屬層3是由利用濺鍍法所形成的銅濺鍍膜4與利用鍍裝法所形成的鍍銅層5所構成的。作爲上述樹脂薄膜1，例如，聚醯亞胺薄膜、聚對苯二甲酸乙二醇酯薄膜、聚碳酸酯薄膜、液晶聚合物薄膜等由於具有優良的耐熱性、機械的安定性、機械的強度、電氣的特性等，故可理想加以使用。在上述在樹脂薄膜1的表面，利用反應性濺鍍法，形 • 成對矽在當量含有0.5〜1.33之氮的氮化矽層2a，來作爲中間層。在當氮對矽的量在當量未滿· 5時，則在高溫下之可靠性的這一點上會產生問題，相反地，在當量超過1.3 3 時則反而會造成密接力變弱。上述氮化矽層2a的厚度，理想圍5〜15nm左右。在未滿5nm時’則無法在筒溫下，充分地防止來自於樹脂薄膜1側的水分透過，在可靠性上會產生問題，相反地，當超過15 nm時，則，會有在膜產生裂縫或因歪斜造成膜剝離，反而會使密接力變弱。特別是期望爲8〜1 2nm，成 -10- 200836609 爲銅系金屬層3的密接力及可靠性優良。在這個例子’上述銅系金屬層3是由形成於上述氮化矽層2a上之銅濺鍍膜4與形成於上述銅濺鍍膜4上之鍍銅層5所構成的。作爲上述銅濺鍍膜4及鍍銅層5即構成 " 銅系金屬層3之銅系金屬’可使用銅或銅合金。 . 上述銅濺鍍膜4是形成50〜1〇〇 ηηι左右的厚度爲佳。這是由於當厚度未滿50nm時，則在進行下一個製程的 • 銅鍍裝之際，不僅容易引起被稱爲「燒焦」之鍍裝層的變色，且銅鍍裝的條件設定之調整困難，並且根據情況，會使密接力降低之故。相反地，當超過1 OOnm時，則濺鍍時間變長，生產速度顯著降低。上述鍍銅層5的厚度，能以電氣傳導度或圖案之線寬等，加以適宜決，但設定於〇·2μιη〜1 5 μιη左右。這是由於當未滿〇·2μπι時，則在電氣傳導度的這一點上會產生問題，相反地，當超過1 5 μιη時，則會有不易形成微細圖案 • 之情況之故。圖2是顯示本發明的第2實施形態的可撓性電路基板 _ 之斷面圖。 - 此可撓性電路基板6是在樹脂薄膜1的表面，形成有對矽在當量含有0.3〜1.1之氮的利用濺鍍法所形成之氧氮化矽層2b，進一步形成有銅系金屬層3。在這個例子，上述銅系金屬層3是由利用濺鍍法所形成的銅濺鍍膜4與利用鍍裝法所形成的鍍銅層5所構成的。上述在樹脂薄膜1的表面，形成利用反應性濺鍍法， -11 - 200836609 對矽在當量含有〇 · 3〜1 · 1之氮的形成氧氮化矽層2b，作爲中間層。當氮對矽的量在當量未滿0.3時’則在高溫下之可靠性的這一點上會產生問題，相反地，當在當量超過 1 .1時，反而會使密接力變弱。 . 上述氧氮化矽層2b的厚度，理想爲5〜20nm左右。 ^ 在未滿5nm時，在高溫下，無法充分地防止來自於樹脂薄膜1側的水分透過，在可靠性上會產生問題，相反地， φ 當超過20nm時，由於在膜產生裂縫或因歪斜造成膜剝離，故，反而會使密接力變弱。特別是期望爲8〜1 5nm，使得成爲銅系金屬層3的密接力及可靠性優良者。上述銅系金屬層3是在這個例子，由形成於上述氧氮化矽層2b上之銅濺鍍膜4與形成於上述銅濺鍍膜4上之鍍銅層5所構成。上述銅濺鍍膜4及鍍銅層5即作爲構成銅系金屬層3之銅系金屬，可使用銅或銅合金。除此以外，其餘是與上述第1實施形態的可撓性電路 φ 基板，對於相同的部分賦予相同符號。圖3及圖4是顯示用來製造上述可撓性電路基板6的裝置之圖。圖3是顯示形成上述氮化矽層2a、氧氮化矽層2b及銅濺鍍膜4之濺鍍環裝置，圖4是顯示形成上述 _ 鍍銅層5之鍍裝裝置。圖3所示的濺鍍環裝置是具備··進行作爲前處理之電漿處理的電漿室10;進行第1濺鍍製程之第1濺鍍室n ;及進行第2濺鍍製程之第2濺鍍室12。上述電漿室1〇、第1濺鍍室1 1以及第2濺鍍室12，分別連接於未圖示 -12- 200836609 的真空泵浦，可分別獨立進行壓力調整。在上述電漿室1 〇，設有：供給捲繞成滾子狀之樹脂薄膜〗的供給滾子13 ;及捲取在第1濺鍍室1 1及第2濺鍍室〗2分別形成有氮化矽層2a及銅濺鍍膜4的具有種晶 * 層之薄膜la的捲取滾子14。又，在上述電漿室1〇，設有 ^ :對由供給滾子13所供給的樹脂薄膜1進行作爲前處理之電漿處理的電漿處理裝置15。 φ 在上述電漿處理裝置1 5，導入對氬氣添加了 5〜60 容量％之氧或氮或這些的混合氣體之氣體作爲電漿處理用氣體。又，藉由對電極施加直流電壓或交流電壓或高頻電壓，產生電漿，使樹脂薄膜1通過此電漿環境中，實施電漿處理。藉由此電漿處理，在樹脂薄膜1表面產生官能基，發揮提高氮化矽層2a及氧氮化矽層2b的密接力之作用。亦可單獨使用氬氣作爲電漿處理用氣體，但，藉由混合氧或氮，可使效果更提昇。 # 在上述電漿室10，進行了電漿處理之樹脂薄膜1被供給至第1濺鍍室11，進行利用反應性濺鍍之氮化矽及 _ 氧氮化矽的成膜。在第1濺鍍室11，設有：矽標靶18; 及在與上述矽標靶18相對面的領域，輸送進行了電漿處理之樹脂薄膜1的第1滾子16。首先，說明形成氮化矽層2a之第1實施形態的方法〇在上述矽標靶1 8，藉由直流電源21施加負電位的電壓。另外，在上述第1滾子16，藉由高頻電源20施加高 -13- 200836609 頻偏向電壓。又，導入作爲反應性濺鍍氣體之氬與氮的混合氣體。氬氣與氮氣的比率，理想範圍由95: 5至50: 5 〇，當氮氣過少時，則膜中的氮變得太少，無法獲得密接力或可靠性。相反地，當氮氣過多時，則膜的析出速度變 - 慢，又，比起化學計量，氮變多。，又’上述氮化矽濺鍍製程是對作爲用來進行薄膜的冷却之被稱爲圓筒滾子（can roll )的行進用滾子來發揮功 # 能之第1滾子16，一邊施加高頻偏向電壓一邊進行。藉此’賦予用來促進反應的能量，促進化學反應。上述高頻偏向電壓，0.05〜〇.2W/cm2的電力爲理想範圍。當未滿 (K〇5W/cm2時，則無法獲得密接力，當超過〇.2W/cm2時 ’則聚醯亞胺薄膜劣化，在可靠性上發生問題。當未施加此高頻偏向電壓時，含於所形成的氮化矽層2a之氮成分變得相當少，無法獲得密接力或可靠性。如此，進行：在樹脂薄膜1的表面，形成對矽在當量 • 含有〇·5〜1.33之氮的氮化矽層2a氮化矽濺鍍製程。在上述氮化矽濺鍍製程形成了氮化矽層2a之樹脂薄 • 膜1被供給至第2濺鍍室1 2，進行銅濺鍍製程。在上述第2濺鍍室12，設有銅標靶19;及與上述銅標靶19相對面的領域，輸送樹脂薄膜1之第2滾子17。在上述銅標靶1 9，藉由直流電源21施加負電位的電壓。又，使用氬氣作爲濺鍍氣體，進行銅濺鍍製程來形成銅縣鍍膜4。 -14 - 200836609 再者，電漿室10、第1濺鍍室11、第2濺鍍室12的氣壓亦可做成大致相同’但將第2濺鍍室1 2做成最高爲佳。這是由於當第2濺鍍室1 2的氣壓變低時，則氮氣會由第1濺鍍室1 1或電漿室1 〇流入，產生銅的氮化物，根 - 據情況，導電性會消失之故。 . 形成有銅濺鍍膜4之具有種晶層之薄膜ia，再次被送至電漿室1 〇，以捲取滾子1 4加以捲取。 • 其次，氮化矽層2a及形成有銅灘鍍膜4之具有種晶層之薄膜1 a以連續鍍銅裝置進行鍍銅製程，形成鍍銅層 5 ° 圖4所示的連續鍍銅裝置是具備鍍裝槽25、水洗槽 26、及乾燥槽27，在以供給滾子28所供給之具有種晶層之薄膜la，以硫酸銅浴等形成鍍銅層5，形成本發明的可燒性電路基板6 ’以捲取滾子2 9加以捲取。圖中，符號 3 0爲直流電源、3 1爲陽極、3 2爲陰極滾子。 • 在這個例子，上述銅濺鍍製程與鍍銅製程爲形成銅系金屬層之本發明的銅系金屬形成製程。 • 其次，說明形成氧氮化矽層2b之第2實施形態的方法。在上述矽標靶1 8，藉由直流電源21施加負電位的電壓。另外，在上述第1滾子16，藉由高頻電源20施加高頻偏向電壓。又，導入作爲反應性濺鍍氣體之氬與氧與氮之混合氣體。氬氣與氧氮之混合氣體的比率，9 0 : 1 〇至 6 0 : 4 0爲理想範圍，上述氧氮混合氣體之氧氣與氮氣的 -15- 200836609 比率，1 0 : 90至20 : 1 0爲理想範圍。當氮氣過少時，則膜中的氮變得太少，無法獲得密接力或可靠性。相反地，當氮氣過多時，則膜的析出速度變慢，又比起化學計量，氮變多。 - 又，上述氧氮化矽濺鍍製程是對作爲用來進行薄膜的，冷却之被稱爲圓筒滾子的行進用滾子來發揮功能之第1滾子1 6，一邊施加高頻偏向電壓一邊進行。藉此，賦予用 φ 來促進反應的能量，促進化學反應。上述高頻偏向電壓， 0.05〜0.3W/cm2的電力爲理想範圍。當未滿〇.〇5W/cm2時，則無法獲得密接力，當超過0.3 W/cm2時，則聚醯亞胺薄膜劣化，在可靠性上發生問題。當未施加此高頻偏向電壓時，含於所形成的氧氮化矽層2b之氮成分變得相當少，無法獲得密接力或可靠性。如此，進行：在樹脂薄膜1的表面，形成對矽在當量含有0·5〜1·33的氮之氧氮化矽層2b之氧氮化矽濺鍍製 • 程。在上述氧氮化矽濺鍍製程形成了氧氮化矽層2b之樹脂薄膜1被供給至第2濺鍍室1 2，進行銅濺鍍製程及鍍銅製程。銅濺鍍製程及鍍銅製程是與上述第1實施形態的方法相同。如以上所述，在第1的實施形態，在樹脂薄膜1的表面，形成對矽在當量含有0.5〜1.33之氮的利用濺鍍法所形成之氮化矽層2a，進一步形成銅系金屬層3。如此，藉由形成氮在當量含有0 · 5〜1 . 3 3之氮化矽層2 a作爲中間層 -16- 200836609 ，使得銅系金屬層3之密接性變得良好。且，由於上述氮化矽層2 a爲絕緣物，故不需要進行蝕刻，僅將銅系金屬層進行蝕刻即可，因此不太會產生側蝕刻，而可進行微細蝕刻。並且，在高溫下即使來自於樹脂薄膜1側的水分或 - 氧滲透，也受到氮化砂層a所封鎖，不會產生銅系金屬層 . 3的氧化或密接力的降低，成爲可靠性優良的可撓性電路基板6。 φ 又，由於上述氮化矽濺鍍製程是對在與矽標靶1 8相對面的領域輸送樹脂薄膜1之第1滾子16, 一邊施加高頻偏向電壓一邊進行，藉由高頻偏向電壓使樹脂薄膜1側的第1滾子1 6對周圍觀看時朝上負電位側轉移，不僅可充分確保氮化矽中的氮量，並且氮化矽層2a的密接力也大幅度上升。如以上所述，在第2的實施形態，在樹脂薄膜1的表面，形成對矽在當量含有0.5〜1 . 3 3之氮的利用濺鍍法所 # 形成之氧氮化矽層2b，進一步形成銅系金屬層3。如此，藉由形成氮在當量含有0.5〜1.33之氧氮化矽層2b作爲中間層’使得銅系金屬層3之密接性變得良好。且，由於上述氧氮化矽層2b爲絕緣物，故不需要進行触刻，僅將銅系金屬層進行蝕刻即可，因此不太會產生側蝕刻，而可進行微細飩刻。並且，在高溫下即使來自於樹脂薄膜1側的水分或氧滲透’也受到氧氮化矽層2b所封鎖，不會產生銅系金屬層3的氧化或密接力的降低，成爲可靠性優良的可撓性電路基板6。 -17- 200836609 又，由於上述氧氮化矽濺鍍製程是對在與矽標靶1 8 相對面的領域輸送樹脂薄膜1之第1滾子1 6，一邊施加高頻偏向電壓一邊進行’故藉由高頻偏向電壓使樹脂薄膜 1側的第1滾子1 6對周圍觀看時朝上負電位側轉移，氧不僅可充分確保氮化矽中的氮量，並且氧氮化矽層2b的密接力也大幅度上升。圖5是說明本發明的第3的實施形態之圖。此濺鍍裝置是藉由高頻電源22對第2濺鍍室12的第 2滾子1 7施加高頻偏向電壓，將銅灑鍍製程以下述方式進行，即，對在與銅標靶1 9相對面的領域輸送樹脂薄膜 1之第2滾子17，一邊施加高頻偏向電壓一邊進行。高頻偏向電壓的電力，〇· 05 W/cm2以上爲理想範圍，如爲該値以下的話則無法獲得充分的密接力提昇之效果。除此以外是與第1及第2的實施形態相同，針對相同的部分賦予相同的符號。藉此，使得銅濺鍍膜4的密接力更進一步提昇。除此以外可達到與上述第1及第2的實施形態相同的作用効果。圖6是說明本發明的第4實施形態之圖。此濺鍍裝置是在第1濺鍍室11與第2濺鍍室12之間設有共通滾子23，藉由高頻電源22對此共通滾子23施加高頻偏向電壓。又，氮化矽漉鍍製程、氧氮化矽濺鍍製程及銅濺鍍製程，利用共通滾子23來進行，均是一邊施加筒頻偏向電壓一邊進行。除此以外是與第1及第2的實施形態相同，針對相同的部分賦予相同的符號。藉此，使 -18 - 200836609 得銅濺鍍膜4的密接力更進一步提昇。除此以外可達到與上述第1〜第3的實施形態相同的作用効果。圖7是用來說明本發明的第5實施形態之圖。此濺鍍裝置是設置進行真空蒸鍍之蒸鍍室37來代替，第2濺鍍室12。在上述蒸鍍室37，供給欲蒸鍍的銅線34 . 之銅供給部33 ;將所供給之銅線34予以融解的坩堝35 ; 及用來加熱坩堝35之加熱器36，形成銅蒸鍍膜來代替銅 φ 濺鍍膜4。除此以外是與第1〜第4實施形態相同，針對相同的部分賦予相同的符號。在這個例子，也可達到與上述第1〜第4實施形態相同的作用効果。圖8是顯示本發明的第6實施形態之圖。此可撓性電路基板是藉由離子披覆或真空蒸鍍法作成銅膜3 a來作爲銅系金屬層，省略鍍銅者。在銅膜3 a的厚度爲Ιμιη以下的情況有效。圖9是顯示本發明的第7實施形態的可撓性電路基板 # 之斷面圖。此可撓性電路基板6是在樹脂薄膜1的表面，形成利用濺鍍法所形成之氮化矽層2a或氧氮化矽層2b，進一步形成由矽、鋁、鎳所選擇之厚度〇.5〜5nm的金屬膜7, 進一步形成有銅系金屬層3。在這個例子，上述銅系金屬層3是由利用濺鍍法所形成的銅濺鍍膜4與利用鍍裝法所形成的鍍銅層5所構成的。作爲上述樹脂薄膜〗，例如，聚醯亞胺薄膜、聚對苯二甲酸乙二醇酯薄膜、聚碳酸酯薄膜、液晶聚合物薄膜等 -19 - 200836609 在耐熱性、機械的安定性、機械的強度、電氣的特性等之這些點上非常優良，可理想地加以使用。上述在樹脂薄膜1的表面，利用反應性濺鍍法，形成氮化矽層2a或氧氮化矽層2b作爲中間層。 . 作爲上述氮化矽層2a，理想爲作成對矽在當量含有參〇·5〜1.33之氮的氮化矽層2a。當氮對矽的量在當量未滿 0.5時，則在高溫下之可靠性的這一點上會產生問題，相 φ 反地，在當量超過1 .3 3時則反而會造成密接力變弱。上述氮化矽層2 a的厚度，理想圍5〜1 5 nm左右。在未滿 5 nm時，在高溫下，無法充分地防止來自於樹脂薄膜1側的水分透過，在可靠性上會產生問題，相反地，當超過 1 5nm時，由於在膜產生裂縫或因歪斜造成膜剝離，故，反而會使密接力變弱。特別是期望爲8〜1 2nm，可使得成爲銅系金屬層3的密接力及可靠性優良者。作爲氧氮化砂層2b，作成對砂在當量含有0.3〜1.1 • 之氮的氧氮化矽層2b爲佳。當氮對矽的量在當量未滿0.3 時，則在高溫下之可靠性的這一點上會產生問題，相反地，當在當量超過1·1時，反而會使密接力變弱。上述氧氮化矽層2b的厚度，理想爲5〜20nm左右。在未滿5nm時，在高溫下，無法充分地防止來自於樹脂薄膜1側的水分透過，在可靠性上會產生問題，相反地，當超過20nm時，由於在膜產生裂縫或因歪斜造成膜剝離，故，反而會使密接力變弱。特別是期望爲8〜1 5nm，使得成爲銅系金屬層3的密接力及可靠性優良者。 -20- 200836609 其次，形成由矽、鋁、鎳所選擇之金屬膜7。其厚度 ’理想爲0.5 n m〜5 n m，更理想爲1 n m〜3 n m。當金屬膜7 的厚度未滿〇.5nm時的情況、超過5nm之情況，使銅系金屬層3的密接力提昇之效果少。成膜法亦可爲蒸鍍法等 • ’但由前後的真空度等之關係及密接力的觀點來看，期望 . 爲濺鍍法。上述銅系金屬層3,在這個例子，是由形成於上述氮 # 化矽層2a或氧氮化矽層2b上的銅濺鍍膜4與形成於上述銅濺鍍膜4上的鍍銅層5所構成。上述銅濺鍍膜4及鍍銅層5即作爲構成銅系金屬層3之銅系金屬，可使用銅或銅合金。上述銅濺鍍膜4是形成50〜10〇nm左右的厚度爲佳。這是由於當厚度未滿5 Onm時，則在進行下一個製程的銅鍍裝之際，容易引起被稱爲「燒焦」之鍍裝層的變色，不僅不易進行銅鍍裝的條件設定的調整，且根據情況，會 # 使密接力降低。相反地，當超過1 OOnm時，則濺鍍時間變長，生產速度顯著降低之故。上述鍍銅層5的厚度，能以電氣傳導度或圖案之線寬 f* t 等予以適宜決定，但設定於〇.2μιη〜15μπι左右。這是由於當未滿〇·2μπι未滿時，則電氣電導度的這一點上會產生問題，相反地’當超過1 5 μ m時，則會有不易形成微細圖案之情況。圖1 0及圖4是顯示製造上述可撓性電路基板6的裝置之圖。圖2顯示用來形成上述氮化矽層2a、氧氮化矽 -21 - 200836609 層2b、金屬膜7及銅濺鍍膜4之濺鍍環裝置，圖3是顯示用來形成上述鍍銅層5之鍍裝裝置。圖1 0所示的濺鍍環裝置是具備：進行作爲前處理之電漿處理的電漿室10;進行第1濺鍍製程之第1濺鍍室 4 及進行第2濺鍍製程之第2濺鍍室12。上述電漿室 ▲ !〇、第1濺鍍室11以及第2濺鍍室12，分別連接於未圖示的真空泵浦，可分別獨立進行壓力調整。 • 在上述電漿室10，設有：供給捲繞成滾子狀之樹脂薄膜1的供給滾子1 3 ;及捲取在第1濺鍍室1 1及第2濺鍍室12分別形成氮化矽層2a或氧氮化矽層2b、金屬膜7 及銅濺鍍膜4之具有種晶層之薄膜la的捲取滾子14。又，在上述電漿室1 0，設有對由供給滾子1 3所供給的樹脂薄膜1進行作爲前處理之電漿處理的電漿處理裝置15。在上述電漿處理裝置1 5，導入對氬氣添加了 5〜60 容量％之氧或氮或這些的混合氣體之氣體作爲電漿處理用 • 氣體。又，藉由對電極施加直流電壓或交流電壓或高頻電壓，產生電漿，使樹脂薄膜1通過此電漿環境中，實施電 β 漿處理。藉由此電漿處理，在樹脂薄膜1表面產生官能基，發揮提高氮化矽層2a及氧氮化矽層2b的密接力之作用。亦可單獨使用氬氣作爲電漿處理用氣體，但，藉由混合氧或氮，可使效果更提昇。在上述電漿室1 〇，進行了電漿處理之樹脂薄膜1被供給至第1濺鍍室Π，進行利用反應性濺鍍之氮化矽或氧氮化矽的成膜。在第1濺鍍室11，設有：矽標靶18; -22- 200836609 及在與上述矽標靶1 8相對面的領域，輸送進行了電漿處理之樹脂薄膜1的第1滾子16。首先，說明形成氮化矽層2a之第1例的方法。在上述砂標IE 1 8，藉由直流電源2 1施加負電位的電 • 壓。另外，在上述第1滾子16，藉由高頻電源20施加高 • 頻偏向電壓。又，導入作爲反應性濺鍍氣體之氬與氮的混合氣體。氬氣與氮氣的比率，理想範圍由95:5至50: • 50，當氮氣過少時，則膜中的氮變得太少，無法獲得密接力或可靠性。相反地，當氮氣過多時，則膜的析出速度變慢，又比起化學計量，氮變多。又’上述氮化矽濺鍍製程是對作爲用來進行薄膜的冷却之被稱爲圓筒滾子的行進用滾子來發揮功能之第1滾子 1 6，一邊施加高頻偏向電壓一邊進行。藉此，賦予用來促進反應的能量，促進化學反應。上述高頻偏向電壓，〇. 05 〜0.2W/cm2的電力爲理想範圍。當未滿0.05W/cm2時， Φ 則無法獲得密接力，當超過0_2W/cm2時，則聚醯亞胺薄膜劣化’在可靠性上發生問題。當未施加此高頻偏向電壓時，含於所形成的氮化矽層2 a之氮成分變得相當少，無法獲得密接力或可靠性。觚如此’進行：在樹脂薄膜1的表面，形成對矽在當量含有0.5〜1.33之氮的氮化矽層2a之氮化矽濺鍍製程。在上述氮化矽濺鍍製程形成了氮化矽層2 a之樹脂薄膜1被供給至第2濺鍍室12，進行行成由矽、鋁、鎳所選擇之厚度0.5〜5nm的金屬膜7之金屬濺鍍製程，並且 -23- 200836609 進行銅濺鍍製程。在上述弟2濺鍍室12，設有：以由砂、銘、鎳所選擇之金屬所構成的金屬標靶24及銅標靶19;和在與上述金屬標靶24及銅標靶1 9相對面的領域，輸送樹脂薄膜1 • 之第2滾子1 7。 • 在上述金屬標祀24，藉由直流電源21a施加負電位的電壓。又，使用氬氣作爲濺鍍氣體，進行金屬濺鍍製程 0 ，形成金屬膜7。此時’對用來進行薄膜的冷却之被稱爲圓筒滾子作爲行進用滾子來發揮功能的第2滾子17，藉由高頻電源22 ’ 一邊施加局頻偏向電壓一邊進行爲佳。藉此，賦予用來促進反應的能量，促進化學反應。上述高頻偏向電壓， 0·03〜0.2W/cm2的電力爲理想範圍。當未滿〇.〇3W/cm2時，則密接力變得稍弱，又，當超過0.2W/cm2時，則聚醯亞胺薄膜劣化，在可靠性上發生問題。 # 在上述銅標靶1 9，藉由直流電源2 1施加負電位的電壓。又’使用氬氣作爲濺鍍氣體，進行銅濺鍍製程來形成銅濺鍍膜4。 η 又，銅濺鍍製程，亦可藉由高頻電源22，對在與銅 m 標靶19相對面的領域輸送樹脂薄膜1之第2滾子17, 一邊施加高頻偏向電壓一邊進行。此時的高頻偏向電壓的電力，0· 03 W/cm2以上爲理想範圍，如爲該値以下的話，則無法獲得密接力提昇之效果。藉此，使得銅濺鍍膜4的密接力更進一步提昇。 -24- 200836609 再者，電漿室10、第1濺鍍室11、第2濺鍍室12的氣壓，亦可做成大致相同，但將第2濺鍍室1 2做成最高爲佳。這是由於當第2濺鍍室12的氣壓變低時，則氮氣會由第1濺鍍室11或電漿室1 〇流入，產生銅的氮化物，、根據情況，導電性會消失之故。 . 形成有銅濺鍍膜4之具有種晶層之薄膜la，再次被送至電漿室1 〇，以捲取滾子1 4加以捲取。 φ 其次，氮化矽層2a或氧氮化矽層2b、金屬膜7及形成有銅濺鍍膜4之具有種晶層之薄膜ia，以連續鍍銅裝置進行鍍銅製程，形成鍍銅層5。圖4所示的連續鍍銅裝置是具備鍍裝槽2 5、水洗槽 26、及乾燥槽27，在以供給滾子28所供給之具有種晶層之薄膜la’以硫酸銅浴等形成鑛銅層5後，形成本發明的可撓性電路基板6，以捲取滾子2 9加以捲取。圖中，付號3 0爲直流電源、31爲陽極、32爲陰極滾子。 ® 在這個例子，上述銅濺鎪製程與鍍銅製程爲形成銅系金屬層之本發明的銅系金屬形成製程。 _ 其次，說明形成氧氮化砂層2b之第2例的方法。在上述矽標靶1 8，藉由直流電源21施加負電位的電壓。另外，在上述第1滾子16，藉由高頻電源20施加高頻偏向電壓。又，導入作爲反應性濺鍍氣體之氬與氧與氮之混合氣體。氬氣與氧氮之混合氣體的比率，9 0 ·· 1 〇至 60 : 40爲理想範圍，上述氧氮混合氣體之氧氣與氮氣的比率，1 0 : 90至40 : 60爲理想範圍。當氮氣過少時，則 -25- 200836609 膜中的織變得太少，無法獲得密接力或可靠性。相反地，當氮氣過多時，則膜的析出速度變慢，又比起化學計量，氮變多。又’上述氧氮化矽濺鍍製程是對作爲用來進行薄膜的 ^ 冷却之被稱爲圓筒滾子的行進用滾子來發揮功能之第1滾 • 子16’ 一邊施加高頻偏向電壓一邊進行。藉此，賦予用來促進反應的能量，促進化學反應。上述高頻偏向電壓， φ 0·05〜〇·3 W/em2的電力爲理想範圍。當未滿〇.〇5W/cm2時，則無法獲得密接力，當超過0.3 W/cm2時，則聚醯亞胺薄膜劣化’在可靠性上發生問題。當未施加此高頻偏向電壓時’含於所形成的氧氮化矽層2b之氮成分變得相當少，無法獲得密接力或可靠性。如此’進行：在樹脂薄膜1的表面，形成對矽在當量含有0.5〜1·33的氮之氧氮化矽層2b之氧氮化矽濺鍍製程。 Φ 在上述氧氮化矽濺鍍製程形成了氧氮化矽層2b之樹脂薄膜1被供給至第2濺鍍室12，進行金屬膜濺鍍製程、銅濺鍍製程及鍍銅製程。金屬膜濺鍍製程、銅濺鍍製程 * 及鍍銅製程，是與上述第1例的方法相同。如以上所述，在本實施形態，在樹脂薄膜1的表面’ 形成利用濺鍍法所形成之氮化矽層2a或氧氮化矽層2b，進一步形成由矽、鋁、鎳所選擇之厚度〜5nm的金屬膜7，進一步形成銅系金屬層3。如此，藉由形成氮化矽層2a或氧氮化矽層2b與由矽、鋁、鎳所選擇之厚度0·5 -26- 200836609 〜5nm的金屬膜7作爲中間層’使得銅系金屬層3之密接性變得良好。且，由於上述氮化矽層2 a或氧氮化矽層2b 爲爲絕緣物，故不需要進行蝕刻，僅將極薄的矽等的金屬膜7與銅系金屬層3進行蝕刻即可，因此，不太會產生側 • 飩刻，而可進行微細鈾刻。並且，在高溫下即使來自於樹 . 脂薄膜1側的水分或氧滲透，氮化矽層2a或也受到氧氮化矽層2b所封鎖，不會產生銅系金屬層3的氧化或密接 # 力的降低，成爲可靠性優良的可撓性電路基板。又，在本發明的第2濺鍍製程，金屬濺鍍製程是對在與金屬標靶24相對面的領域輸送樹脂薄膜1之第2滾子 1 7，一邊施加高頻偏向電壓一邊進行之情況，由於藉由高頻偏向電壓，使捌樹脂薄膜1側的第2滾子1 7對周圍觀看時朝上負電位側轉移，故，金屬膜7的密接力也大幅度上升。作爲上述濺鍍裝置，亦可在第1濺鍍室11與第2濺 • 鍍室1 2之間，設置共通滾子，對此共通滾子，藉由高頻電源施加高頻偏向電壓。又，氮化矽或氧氮化矽濺鍍製程 . 、金屬灘鍍製程及銅濺鍍製程，亦可利用共通滾子來進行，均是一邊施加高頻偏向電壓一邊進行。圖1 1是顯示本發明的第8實施形態的圖。此可撓性電路基板6是藉由離子披覆或真空蒸鍍法作成銅膜3a，作爲銅系金屬層3，而省略鍍銅者。在銅膜 3 a的厚度爲1 μ m以下的情況有效。以下，說明關於實施例。 -27- 200836609 〔實施例1〕使用圖3所示的成膜裝置，製作具有導電性的薄膜。聚醯亞胺薄膜，使用厚度 25μιη、寬度 25cm之曰本 • Kaneka公司製聚醯亞胺薄膜NPI。薄膜的搬送速度設爲，〇.8m/分。電漿處理室氣體，對氬添加30%的氮之混合氣體，調節氣體流量，使電漿處理室內的氣壓成爲0.5Pa， φ 施加交流電壓3 80V，產生電漿，使薄膜通過電漿環境中〇在下一個反應性濺鍍室，在氬70%、30%的氮之混合氣體的條件下，成爲〇.4Pa的方式調整流量，在直流電壓 410V，對寬度 26cm、直徑 20cm的第 1滾子 16，將 13.56MHz的高頻施加160W。所產生的膜的厚度爲10nm ，組成爲SiNl .2。其次，銅濺鍍，使用寬度26cm、直徑40cm第2滾子 Φ 17，在氬氣壓0.6Pa、直流電壓400V的條件進行成膜。其次，以圖4所示的銅鍍裝裝置，進行鍍裝使銅的厚度成爲10 μιη，製作出本發明的可撓性電路基板。 m < 〔評價法〕在3mm寬度以銅鍍裝膜殘留的方式進行飩刻，如JIS C 5 0 1 6所制定的方式，進行垂直方向之拉引試驗，測定密接力。又，可靠性爲將在3mm寬度進行了蝕刻之樣品在1 8 0 °C中放置1日，同樣地測定密接力。 -28— 200836609 〔實施例2〕在實施例2，改變氮化矽濺鍍製程的氮氣濃度、直流電壓、高頻電力，替換膜組成、膜厚以外，其餘以相同的條件進行成膜。比較例1 作爲比較例1，改變氮化矽成膜室的氮氣濃度、直流電壓、高頻電力，製作形成組成爲SiN0.3的氮化矽膜。實施例1、實施例2及比較例1之氮化矽作成條件與評價結果，顯示於下述的表1。表1 試料氣壓氣體組成直流電壓高頻電力膜組成膜厚密接力(N/mm) No (Pa) (Ar:N2) (V) (W/cm2) (nm) 初期 180°〇1 日實施例1 0.5 7:3 410 0.098 SiNl.2 10 0.8 0.9 實施例2-1 0.5 7:3 410 0.051 SiN0.7 10 0.6 0.7 實施例2-2 0.5 7:3 410 0.196 SiNL2 10 0.8 0.8 實施例2-3 0.5 9:1 400 0.051 SiN0.5 10 0.5 0.5 實施例2-4 0.5 5:5 420 0.15 SiNl.3 10 0.6 0.7 實施例2-5 0.5 8:2 390 0.098 SiN1.2 5 0.7 0.5 實施例2-6 0.7 7:3 425 0.098 SiN1.2 15 0.5 0.7 比較例1 0.5 9:1 400 0.01 SiNO.3 10 0.3 0.2[Technical Field] The present invention relates to a flexible circuit board in which a copper-based metal layer is formed on the surface of a resin film such as a polyimide film, and a method for producing the same. Ir _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ ), is also required to be highly refined. A method of producing a flexible printed circuit board as one of the circuit boards, a method of forming a copper film on a heat-resistant film, pattern etching a copper film, and wafer-welding 1C or the like to form a flexible circuit board . The flexible circuit board used as the circuit is generally formed by laminating a copper foil and a polyimide film, and forming a bonding force on the polyimide film. A nickel-chromium alloy sputter film and a copper sputter film for imparting conductivity, on which a copper film is formed by a plating method. The latter, which is formed by the sputtering method described later, has a feature of being able to make copper thin, etc., and will be widely used from a future point of view. However, since the thickness of the copper film is reduced and the fine patterning is performed, the nickel-chromium alloy sputtering film for imparting the adhesion is not easily etched. Therefore, there is a problem in that side etching is performed and formation is impossible. A fine pattern with a line width of 3 5 μηι or less. Moreover, in the storage test at a high temperature, due to the moisture or oxygen permeation from the side of the polyimide film on -4-200836609, the adhesion of the nickel-chromium alloy is lowered, and from the viewpoint of reliability, there is problem. In order to solve these problems, it is proposed to use a metal such as a nickel-copper alloy or the like instead of a nickel-chromium alloy (Patent Document 1 below). However, in the method of Patent Document 1, the fine pattern is improved. However, there is still a problem at this point of reliability. As a countermeasure against this problem, there has been proposed a method of forming an oxide on a polyimide surface of Φ opposite to the copper sputtering film (Patent Documents 1 and 2 below). However, in these methods, since the film forming process is large, the device is revived, which causes an increase in cost. As a countermeasure against this problem, an oxide such as ruthenium oxide or chromium oxide is formed at the interface between the film and the copper sputtering (Patent Document 3 below). However, in this method, the adhesion is not sufficient. Therefore, in order to obtain a film of a metal such as ruthenium, chromium, or nickel, and a compound film of copper and copper, a film having a small amount of nitrogen is used on the copper side to improve the adhesion and prevent moisture from being transmitted (described below). Patent Document 4). Further, it has been proposed to form a copper oxynitride layer instead of a nitride (Patent Document 5 below). Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 2005-219259. [Problem to be Solved by the Invention] However, the compound film with nitrogen on the polyimine side formed by the method of Patent Document 4 described above does not sufficiently promote nitrogen. Since the chemical reaction does not become a stoichiometric nitride, there is a problem that sufficient adhesion cannot be obtained unless the film thickness is made very thick. In addition, in the vacuum deposition, the chemical reaction cannot be promoted even if nitrogen gas is introduced. Therefore, it is not possible to form a nitride, and it is impossible to obtain a nitride. Only a film close to a metal state can be obtained, and reliability cannot be improved. Further, 'in order to improve the adhesion, a metal layer such as tantalum or nickel or chromium is added, but as a result, there is a problem that etching of the etching of the post-process is difficult, and fine patterning is performed. The problem of side etching travels. Further, in terms of the device, since the number of targets increases, problems such as a large device may occur. Moreover, the method of the above-mentioned Patent Document 5 is not sufficient in terms of adhesion to the polyimide film. The present invention has been developed in view of the above circumstances, and an object of the present invention is to provide a flexible circuit board which has excellent adhesion of a copper-based metal layer and which can be micro-etched and has high reliability, and a method for producing the same. [Means for Solving the Problem] In order to achieve the above object, the first object of the flexible circuit board of the present invention is that the surface of the resin film is formed to have an equivalent of 0. The nitrogen nitride layer of 5 to 1.33 is further formed with a copper-based metal layer by a tantalum nitride layer formed by a sputtering method. In order to achieve the above object, the flexible circuit board of the present invention, the second -6 - 200836609 is intended to have a pair of bismuth equivalents in the surface of the resin film. 3~1 a nitrogen oxynitride layer formed by sputtering. Further, a copper-based metal layer is formed. In order to achieve the above object, in the flexible circuit board of the present invention, the third object is to form a nitrogen formed by a sputtering method on the surface of the resin film. The ruthenium layer or the yttrium oxynitride layer is formed with a metal film having a thickness of 0·5 to 5 nm selected from ruthenium, aluminum, and nickel, and a copper-based metal layer is further formed. In order to achieve the above object, the first method of the method for producing a flexible circuit board of the present invention includes the use of a sputtering method for forming a nitrogen having an equivalent of 0·5 to 1.33 in an equivalent amount on the surface of the resin film. a tantalum nitride sputtering process of the formed tantalum nitride layer; and a copper-based metal forming process for further forming a copper-based metal layer. In order to achieve the above object, the second method of the method for producing a flexible circuit board of the present invention is to provide a sputtering method for forming a nitrogen having an equivalent of 〇·3 to 1:1 in the surface of the resin film. The process of forming the oxynitride® layer; and further forming a copper-based metal layer. . In order to achieve the above object, the third method of the method for producing a flexible circuit board of the present invention is to form a tantalum nitride layer or a hafnium oxynitride layer formed by a sputtering method on the surface of the resin film. 1 a sputtering process; a second sputtering process for forming a metal film having a thickness of 0·5 to 5 nm selected from ruthenium, aluminum, and nickel; and a copper-based metal formation process for further forming a copper-based metal layer. [Effect of the Invention] That is, in the first aspect of the invention, the surface of the resin film is formed with a pair of 矽 200836609 in an equivalent content of 0. A nitrided layer formed by a sputtering method of 5 to 1 · 3 3 is further formed with a copper-based metal layer. As described above, by forming a tantalum nitride layer having a nitrogen content of 0·5 to 1·3 3 as an intermediate layer, the adhesion of the copper-based metal layer can be improved. Further, since the tantalum nitride layer is an insulator, it is not necessary to perform etching, and only the copper-based metal layer may be etched, so that side etching is less likely to occur, and fine etching can be performed. Further, even at a high temperature, moisture or oxygen permeation from the resin film side is blocked by the nitrogen φ layer, and oxidation of the copper-based metal layer or a decrease in adhesion is not caused, and flexibility is excellent in reliability. Circuit board. That is, the second invention is formed on the surface of the resin film, and has a pair of 矽 in the equivalent content of 0. 3~1. The nitrogen oxynitride layer formed by the sputtering method is further formed with a copper-based metal layer. Thus, formed by the equivalent contains 0. 3~1. The nitrogen nitride layer of 1 nitrogen serves as an intermediate layer, and the adhesion of the copper-based metal layer can be made good. Further, since the yttrium oxynitride layer is an insulator, it is not necessary to perform etching, and only the copper-based metal layer can be etched. Therefore, side etching is less likely to occur, and fine etching can be performed. Further, even at a high temperature, moisture or oxygen permeation from the resin film side is blocked by the tantalum nitride layer, and oxidation of the copper-based metal layer or a decrease in adhesion is not caused, and the flexible circuit is excellent in reliability. Substrate. * In the third aspect of the invention, a tantalum nitride layer or a hafnium oxynitride layer formed by a sputtering method is formed on the surface of the resin film, and a thickness selected from sand, aluminum, and nickel is formed. A metal film of 5 to 5 nm is further formed with a copper-based metal layer. Thus, by forming a tantalum nitride layer or a oxynitridation layer and a metal film having a thickness of 〇·5 to 5 nm selected from ruthenium, aluminum, and nickel as the intermediate layer -8-200836609, the copper-based metal layer can be formed. The adhesion is good. Further, since the tantalum nitride layer or the hafnium oxynitride layer is an insulator, etching is not required, and only a thin metal film such as tantalum or a copper metal layer is etched. Side etching is produced, and fine touch can be performed. Further, even if the water or oxygen from the resin film side penetrates at a high temperature, the tantalum nitride layer or the oxygen is blocked by the tantalum nitride layer, and the oxidation of the copper-based metal layer or the decrease in the adhesion force does not occur. A flexible circuit board with excellent reliability. In the method for producing a flexible circuit board according to the first aspect of the invention, the tantalum nitride sputtering process is performed by applying a high-frequency bias voltage to an electrode roller that transports a resin film in a region facing the target surface. In the case where the electrode roller on the resin film side is shifted toward the upper negative potential side by the high-frequency bias voltage, not only the amount of nitrogen in the nitriding sand but also the nitriding can be sufficiently increased. The close connection of the enamel layer. In the second method of manufacturing the flexible circuit board of the present invention, the yttrium oxynitride sputtering process is performed by applying a high-frequency bias voltage to the electrode roller that transports the resin film β in a region facing the target. In this case, since the electrode roller on the side of the resin film is transferred to the peripheral side and the upper side to the negative potential side by the high-frequency bias voltage, not only the amount of nitrogen in the tantalum nitride but also the nitriding can be sufficiently increased. The close connection of the enamel layer. In the third method of manufacturing the flexible circuit board of the present invention, the second sputtering process is performed by applying a high-frequency bias voltage to the electrode roller that transports the resin film in the region facing the target. By the partial frequency bias voltage, the electrode roller on the resin film side is shifted toward the upper negative potential side when viewed from the periphery, so that the adhesion force of the metal film is also increased in width. Winter 200836609 [Embodiment] Next, a preferred embodiment for carrying out the invention will be described. Fig. 1 is a cross-sectional view showing a flexible circuit board - according to a first embodiment of the present invention. . The flexible circuit substrate 6 is formed on the surface of the resin film 1 to form a confrontation of 0. 5~1. The nitrogen nitride of 33 is formed by a nitrided Φ layer 2a formed by a sputtering method, and a copper-based metal layer 3 is further formed. In this example, the copper-based metal layer 3 is composed of a copper sputter film 4 formed by a sputtering method and a copper plating layer 5 formed by a plating method. As the resin film 1, for example, a polyimide film, a polyethylene terephthalate film, a polycarbonate film, a liquid crystal polymer film, or the like has excellent heat resistance, mechanical stability, and mechanical strength. It is ideal for electrical characteristics and electrical properties. In the above-mentioned surface of the resin film 1, by reactive sputtering, the shape of the pair is in the equivalent of 0. 5~1. A nitrogen nitride layer 2a of 33 nitrogen is used as the intermediate layer. When the amount of nitrogen to rhodium is less than or equal to 5, there is a problem at the point of reliability at a high temperature, and conversely, the equivalent exceeds 1. At 3 3, the adhesion will be weakened. The thickness of the tantalum nitride layer 2a is preferably about 5 to 15 nm. When it is less than 5 nm, it is impossible to sufficiently prevent the permeation of water from the resin film 1 side at the barrel temperature, which causes a problem in reliability. Conversely, when it exceeds 15 nm, it may be generated in the film. Cracks or peeling of the film caused by skewing will weaken the adhesion. In particular, it is desirable that the copper-based metal layer 3 is excellent in adhesion and reliability in the range of 8 to 12 nm to -10-200836609. In this example, the copper-based metal layer 3 is composed of a copper sputter film 4 formed on the tantalum nitride layer 2a and a copper plating layer 5 formed on the copper sputter film 4. As the copper sputter film 4 and the copper plating layer 5, a copper-based metal constituting the "copper-based metal layer 3" may be copper or a copper alloy. . The copper sputter film 4 is preferably formed to have a thickness of about 50 to 1 〇〇 ηηι. This is because when the thickness is less than 50 nm, it is not only easy to cause discoloration of the plating layer called "scorch" but also the adjustment of the condition setting of the copper plating when performing the next process of copper plating. Difficulties, and depending on the situation, will reduce the adhesion. Conversely, when it exceeds 100 nm, the sputtering time becomes long and the production speed is remarkably lowered. The thickness of the copper plating layer 5 can be suitably determined by electrical conductivity or line width of the pattern, but is set to about 2 μm to about 15 μm. This is because when the temperature is less than 2 μm, there is a problem in electrical conductivity. Conversely, when it exceeds 15 μm, there is a case where it is difficult to form a fine pattern. Fig. 2 is a cross-sectional view showing a flexible circuit board _ according to a second embodiment of the present invention. - The flexible circuit board 6 is formed on the surface of the resin film 1, and has a confrontation of 0. 3~1. The nitrogen oxynitride layer 2b formed by the sputtering method is further formed with the copper-based metal layer 3. In this example, the copper-based metal layer 3 is composed of a copper-sputtered film 4 formed by a sputtering method and a copper-plated layer 5 formed by a plating method. On the surface of the resin film 1, a yttrium oxynitride layer 2b containing a nitrogen of 〇 · 3 to 1 · 1 in an equivalent amount is formed as a middle layer by a reactive sputtering method, -11 - 200836609. When the amount of nitrogen to rhodium is less than 0 in the equivalent. At 3 o'clock, there is a problem at the point of reliability at high temperatures, and conversely, when the equivalent exceeds 1 . At 1 o'clock, the adhesion will be weakened. . The thickness of the yttrium oxynitride layer 2b is preferably about 5 to 20 nm. ^ When the temperature is less than 5 nm, the moisture from the resin film 1 side cannot be sufficiently prevented from permeating at the high temperature, which causes a problem in reliability. Conversely, when φ exceeds 20 nm, cracks or skews occur in the film. The film is peeled off, so that the adhesion is weakened. In particular, it is desirable that it is 8 to 15 nm, and the adhesion and reliability of the copper-based metal layer 3 are excellent. The copper-based metal layer 3 is composed of a copper-sputtered film 4 formed on the above-described yttria layer 2b and a copper-plated layer 5 formed on the copper-sputtered film 4 in this example. The copper sputter film 4 and the copper plating layer 5 are copper-based metals constituting the copper-based metal layer 3, and copper or a copper alloy can be used. Other than the above, the flexible circuit φ substrate of the above-described first embodiment is denoted by the same reference numerals. 3 and 4 are views showing a device for manufacturing the above-described flexible circuit board 6. Fig. 3 is a view showing a sputtering ring device for forming the above-described tantalum nitride layer 2a, a hafnium oxynitride layer 2b and a copper sputtering film 4, and Fig. 4 shows a plating apparatus for forming the above-mentioned copper plating layer 5. The sputtering ring device shown in FIG. 3 is provided with a plasma chamber 10 that performs plasma treatment as a pretreatment, a first sputtering chamber n that performs a first sputtering process, and a second sputtering process. 2 sputtering chamber 12. The plasma chamber 1〇, the first sputtering chamber 1 1 and the second sputtering chamber 12 are respectively connected to a vacuum pump not shown in -12-200836609, and the pressure can be independently adjusted. In the plasma chamber 1 〇, a supply roller 13 for supplying a resin film wound in a roller shape is provided; and winding is formed in each of the first sputtering chamber 1 1 and the second sputtering chamber 2 The winding roller 14 of the tantalum nitride layer 2a and the thin film la of the seed crystal* of the copper sputter film 4. Further, in the plasma chamber 1A, a plasma processing apparatus 15 for performing plasma treatment as a pretreatment on the resin film 1 supplied from the supply roller 13 is provided. φ In the plasma processing apparatus 15 described above, a gas in which 5 to 60% by volume of oxygen or nitrogen or a mixed gas of these is added to the argon gas is introduced as a plasma processing gas. Further, by applying a direct current voltage, an alternating current voltage or a high frequency voltage to the electrodes, plasma is generated, and the resin film 1 is passed through the plasma environment to carry out plasma treatment. By the plasma treatment, a functional group is generated on the surface of the resin film 1, and the effect of improving the adhesion between the tantalum nitride layer 2a and the hafnium oxynitride layer 2b is exhibited. Argon gas can also be used alone as a gas for plasma treatment, but the effect can be further improved by mixing oxygen or nitrogen. In the plasma chamber 10, the resin film 1 subjected to the plasma treatment is supplied to the first sputtering chamber 11, and a film of tantalum nitride and yttrium oxynitride by reactive sputtering is formed. In the first sputtering chamber 11, a target target 18; and a first roller 16 for transporting the resin film 1 subjected to the plasma treatment in a region facing the target target 18 is provided. First, a method of forming the tantalum nitride layer 2a according to the first embodiment will be described. 〇 A voltage of a negative potential is applied to the target target 18 by the DC power source 21. Further, in the first roller 16, a high-frequency power supply voltage of -13 - 200836609 is applied by the high-frequency power source 20. Further, a mixed gas of argon and nitrogen as a reactive sputtering gas was introduced. The ratio of argon to nitrogen is desirably in the range of 95: 5 to 50: 5 Torr. When the amount of nitrogen is too small, the nitrogen in the film becomes too small to obtain close contact force or reliability. Conversely, when the amount of nitrogen is too large, the precipitation rate of the film becomes slow, and further, the amount of nitrogen increases more than the stoichiometric amount. Further, the above-described tantalum nitride sputtering process is applied to the first roller 16 which functions as a traveling roller called a can roll for cooling the film. The high frequency is biased toward the voltage side. By this, the energy used to promote the reaction is imparted to promote the chemical reaction. The above high frequency bias voltage, 0. 05~〇. The power of 2 W/cm 2 is an ideal range. When it is not full (K〇5W/cm2, it is impossible to obtain the adhesion, when it exceeds 〇. At 2 W/cm2, the polyimide film is deteriorated, which causes a problem in reliability. When the high-frequency bias voltage is not applied, the nitrogen component contained in the formed tantalum nitride layer 2a becomes relatively small, and the adhesion or reliability cannot be obtained. Thus, it is carried out: on the surface of the resin film 1, a pair of 矽 is formed in the equivalent of 〇·5~1. 33 nitrogen nitride tantalum layer 2a tantalum nitride sputtering process. The resin thin film of the tantalum nitride layer 2a is formed in the above-described tantalum nitride sputtering process. The film 1 is supplied to the second sputtering chamber 12 to perform a copper sputtering process. In the second sputtering chamber 12, a copper target 19 is provided, and a second roller 17 of the resin film 1 is transported in a region facing the copper target 19. A voltage of a negative potential is applied to the copper target 19 by a DC power source 21. Further, argon gas was used as a sputtering gas, and a copper sputtering process was performed to form a copper film 4 . Further, the air pressure in the plasma chamber 10, the first sputtering chamber 11, and the second sputtering chamber 12 may be substantially the same 'but the second sputtering chamber 12 is preferably the highest. This is because when the gas pressure in the second sputtering chamber 12 is lowered, nitrogen gas flows in from the first sputtering chamber 1 1 or the plasma chamber 1 to generate copper nitride, and the conductivity may be based on the case. Disappeared. . The film ia having the seed layer formed of the copper sputter film 4 is again sent to the plasma chamber 1 〇 to take up the roller 14 for winding. • Next, the tantalum nitride layer 2a and the thin film 1 a having the seed layer formed with the copper beach coating 4 are subjected to a copper plating process by a continuous copper plating apparatus to form a copper plating layer 5 °. The continuous copper plating apparatus shown in FIG. 4 is The plating tank 25, the water washing tank 26, and the drying tank 27 are provided, and the copper plating layer 5 is formed by the copper oxide bath or the like by the film la having the seed layer supplied from the roller 28, and the flammability of the present invention is formed. The circuit board 6' is taken up by the take-up roller 29. In the figure, the symbol 30 is a direct current power source, 31 is an anode, and 32 is a cathode roller. • In this example, the copper sputtering process and the copper plating process are formed into a copper-based metal of the present invention which forms a copper-based metal layer. • Next, a method of forming the second embodiment of the hafnium oxynitride layer 2b will be described. A voltage of a negative potential is applied to the target target 18 by the DC power source 21. Further, in the first roller 16, the high frequency power supply 20 applies a high frequency bias voltage. Further, a mixed gas of argon and oxygen and nitrogen as a reactive sputtering gas is introduced. The ratio of argon to oxygen-nitrogen mixed gas, 9 0 : 1 〇 to 60: 40 is the ideal range, the ratio of oxygen to nitrogen of the above-mentioned oxygen-nitrogen mixed gas is -15-200836609, 1 0 : 90 to 20: 1 0 is the ideal range. When the amount of nitrogen is too small, the nitrogen in the film becomes too small, and the adhesion or reliability cannot be obtained. Conversely, when the amount of nitrogen is too large, the precipitation rate of the film becomes slow, and nitrogen is more than the stoichiometric amount. Further, the yttrium oxynitride sputtering process applies a high frequency bias to the first roller 16 which functions as a traveling roller called a cylindrical roller for cooling the film. The voltage is carried out on one side. Thereby, the energy which promotes the reaction by φ is imparted, and the chemical reaction is promoted. The above high frequency bias voltage, 0. 05~0. The power of 3 W/cm 2 is an ideal range. When not full. When 〇5W/cm2, the adhesion cannot be obtained when it exceeds 0. At 3 W/cm2, the polyimide film was deteriorated, which caused a problem in reliability. When the high-frequency bias voltage is not applied, the nitrogen component contained in the formed yttrium oxynitride layer 2b becomes relatively small, and the adhesion or reliability cannot be obtained. Thus, on the surface of the resin film 1, a yttrium oxynitride sputtering method for forming a yttrium oxynitride layer 2b having an equivalent of 0·5 to 1.33 is formed. The resin film 1 in which the hafnium oxynitride layer 2b is formed in the above-described yttria sputtering process is supplied to the second sputtering chamber 12, and a copper sputtering process and a copper plating process are performed. The copper sputtering process and the copper plating process are the same as those of the first embodiment described above. As described above, in the first embodiment, the surface of the resin film 1 is formed to have a confrontation of 0. 5~1. The nitrogen nitride of 33 is further formed into a copper-based metal layer 3 by a tantalum nitride layer 2a formed by a sputtering method. Thus, by forming nitrogen in the equivalent containing 0 · 5~1. The 3 3 tantalum nitride layer 2 a serves as the intermediate layer -16-200836609, so that the adhesion of the copper-based metal layer 3 becomes good. Further, since the yttrium nitride layer 2a is an insulator, it is not necessary to perform etching, and only the copper-based metal layer is etched. Therefore, side etching is less likely to occur, and fine etching can be performed. Further, even if moisture or oxygen permeation from the resin film 1 side permeates at a high temperature, it is blocked by the nitride sand layer a, and a copper-based metal layer is not generated. The oxidation or adhesion of 3 is lowered, and the flexible circuit board 6 is excellent in reliability. φ Further, since the tantalum nitride sputtering process is performed by applying the high-frequency bias voltage to the first roller 16 that transports the resin film 1 in the region opposite to the target target 18, the high-frequency bias voltage is applied. When the first roller 16 on the resin film 1 side is shifted toward the upper negative potential side when viewed from the periphery, not only the amount of nitrogen in the tantalum nitride but also the adhesion force of the tantalum nitride layer 2a is greatly increased. As described above, in the second embodiment, the surface of the resin film 1 is formed to have a confrontation of 0. 5~1. The copper oxynitride layer 2b is formed by the sputtering method #3, and the copper-based metal layer 3 is further formed. Thus, by forming nitrogen, the equivalent contains 0. 5~1. The yttrium oxynitride layer 2b of 33 is used as the intermediate layer to make the adhesion of the copper-based metal layer 3 good. Further, since the yttrium oxynitride layer 2b is an insulator, it is not necessary to perform the etching, and only the copper-based metal layer is etched. Therefore, side etching is less likely to occur, and fine etching can be performed. In addition, even if moisture or oxygen permeation from the side of the resin film 1 is blocked at a high temperature, the yttrium oxynitride layer 2b is blocked, and oxidation of the copper-based metal layer 3 or a decrease in adhesion is not caused, and reliability is excellent. Flexible circuit board 6. -17- 200836609 In addition, the yttrium oxynitride sputtering process is performed by applying a high-frequency bias voltage to the first roller 16 of the resin film 1 in the region opposite to the target target 18; By the high-frequency bias voltage, the first roller 16 on the resin film 1 side is transferred to the upper negative potential side when viewed from the periphery, and oxygen can sufficiently ensure not only the amount of nitrogen in the tantalum nitride but also the hafnium oxynitride layer 2b. The adhesion has also increased significantly. Fig. 5 is a view for explaining a third embodiment of the present invention. In the sputtering apparatus, a high-frequency bias voltage is applied to the second roller 17 of the second sputtering chamber 12 by the high-frequency power source 22, and the copper sputtering process is performed as follows, that is, the copper target 1 is used. In the field of the opposite surface, the second roller 17 of the resin film 1 is conveyed while applying a high-frequency bias voltage. The power of the high-frequency bias voltage is 理想· 05 W/cm2 or more, which is an ideal range. If it is less than this, the effect of improving the adhesion can not be obtained. Other than the above, the same reference numerals are given to the same portions as in the first and second embodiments. Thereby, the adhesion of the copper sputter film 4 is further improved. In addition to the above, the same effects as those of the first and second embodiments described above can be achieved. Fig. 6 is a view for explaining a fourth embodiment of the present invention. In the sputtering apparatus, a common roller 23 is provided between the first sputtering chamber 11 and the second sputtering chamber 12, and the high-frequency power source 22 applies a high-frequency bias voltage to the common roller 23. Further, the tantalum nitride plating process, the yttrium oxynitride sputtering process, and the copper sputtering process are performed by the common roller 23, and both are applied while applying the tube frequency bias voltage. Other than the first and second embodiments, the same portions are denoted by the same reference numerals. Thereby, the adhesion of the copper sputter film 4 of -18 - 200836609 is further improved. In addition to the above, the same operational effects as those of the first to third embodiments described above can be achieved. Fig. 7 is a view for explaining a fifth embodiment of the present invention. This sputtering apparatus is provided instead of the vapor deposition chamber 37 for performing vacuum evaporation, and the second sputtering chamber 12. The copper wire 34 to be vapor-deposited is supplied to the vapor deposition chamber 37. The copper supply portion 33; the crucible 35 that melts the supplied copper wire 34; and the heater 36 for heating the crucible 35 form a copper vapor deposition film instead of the copper φ sputtering film 4. Other than the first to fourth embodiments, the same portions are denoted by the same reference numerals. Also in this example, the same operational effects as those of the first to fourth embodiments described above can be achieved. Fig. 8 is a view showing a sixth embodiment of the present invention. In the flexible circuit board, the copper film 3a is formed as a copper-based metal layer by ion coating or vacuum deposition, and the copper plating is omitted. It is effective when the thickness of the copper film 3a is Ιμηη or less. Fig. 9 is a cross-sectional view showing a flexible circuit board # according to a seventh embodiment of the present invention. The flexible circuit board 6 is formed on the surface of the resin film 1 by a tantalum nitride layer 2a or a hafnium oxynitride layer 2b formed by sputtering, and further has a thickness selected from tantalum, aluminum, and nickel. The metal film 7 of 5 to 5 nm is further formed with the copper-based metal layer 3. In this example, the copper-based metal layer 3 is composed of a copper-sputtered film 4 formed by a sputtering method and a copper-plated layer 5 formed by a plating method. As the above-mentioned resin film, for example, a polyimide film, a polyethylene terephthalate film, a polycarbonate film, a liquid crystal polymer film, etc. -19 - 200836609, heat resistance, mechanical stability, mechanical These points, which are excellent in strength and electrical properties, are excellent and can be preferably used. On the surface of the resin film 1, the tantalum nitride layer 2a or the hafnium oxynitride layer 2b is formed as an intermediate layer by a reactive sputtering method. . As the above-mentioned tantalum nitride layer 2a, it is preferable to form a pair of tantalum in an equivalent amount of 参·5~1. 33 nitrogen nitride layer 2a. When the amount of nitrogen to rhodium is less than 0 in the equivalent. At 5 o'clock, there is a problem at the point of reliability at high temperatures, and the phase φ is inversely greater than 1 in the equivalent. At 3 o'clock, the adhesion will be weakened. The thickness of the tantalum nitride layer 2a is preferably about 5 to 15 nm. When the temperature is less than 5 nm, the moisture permeation from the resin film 1 side cannot be sufficiently prevented from being transmitted at a high temperature, which causes a problem in reliability. Conversely, when it exceeds 15 nm, cracks or skews occur in the film. The film is peeled off, so that the adhesion is weakened. In particular, it is desirable that it is 8 to 12 nm, and the adhesion and reliability of the copper-based metal layer 3 can be made excellent. As the oxynitriding sand layer 2b, the paired sand has an equivalent weight of 0. 3~1. 1 • Nitrogen oxynitride layer 2b is preferred. When the amount of nitrogen to rhodium is less than 0 in the equivalent. At 3 o'clock, there is a problem in the reliability at a high temperature. Conversely, when the equivalent exceeds 1:1, the adhesion is weakened. The thickness of the above oxynitride layer 2b is preferably about 5 to 20 nm. When the thickness is less than 5 nm, moisture permeation from the resin film 1 side cannot be sufficiently prevented from being transmitted at a high temperature, which causes a problem in reliability. Conversely, when it exceeds 20 nm, the film is caused by cracks or skew due to skew Peeling, it will weaken the adhesion. In particular, it is desirably 8 to 15 nm, which makes the copper-based metal layer 3 excellent in adhesion and reliability. -20- 200836609 Next, a metal film 7 selected from bismuth, aluminum, and nickel is formed. Its thickness is ideally 0. 5 n m to 5 n m, more preferably 1 n m to 3 n m. When the thickness of the metal film 7 is not full. In the case of 5 nm and more than 5 nm, the effect of improving the adhesion of the copper-based metal layer 3 is small. The film formation method may be a vapor deposition method or the like, but it is desirable from the viewpoint of the relationship between the front and rear vacuum degrees and the adhesion. For sputtering. The copper-based metal layer 3 is, in this example, a copper-sputtered film 4 formed on the above-described nitrogen-based layer 2a or yttrium-oxynitride layer 2b, and a copper-plated layer 5 formed on the copper-sputtered film 4. Composition. The copper sputter film 4 and the copper plating layer 5 are copper-based metals constituting the copper-based metal layer 3, and copper or a copper alloy can be used. The copper sputter film 4 is preferably formed to have a thickness of about 50 to 10 Å. This is because when the thickness is less than 5 Onm, the copper plating of the next process is likely to cause discoloration of the plating layer called "scorch", which makes it difficult to set the condition of the copper plating. Adjust, and depending on the situation, will # reduce the adhesion. On the contrary, when it exceeds 100 nm, the sputtering time becomes long and the production speed is remarkably lowered. The thickness of the copper plating layer 5 can be appropriately determined by electrical conductivity or line width f* t of the pattern, but is set in 〇. 2μιη~15μπι or so. This is because when the temperature is less than 2 μm, the electrical conductivity is problematic. On the contrary, when it exceeds 15 μm, it is difficult to form a fine pattern. 10 and 4 are views showing a device for manufacturing the above-described flexible circuit board 6. 2 shows a sputtering ring device for forming the above-described tantalum nitride layer 2a, yttrium oxynitride-21 - 200836609 layer 2b, metal film 7 and copper sputtering film 4, and FIG. 3 is a view for forming the above copper plating layer 5 Plating device. The sputter ring device shown in Fig. 10 is provided with a plasma chamber 10 for performing plasma treatment as a pretreatment, a first sputtering chamber 4 for performing a first sputtering process, and a second sputtering process for performing a second sputtering process. Sputter chamber 12. The plasma chamber ▲, 第, the first sputtering chamber 11, and the second sputtering chamber 12 are respectively connected to a vacuum pump (not shown), and the pressure can be independently adjusted. In the plasma chamber 10, a supply roller 13 for supplying a resin film 1 wound in a roller shape is provided, and a nitrogen is formed in the first sputtering chamber 1 1 and the second sputtering chamber 12, respectively. The winding roller 14 of the film la of the seed layer 1a, the yttrium oxynitride layer 2b, the metal film 7, and the copper sputter film 4. Further, in the plasma chamber 10, a plasma processing apparatus 15 for performing plasma treatment as a pretreatment on the resin film 1 supplied from the supply roller 13 is provided. In the plasma processing apparatus 15 described above, a gas in which 5 to 60% by volume of oxygen or nitrogen or a mixed gas of these is added to the argon gas is introduced as a gas for plasma treatment. Further, by applying a direct current voltage, an alternating current voltage or a high frequency voltage to the electrodes, a plasma is generated, and the resin film 1 is passed through the plasma environment to carry out an electric beta slurry treatment. By the plasma treatment, a functional group is generated on the surface of the resin film 1, and the effect of improving the adhesion between the tantalum nitride layer 2a and the hafnium oxynitride layer 2b is exhibited. Argon gas can also be used alone as a gas for plasma treatment, but the effect can be further improved by mixing oxygen or nitrogen. In the plasma chamber 1, the resin film 1 subjected to the plasma treatment is supplied to the first sputtering chamber, and a film of tantalum nitride or yttrium oxynitride by reactive sputtering is formed. In the first sputtering chamber 11, a first target 16 for transporting the plasma-treated resin film 1 is provided in the first sputtering unit 11; -22-200836609 and in a region facing the target target 18; . First, a method of forming the first example of the tantalum nitride layer 2a will be described. In the above sand mark IE 1 8, a negative potential is applied by a DC power source 2 1 . Further, in the first roller 16, the high frequency power supply 20 applies a high frequency bias voltage. Further, a mixed gas of argon and nitrogen as a reactive sputtering gas was introduced. The ratio of argon to nitrogen is desirably in the range of 95:5 to 50: • 50. When the amount of nitrogen is too small, the nitrogen in the film becomes too small to obtain close contact force or reliability. On the contrary, when the amount of nitrogen is too large, the precipitation rate of the film becomes slow, and the amount of nitrogen increases more than the stoichiometric amount. Further, the above-described tantalum nitride sputtering process is performed by applying a high-frequency bias voltage to the first roller 16 which functions as a traveling roller called a cylindrical roller for cooling the film. . Thereby, the energy for promoting the reaction is imparted, and the chemical reaction is promoted. The above high frequency bias voltage, 〇. 05 ~ 0. The power of 2 W/cm 2 is an ideal range. When less than 0. At 05 W/cm2, Φ cannot obtain the adhesion, and when it exceeds 0_2 W/cm2, the polyimide film is deteriorated, which causes a problem in reliability. When the high-frequency bias voltage is not applied, the nitrogen component contained in the formed tantalum nitride layer 2a becomes relatively small, and the adhesion or reliability cannot be obtained.觚 So carried out: on the surface of the resin film 1, the formation of the opposite 含有 in the equivalent contains 0. 5~1. A zirconium nitride sputtering process of a nitrogen nitride layer 2a of 33 nitrogen. The resin film 1 in which the tantalum nitride layer 2a is formed in the above-described tantalum nitride sputtering process is supplied to the second sputtering chamber 12, and is formed to have a thickness selected from ruthenium, aluminum, and nickel. 5 to 5 nm metal film 7 metal sputtering process, and -23- 200836609 copper sputtering process. In the above-described second sputtering chamber 12, a metal target 24 and a copper target 19 composed of a metal selected from sand, indium, and nickel are provided; and the metal target 24 and the copper target 19 are In the field of the opposite surface, the second roller 17 of the resin film 1 is transported. • A voltage of a negative potential is applied to the metal tag 24 by the DC power source 21a. Further, argon gas was used as a sputtering gas, and a metal sputtering process was performed to form a metal film 7. At this time, it is preferable that the second roller 17 functioning as a traveling roller for cooling the film is applied by applying the local frequency bias voltage to the high-frequency power source 22'. . Thereby, the energy for promoting the reaction is imparted, and the chemical reaction is promoted. The above high frequency bias voltage, 0·03~0. The power of 2 W/cm 2 is an ideal range. When not full. When 〇3W/cm2, the adhesion becomes slightly weaker, and when it exceeds 0. At 2 W/cm2, the polyimide film is deteriorated, which causes a problem in reliability. # On the above copper target 1, a negative potential voltage is applied by the DC power source 2 1 . Further, using a argon gas as a sputtering gas, a copper sputtering process is performed to form a copper sputter film 4. In addition, the copper sputtering process may be performed by applying the high-frequency bias voltage to the second roller 17 of the resin film 1 in the region facing the copper m target 19 by the high-frequency power source 22. At this time, the electric power of the high-frequency bias voltage is not more than 0·03 W/cm2, and if it is below this, the effect of improving the adhesion cannot be obtained. Thereby, the adhesion of the copper sputter film 4 is further improved. Further, the air pressure in the plasma chamber 10, the first sputtering chamber 11, and the second sputtering chamber 12 may be substantially the same, but the second sputtering chamber 12 is preferably the highest. This is because when the gas pressure of the second sputtering chamber 12 is lowered, nitrogen gas flows in from the first sputtering chamber 11 or the plasma chamber 1 to generate copper nitride, and the conductivity disappears depending on the case. . . The film 1a having the seed layer formed of the copper sputter film 4 is again sent to the plasma chamber 1 to be wound up by winding the roller 14. φ Next, the tantalum nitride layer 2a or the hafnium oxynitride layer 2b, the metal film 7, and the thin film ia having the seed layer formed of the copper sputter film 4 are subjected to a copper plating process by a continuous copper plating apparatus to form a copper plating layer 5 . The continuous copper plating apparatus shown in Fig. 4 includes a plating tank 25, a water washing tank 26, and a drying tank 27, and forms a deposit with a copper sulfate bath or the like in a film la' having a seed layer supplied from a supply roller 28. After the copper layer 5, the flexible circuit board 6 of the present invention is formed and wound up by winding the roller 29. In the figure, the weight 30 is a DC power source, 31 is an anode, and 32 is a cathode roller. ® In this example, the copper sputtering process and the copper plating process are formed into a copper-based metal of the present invention which forms a copper-based metal layer. Next, a method of forming the second example of the oxynitride sand layer 2b will be described. A voltage of a negative potential is applied to the target target 18 by the DC power source 21. Further, in the first roller 16, the high frequency power supply 20 applies a high frequency bias voltage. Further, a mixed gas of argon and oxygen and nitrogen as a reactive sputtering gas is introduced. The ratio of the mixed gas of argon and oxygen to nitrogen is preferably in the range of from 90 to 1 : 60 to 40, and the ratio of oxygen to nitrogen of the above oxygen-nitrogen mixed gas is preferably in the range of 10:90 to 40:60. When the amount of nitrogen is too small, the weaving in the film becomes too small to obtain the adhesion or reliability. Conversely, when the amount of nitrogen is too large, the precipitation rate of the film becomes slow, and nitrogen is more than the stoichiometric amount. Further, the above-described yttrium oxynitride sputtering process applies a high-frequency bias voltage to the first roller 16' which functions as a traveling roller called a cylindrical roller for cooling the thin film. Do it on one side. Thereby, the energy used to promote the reaction is imparted, and the chemical reaction is promoted. The above-mentioned high-frequency bias voltage, the power of φ 0·05 〇·3 W/em2 is an ideal range. When not full. When 〇5W/cm2, the adhesion cannot be obtained when it exceeds 0. At 3 W/cm2, the polyimide film was deteriorated, which caused a problem in reliability. When the high-frequency bias voltage is not applied, the nitrogen component contained in the formed yttrium oxynitride layer 2b becomes relatively small, and the adhesion or reliability cannot be obtained. Thus, it is carried out: on the surface of the resin film 1, the pair is formed to have an equivalent of 0. 5 to 1.33 of the yttrium oxynitride layer 2b of the yttrium oxynitride sputtering process. Φ The resin film 1 in which the yttrium oxynitride layer 2b is formed in the above-described yttria sputtering process is supplied to the second sputtering chamber 12, and a metal film sputtering process, a copper sputtering process, and a copper plating process are performed. The metal film sputtering process, the copper sputtering process*, and the copper plating process are the same as those of the first example described above. As described above, in the present embodiment, the tantalum nitride layer 2a or the hafnium oxynitride layer 2b formed by the sputtering method is formed on the surface of the resin film 1, and the thickness selected from tantalum, aluminum, and nickel is further formed. The metal film 7 of 〜5 nm further forms the copper-based metal layer 3. Thus, the copper-based metal layer is formed by forming the tantalum nitride layer 2a or the hafnium oxynitride layer 2b and the metal film 7 having a thickness of 0·5 -26-200836609 to 5 nm selected from tantalum, aluminum, and nickel as the intermediate layer. The adhesion of 3 becomes good. Further, since the tantalum nitride layer 2 a or the hafnium oxynitride layer 2 b is an insulator, etching is not required, and only the metal film 7 such as an extremely thin tantalum or the copper-based metal layer 3 may be etched. Therefore, it is less likely to produce a side • engraving, but a fine uranium engraving. And, even at high temperatures, it comes from trees. The moisture or oxygen permeates on the side of the fat film 1, and the tantalum nitride layer 2a is also blocked by the yttrium oxynitride layer 2b, so that the oxidation or the adhesion of the copper-based metal layer 3 does not occur, and the reliability is excellent. Flexible circuit board. Further, in the second sputtering process of the present invention, the metal sputtering process is performed while the high-frequency bias voltage is applied to the second roller 17 of the resin film 1 in the region facing the metal target 24. By the high-frequency bias voltage, the second roller 17 on the side of the resin film 1 is shifted toward the upper negative potential side when viewed from the periphery, so that the adhesion of the metal film 7 is also greatly increased. As the sputtering apparatus, a common roller may be provided between the first sputtering chamber 11 and the second sputtering chamber 1 2, and a high-frequency bias voltage may be applied to the common roller by the high-frequency power source. Also, a tantalum nitride or yttria sputtering process. The metal beach plating process and the copper sputtering process can also be carried out by using a common roller, both while applying a high-frequency bias voltage. Fig. 11 is a view showing an eighth embodiment of the present invention. In the flexible circuit board 6, the copper film 3a is formed by ion coating or vacuum deposition, and the copper-based metal layer 3 is omitted, and the copper plating is omitted. It is effective when the thickness of the copper film 3a is 1 μm or less. Hereinafter, the embodiments will be described. -27-200836609 [Example 1] A film having conductivity was produced by using the film forming apparatus shown in Fig. 3 . A polyimide film using a thickness of 25 μm and a width of 25 cm • Polyamide film NPI made by Kaneka. The conveying speed of the film is set to 〇. 8m / min. The plasma is treated in the chamber, and a mixture of 30% nitrogen is added to the argon to adjust the gas flow rate so that the gas pressure in the plasma processing chamber becomes zero. 5Pa, φ Apply an AC voltage of 3 80V to generate plasma, so that the film passes through the plasma environment. In the next reactive sputtering chamber, under the condition of 70% argon and 30% nitrogen mixed gas, it becomes 〇. The flow rate is adjusted by 4Pa, the DC voltage is 410V, and the first roller 16 with a width of 26cm and a diameter of 20cm will be 13. A high frequency of 56 MHz is applied to 160W. The resulting film had a thickness of 10 nm and was composed of SiNl. 2. Secondly, copper sputtering, using a width of 26cm, a diameter of 40cm, the second roller Φ 17, at argon pressure 0. Film formation was carried out under the conditions of 6 Pa and a DC voltage of 400 V. Next, the flexible circuit board of the present invention was produced by plating in a copper plating apparatus shown in Fig. 4 so that the thickness of copper was 10 μm. m < [Evaluation method] The engraving was carried out so that the copper plating film remained in the width of 3 mm, and the tensile test in the vertical direction was carried out in the manner defined in JIS C 5 0 16 to measure the adhesion. Further, the reliability was such that the sample etched at a width of 3 mm was placed at 180 ° C for one day, and the adhesion was measured in the same manner. -28 - 200836609 [Embodiment 2] In Example 2, the nitrogen concentration, the DC voltage, and the high-frequency power of the tantalum nitride sputtering process were changed, and the film composition and film thickness were replaced, and film formation was carried out under the same conditions. Comparative Example 1 As Comparative Example 1, the nitrogen gas concentration, the direct current voltage, and the high frequency electric power of the tantalum nitride film forming chamber were changed to form a tantalum nitride film having a composition of SiN0.3. The conditions for the formation of tantalum nitride of Example 1, Example 2 and Comparative Example 1 and the evaluation results are shown in Table 1 below. Table 1 Sample gas pressure gas composition DC voltage high-frequency power film composition Film thickness adhesion (N/mm) No (Pa) (Ar: N2) (V) (W/cm2) (nm) Initial 180 ° 〇 1 day Example 1 0.5 7:3 410 0.098 SiNl.2 10 0.8 0.9 Example 2-1 0.5 7:3 410 0.051 SiN0.7 10 0.6 0.7 Example 2-2 0.5 7:3 410 0.196 SiNL2 10 0.8 0.8 Example 2-3 0.5 9:1 400 0.051 SiN0.5 10 0.5 0.5 Example 2-4 0.5 5:5 420 0.15 SiNl.3 10 0.6 0.7 Example 2-5 0.5 8:2 390 0.098 SiN1.2 5 0.7 0.5 Example 2 6 0.7 7:3 425 0.098 SiN1.2 15 0.5 0.7 Comparative Example 1 0.5 9:1 400 0.01 SiNO.3 10 0.3 0.2

〔實施例3〕使用圖5所示的裝置，在實施例1的條件，除了對銅 -29· 200836609 濺鍍用圓筒滾子施加高頻電力以外，其餘以相同的條件進行成膜。實施例3之銅濺鍍時的高頻偏向條件與評價結果，顯示於下述的表2。表2 試料No 筒頻電力 (W/cm2) 密接力< [N/mm) 初期 180°C-1 日實施例3-1 0.05 0.9 0.8 . 實施例3-2 0.1 1 . 1 0.9 實施例3·3 0.2 1 .1 0.6[Example 3] Using the apparatus shown in Fig. 5, the film was formed under the same conditions except that high-frequency power was applied to the copper -29·200836609 sputtering cylindrical roller under the conditions of the first embodiment. The high frequency bias conditions and evaluation results at the time of copper sputtering in Example 3 are shown in Table 2 below. Table 2 Sample No. Tube frequency power (W/cm2) Adhesion <L/mm) Initial 180 °C-1 Day Example 3-1 0.05 0.9 0.8 . Example 3-2 0.1 1 . 1 0.9 Example 3 ·3 0.2 1 .1 0.6

〔評價結果〕在規格上，初期値成爲0.5N/mm以上，針對高溫保存後，無特別規定，但一般爲0.4N/mm以上即可。由評價結果’可得知在各實施例，初期的密接力、高溫保存後 φ 均獲得良好的結果。相對於此，比較例初期密接力、高溫保存後均顯現低的値。 ^ 〔實施例4〕 * 使用圖3所示的成膜裝置，製作具有導電性的薄膜。聚醯亞胺薄膜，使用厚度25 μιη、寬度25cm之Kaneka製聚醯亞胺薄膜NPI。薄膜的搬送速度設爲lm/分。電漿處理室氣體，對氬添加10%之氧與20%的氮之混合氣體，調節氣體流量，使電漿處理室內的氣壓成爲0.5Pa，施加交流電壓38 0V，產生電漿，使薄膜通過電漿環境中。 -30- 200836609 在下一個反應性濺鍍室，在氬70%、氧10%、氮20% 之混合氣體的條件下，成爲0.4Pa的方式調整流量，在直流電壓440V，對寬度26cm、直徑20cm的第1滾子16，將13.5 6MHz的高頻施加245W。所產生的膜的厚度爲 « 12nm，組成爲 SiONO.7。一其次，銅濺鍍是使用寬度26cm、直徑40cm第2滾子 17，在氬氣壓0.6Pa、直流電壓400V的條件進行成膜。 Φ 其次’以圖4所示的銅鍍裝裝置，進行鍍裝使銅的厚度成爲ΙΟμπι，製作出本發明的可撓性電路基板。〔評價法〕在3mm寬度以銅鍍裝膜殘留的方式進行蝕刻，如JIS C 5016所制定的方式，進行垂直方向之拉引試驗，測定密接力。又，可靠性爲將在3mm寬度進行了蝕刻之樣品在1 80t中放置1日，同樣地測定密接力。〔實施例5〕針對實施例1，除了改變氧氮化矽濺鍍製程的氮氣濃度、直流電壓、高頻電力，替換膜組成、膜厚以外，其餘以相同的條件，進行成膜。〔比較例2〕作爲比較例2，改變氧氮化矽成膜室的氮氣濃度、直流電壓、高頻電力，製作組成爲SiN0.3的氧氮化矽膜者 -31 - 200836609 實施例4、實施例5及比較例2之氧氮化矽作成條件與評價結果，顯示於下述的表3。表3 試料No 氣壓 (Pa) 氣體組成 (Ar:N2) 直流電壓 (V) 高頻電力 (W/cm2) 膜組成膜厚 (nm) 密接力(N/mm) 初期 180〇C-1 日實施例4 0.5 7:1:2 440 0.15 SiONO.7 12 0.6 0.7 實施例5-1 0.5 7:1:2 425 0.15 SiONO.7 6 0.8 0.7 實施例5-2 0.6 6:1:3 465 0.18 SiONO.7 28 0.5 0.8 實施例5·3 0.5 7:2:1 450 0.1 SiO1.5N0.3 15 0.5 0.6 實施例5-4 0.6 6:0.5:3.5 440 0.2 SiO0.3Nl.l 12 0.7 0.8 比較例2-1 0.5 7:2:1 450 0.03 SiO1.8N0.1 15 0.1 0.3 比較例2-2 0.6 6:0.3:3.7 440 0.25 SiO0.2N1.2 12 0.2 0.4 〔實施例6〕使用圖5所示的裝置，在實施例4的條件，除了對銅濺鍍用圓筒滾子施加高頻電力以外，其餘以相同的條件，進行成膜。實施例6之銅濺鍍時的高頻偏向條件與評價結果，顯示於下述的表4。表4 試料No 局頻電力 (W/cm2) 密接力< (N/mm) 初期 180〇C-1 日實施例6-1 0.05 0.9 0.8 實施例6-2 0.1 1.1 0.9 實施例6-3 0.2 1.2 0.7 -32- 200836609 寬度26em、直徑40cm第2滾子17，在氬氣壓〇.6Pa、直流電壓400V的條件進行成膜。其次，以圖3所示的銅鍍裝裝置，進行鍍裝使銅的厚度成爲ΙΟμιη，製作了本發明的可撓性電路基板6。 . 〔實施例8〕 .針對實施例1，除了改變氧氮化矽濺鍍製程的氮氣濃 Φ 度、直流電壓、高頻電力，變更膜組成、膜厚以外，其餘以相同的條件下，進行成膜。〔實施例9〕針對實施例1，除了形成鋁膜及鎳膜來代替矽膜作爲金屬膜7，變更電壓使來成爲相同的膜厚以外，其餘以相同的條件下進行成膜。〔實施例1 〇〕針對實施例1，除了變更作爲金屬膜7之矽膜的膜厚以外，其餘以相同的條件下進行成膜。〔實施例11〕在實施例1的條件，進行銅濺鍍之際，對第2滾子 1 7施加高頻偏向電壓以外，其餘以相同的條件下進行成膜。 -34 - 200836609 〔實施例1 2〕使用圖10所示的成膜裝置，製作具有導電性。聚醯亞胺薄膜，使用厚度2 5 μπι、寬度25 cm之製聚醯亞胺薄膜NPI。薄膜的搬送速度設爲lm/分處理室氣體，對氬添加氧10%與氮20%之混合氣體氣體流量，使電漿處理室內的氣壓成爲〇· 5 Pa，施電壓38 0V，產生電漿，使薄膜通過電漿環境中。在下一個反應性濺鍍室，在氬70%、氧10%、之混合氣體的條件下，成爲〇.4Pa的方式調整流量流電壓410V，對寬度26cm、直徑20cm的第1滾將 13.56MHz的高頻施加245W。所產生的膜的 12nm，組成爲 SiONO.7。其次，產生作爲金屬膜7之矽膜的矽濺鍍是使 2 6cm、直徑40cm第2滾子17。矽濺鍍是在氬氣遷、直流電壓320V的條件進行了成膜。又，銅濺鍍氣壓0.6Pa、直流電壓400V的條件進行成膜。其圖3所示的銅鍍裝裝置，以銅的厚度成爲15 μπι的行鍍裝，製作出本發明的可撓性電路基板。〔實施例1 3〕針對實施例1 2，除了改變氧氮化矽濺鍍製程濃度、直流電壓、高頻電力，變更膜組成、膜厚以餘以相同的條件進行成膜。的薄膜 Kaneka 。電漿，調節加交流氮2 0 % ，在直子16，厚度爲用寬度 ! 0.6Pa 是在氬次，以方式進的氮氣外，其 -35- 200836609 〔實施例1 4〕針對實施例1 2，除了形成鋁膜及鎳膜來代替矽膜作爲金屬膜7，變更電壓使來成爲相同的膜厚以外，其餘以相同的條件進行成膜。 φ . 〔實施例1 5〕針對實施例6，除了變更作爲金屬膜7之矽膜的膜壓 • 以外，其餘以相同的條件進行成膜。〔實施例1 6〕在實施例1 2的條件，進行銅濺鍍之際’除了對第2 滾子1施加高頻偏向電壓以外，其餘與實施例12相同的條件下進行成膜。〔實驗例1〕 % 針對實施例7，變更氮化矽成膜室的氮氣濃度、直流電壓、高頻電力，替換膜組成、膜厚以外’其餘以相同的條件進行成膜。 •i 〔實驗例2〕針對實施例1 0，除了變更作爲金屬膜7之砂膜的膜厚以外，其餘以相同的條件進行成膜。〔評價法〕 -36 - 200836609 在3mm寬度以銅鍍裝膜殘留的方式進行蝕刻，如JIS C 5016所制定的方式，進行垂直方向之拉引試驗，測定密接力。又，可靠性爲將在3 mm寬度進行了鈾刻之樣品在1801中放置1日，同樣地測定密接力。實施例7〜1 0之氮化矽作成條件與評價結果，顯示於下述的表5。[Evaluation Result] In the specification, the initial enthalpy is 0.5 N/mm or more, and it is not particularly limited after the high temperature is stored, but it is generally 0.4 N/mm or more. From the evaluation results, it was found that in each of the examples, excellent results were obtained in the initial adhesion and φ after high-temperature storage. On the other hand, in the comparative examples, the initial adhesion and the high-temperature storage showed a low enthalpy. [Example 4] * A conductive film was produced using the film forming apparatus shown in Fig. 3 . A polyimide film of Neneimine film made of Kaneka having a thickness of 25 μm and a width of 25 cm was used. The transport speed of the film was set to lm/min. Plasma treatment chamber gas, a mixture of 10% oxygen and 20% nitrogen is added to argon to adjust the gas flow rate so that the gas pressure in the plasma processing chamber becomes 0.5 Pa, and an alternating voltage of 38 0 V is applied to generate a plasma to pass the film. In a plasma environment. -30- 200836609 In the next reactive sputtering chamber, the flow rate is adjusted to 0.4 Pa in a mixed gas of 70% argon, 10% oxygen, and 20% nitrogen. The DC voltage is 440V, the width is 26cm, and the diameter is 20cm. The first roller 16 applies 245 W to a high frequency of 13.56 MHz. The resulting film has a thickness of «12 nm and a composition of SiONO.7. First, copper sputtering was carried out using a second roller having a width of 26 cm and a diameter of 40 cm, and a film was formed under the conditions of an argon gas pressure of 0.6 Pa and a DC voltage of 400 V. Φ Next, the flexible circuit board of the present invention was produced by plating with a copper plating apparatus shown in Fig. 4 so that the thickness of copper was ΙΟμπι. [Evaluation method] The copper plating film was left to be etched at a width of 3 mm, and the tensile test in the vertical direction was carried out in a manner as defined in JIS C 5016, and the adhesion was measured. Further, the reliability was a sample in which the thickness was etched at a width of 3 mm, and the adhesion was measured in the same manner at 180 ° for one day. [Example 5] With respect to Example 1, a film formation was carried out under the same conditions except that the nitrogen concentration, the direct current voltage, and the high frequency power of the yttrium oxynitride sputtering process were changed, and the film composition and film thickness were replaced. [Comparative Example 2] As a comparative example 2, the nitrogen concentration, the direct current voltage, and the high-frequency electric power of the yttrium oxynitride film forming chamber were changed to prepare a yttrium oxynitride film having a composition of SiN0.3 - 31 - 200836609. The preparation conditions and evaluation results of yttrium oxynitride of Example 5 and Comparative Example 2 are shown in Table 3 below. Table 3 Sample No. Air pressure (Pa) Gas composition (Ar: N2) DC voltage (V) High-frequency power (W/cm2) Film composition film thickness (nm) Adhesion (N/mm) Initial 180〇C-1 Example 4 0.5 7:1:2 440 0.15 SiONO.7 12 0.6 0.7 Example 5-1 0.5 7:1:2 425 0.15 SiONO.7 6 0.8 0.7 Example 5-2 0.6 6:1:3 465 0.18 SiONO. 7 28 0.5 0.8 Example 5·3 0.5 7:2:1 450 0.1 SiO1.5N0.3 15 0.5 0.6 Example 5-4 0.6 6:0.5:3.5 440 0.2 SiO0.3Nl.l 12 0.7 0.8 Comparative Example 2 1 0.5 7:2:1 450 0.03 SiO1.8N0.1 15 0.1 0.3 Comparative Example 2-2 0.6 6:0.3:3.7 440 0.25 SiO0.2N1.2 12 0.2 0.4 [Example 6] The apparatus shown in Fig. 5 was used. In the conditions of Example 4, film formation was carried out under the same conditions except that high-frequency power was applied to the cylindrical roller for copper sputtering. The high frequency deflection conditions and evaluation results at the time of copper sputtering in Example 6 are shown in Table 4 below. Table 4 Sample No. Local Frequency Power (W/cm2) Adhesion <T/mm) Initial 180〇C-1 Day Example 6-1 0.05 0.9 0.8 Example 6-2 0.1 1.1 0.9 Example 6-3 0.2 1.2 0.7 - 32 - 200836609 The second roller 17 having a width of 26 em and a diameter of 40 cm was formed under the conditions of an argon gas pressure of .6 Pa and a DC voltage of 400 V. Then, the flexible circuit board 6 of the present invention was produced by plating in a copper plating apparatus shown in Fig. 3 so that the thickness of copper was ΙΟμηη. [Embodiment 8] In the first embodiment, except for changing the nitrogen concentration, the direct current voltage, and the high-frequency power of the yttrium oxynitride sputtering process, the film composition and the film thickness were changed, and the same conditions were carried out under the same conditions. Film formation. [Embodiment 9] In the first embodiment, an aluminum film and a nickel film were formed instead of the ruthenium film as the metal film 7, and the voltage was changed to have the same film thickness, and the film formation was carried out under the same conditions. [Example 1] In Example 1, except that the film thickness of the ruthenium film as the metal film 7 was changed, film formation was carried out under the same conditions. [Example 11] A film was formed under the same conditions except that a high-frequency bias voltage was applied to the second roller 17 under the conditions of the first embodiment. -34 - 200836609 [Example 1 2] Conductivity was produced by using the film forming apparatus shown in Fig. 10 . Polyimine film, a polyimine film NPI having a thickness of 25 μm and a width of 25 cm was used. The transport speed of the film is lm/min processing chamber gas, and a mixed gas gas flow rate of 10% of oxygen and 20% of nitrogen is added to argon, and the gas pressure in the plasma processing chamber is 〇·5 Pa, and the applied voltage is 38 0 V, and plasma is generated. To allow the film to pass through the plasma environment. In the next reactive sputtering chamber, the flow rate voltage was adjusted to 410 V in a mixture of argon 70% and oxygen 10%, and the first roll having a width of 26 cm and a diameter of 20 cm was 13.56 MHz. 245W is applied at high frequency. The resulting film had a composition of 12 nm and a composition of SiONO. Next, the ruthenium sputtering which is a tantalum film of the metal film 7 is a second roller 17 having a diameter of 26 cm and a diameter of 40 cm. The sputtering was carried out under conditions of argon gas flow and a direct current voltage of 320V. Further, film formation was carried out under the conditions of a copper sputtering pressure of 0.6 Pa and a DC voltage of 400 V. The copper plating apparatus shown in Fig. 3 was plated in a row having a copper thickness of 15 μm to produce a flexible circuit board of the present invention. [Example 1 3] In the case of Example 12, the film composition and the film thickness were changed, and the film formation was carried out under the same conditions except that the yttrium oxynitride sputtering process concentration, the DC voltage, and the high-frequency power were changed. The film Kaneka. Plasma, adjusted to add AC nitrogen 20%, in straight son 16, thickness is used width! 0.6Pa is in argon, in addition to nitrogen in the way, its -35-200836609 [Example 14] For Example 1 2 In addition to forming an aluminum film and a nickel film instead of the ruthenium film as the metal film 7, the film was changed under the same film thickness except that the voltage was changed to the same film thickness. [Example 1 5] In the same manner as in Example 6, except that the film pressure of the tantalum film as the metal film 7 was changed, the film formation was carried out under the same conditions. [Example 1 6] When copper sputtering was performed under the conditions of Example 12, film formation was carried out under the same conditions as in Example 12 except that the high-frequency deflection voltage was applied to the second roller 1. [Experimental Example 1] % In Example 7, the nitrogen concentration, the direct current voltage, and the high-frequency electric power of the tantalum nitride film forming chamber were changed, and the film composition was changed except for the film composition and film thickness, and the film formation was carried out under the same conditions. (i) [Experimental Example 2] With respect to Example 10, film formation was carried out under the same conditions except that the film thickness of the sand film as the metal film 7 was changed. [Evaluation Method] -36 - 200836609 Etching was carried out so that the copper plating film remained in the width of 3 mm, and the tensile test in the vertical direction was carried out in the manner as defined in JIS C 5016, and the adhesion was measured. Further, the reliability was a sample in which uranium engraving was performed at a width of 3 mm, and it was placed in 1801 for one day, and the adhesion was measured in the same manner. The conditions for the formation and evaluation of the tantalum nitride of Examples 7 to 10 are shown in Table 5 below.

表5 試料No 氣壓氣體組成直流電壓高頻電力膜組成膜厚金屬膜厚密接力(N/mm) (Pa) (Ar:N2) (V) (W/cm2) (nm) (nm) 初期 180〇〇1 曰實施例7 0.5 7:3 410 0.098 SiNl.2 10 矽 2 1.2 實施例8-1 0.5 7:3 410 0.051 SiNO.7 10 矽 2 1 0.9 實施例8-2 0.5 7:3 410 0.196 SiN1.2 10 矽 2 0.9 0.8 實施例8-3 0.5 9:1 400 0.051 SiN0.5 10 矽 2 0.7 0.8 實施例8-4 0.5 5:5 420 0.15 SiN1.3 10 矽 2 0.7 0.9 實施例8-5 0.5 8:2 390 0.098 SiN1.2 5 鋁 2 0.8 0.8 實施例8-6 0.7 7:3 425 0.098 SiN1.2 15 矽 2 0.7 0.9 實施例9·1 0.5 7:3 410 0.098 SiN1.2 10 鋁 2 0.9 0.7 實施例9-2 0.5 7:3 410 0.098 SiNl.2 10 鎳 2 0.8 0.7 實施例ί〇·1 0.5 7:3 410 0.098 SiN1.2 10 矽 0.5 0.7 0.7 實施例10-2 0.5 7:3 410 0.098 SiN1.2 10 矽 5 0.8 1.1 實施例1 1之銅濺鍍時的高頻偏向條件與評價結果’ 顯示於下述的表6。 -37- 200836609 表6 試料No 局頻電力 (W/cm2) _ 密接力 [N/mm) 初期 180°C-1 日實施例11-1 0.05 1 0.9 實施例11-2 0.1 1.2 0.9 實施例11-3 0.2 1 . 1 0.8Table 5 Sample No. Gas Pressure Composition DC Voltage High Frequency Power Film Composition Thickness Metal Film Thickness Adhesion (N/mm) (Pa) (Ar: N2) (V) (W/cm2) (nm) (nm) Initial 180 〇〇1 曰Example 7 0.5 7:3 410 0.098 SiNl.2 10 矽2 1.2 Example 8-1 0.5 7:3 410 0.051 SiNO.7 10 矽2 1 0.9 Example 8-2 0.5 7:3 410 0.196 SiN1.2 10 矽2 0.9 0.8 Example 8-3 0.5 9:1 400 0.051 SiN0.5 10 矽2 0.7 0.8 Example 8-4 0.5 5:5 420 0.15 SiN1.3 10 矽2 0.7 0.9 Example 8- 5 0.5 8:2 390 0.098 SiN1.2 5 Aluminum 2 0.8 0.8 Example 8-6 0.7 7:3 425 0.098 SiN1.2 15 矽2 0.7 0.9 Example 9·1 0.5 7:3 410 0.098 SiN1.2 10 Aluminium 2 0.9 0.7 Example 9-2 0.5 7:3 410 0.098 SiNl.2 10 Nickel 2 0.8 0.7 Example ί〇·1 0.5 7:3 410 0.098 SiN1.2 10 矽0.5 0.7 0.7 Example 10-2 0.5 7: 3 410 0.098 SiN1.2 10 矽5 0.8 1.1 Example 1 High-frequency bias conditions and evaluation results at the time of copper sputtering of 1 are shown in Table 6 below. -37- 200836609 Table 6 Sample No. Local Frequency Power (W/cm2) _ Adhesion [N/mm) Initial 180 °C-1 Day Example 11-1 0.05 1 0.9 Example 11-2 0.1 1.2 0.9 Example 11 -3 0.2 1 . 1 0.8

實施例1 2〜1 5之氧氮化矽作成條件與評價結果，顯示於下述的表7。表7 試料No 氣壓氣體組成直流電壓高頻電力膜組成膜厚金屬膜厚密接力(N/nrni) (Pa) (Ar:N2) (V) (W/cm2) (rnn) (細）初期 180〇〇1 曰實施例12 0.5 7:1:2 440 0.15 SiONO.7 12 矽 2 1.1 0.9 實施例13-1 0.5 7:1:2 425 0.15 SiONG.7 6 矽 2 1.2 0.8 實施例13-2 0.6 6:1:3 465 0.18 SiONO.7 28 矽 2 1 0.9 實施例13-3 0.5 7:2:1 450 0.1 SiO1.5N0.3 15 矽 2 I 0.7 實施例13-4 0.6 6:0.5:3.5 440 0.2 SiO0.3NI.l 12 矽 2 1.1 0.9 實施例14-1 0.5 7:1:2 440 0.15 SiONO.7 12 鋁 2 1 0.9 實施例14-2 0.5 7:1:2 440 0.15 SiONO.7 12 鎳 2 0.9 0.8 實施例15-1 0.5 7:1:2 440 0.15 SiONO.7 12 矽 0.5 0.9 0.6 實施例15-2 0.5 7:1:2 440 0.15 SiONO.7 12 矽 5 0.8 0.8 實施例1 6之銅濺鍍時的高頻偏向條件與評價結果，顯示於下述的表8。 -38- 200836609 表8 試料N 〇局頻電力 (W/cm2) 密接力ί [N/mm) 初期 180〇〇1 日實施例164 0.0 5 1 .1 0.9 實施例16-2 0.1 1.2 1 實施例16-3 0.2 1.2 0.9 實驗例1〜2之氮化矽作成條件與評價結果，顯示於Example 1 The conditions for the preparation of yttrium oxynitride of 2 to 15 and the evaluation results are shown in Table 7 below. Table 7 Sample No. Gas pressure composition DC voltage High-frequency power film composition Film thickness Metal film thickness adhesion (N/nrni) (Pa) (Ar: N2) (V) (W/cm2) (rnn) (fine) Initial 180 〇〇1 曰Example 12 0.5 7:1:2 440 0.15 SiONO.7 12 矽2 1.1 0.9 Example 13-1 0.5 7:1:2 425 0.15 SiONG.7 6 矽2 1.2 0.8 Example 13-2 0.6 6:1:3 465 0.18 SiONO.7 28 矽2 1 0.9 Example 13-3 0.5 7:2:1 450 0.1 SiO1.5N0.3 15 矽2 I 0.7 Example 13-4 0.6 6:0.5:3.5 440 0.2 SiO0.3NI.l 12 矽2 1.1 0.9 Example 14-1 0.5 7:1:2 440 0.15 SiONO.7 12 Aluminum 2 1 0.9 Example 14-2 0.5 7:1:2 440 0.15 SiONO.7 12 Nickel 2 0.9 0.8 Example 15-1 0.5 7:1:2 440 0.15 SiONO.7 12 矽0.5 0.9 0.6 Example 15-2 0.5 7:1:2 440 0.15 SiONO.7 12 矽5 0.8 0.8 Example 1 6 The high frequency deflection conditions and evaluation results at the time of copper sputtering were shown in Table 8 below. -38- 200836609 Table 8 Sample N 〇 Local Frequency Power (W/cm2) Bonding force ί [N/mm) Initial 180 〇〇 1 Day Example 164 0.0 5 1 .1 0.9 Example 16-2 0.1 1.2 1 Example 16-3 0.2 1.2 0.9 The conditions and evaluation results of the tantalum nitride of the experimental examples 1 to 2 are shown in

下述的表9。Table 9 below.

表9 試料No 氣壓氣體組成直流電壓高頻電力膜組成膜厚金屬膜厚密接力(N/mm) (Pa) (Ar:N2) (V) (W/cm2) (nm) (nm) 初期 180〇C-1 曰實驗例1-1 0.5 8:2 385 0.098 SiN1.2 3 矽 2 0.9 0.3 實驗例1-2 0.5 7:3 430 0.15 SiNl.l 20 矽 2 0.3 0.6 實驗例1·3 0.5 9:1 400 0.01 SiN0.3 10 矽 2 0.3 0.2 實驗例1-4 0.6 5:5 415 0.25 SiN1.4 10 矽 2 0.9 03 實驗例2-1 0.5 7:3 410 0.098 SiN1.2 10 矽 0.3 0.4 0.5 實驗例2-2 0.5 7:3 410 0.098 SiN1.2 10 矽 6 0.4 0.7 〔評價結果〕在規格上，初期値成爲〇.5N/mm以上，針對高溫保存後，無特別規定，但一般爲0.4N/mm以上即可。由評價結果可得知，初期的密接力、高溫保存後均可獲得良好的結果，又，由於爲絕緣物，故不會有蝕刻之問題產生，能獲得可進行微細圖案之可撓性電路基板。【圖式簡單說明】 -39- 200836609 圖1是顯示本發明的第1實施形態的可撓性電路基板之斷面圖。圖2是顯示本發明的第2實施形態的可撓性電路基板之斷面圖。圖3是顯示濺鍍環裝置之構成圖。圖4是顯示鍍裝裝置之構成圖。圖5是顯示濺鍍環裝置的第2例之構成圖。圖6是顯示濺鍍環裝置的第3例之構成圖。圖7是顯示濺鍍環裝置的第4例之構成圖。圖8是顯示本發明的其他實施形態的可撓性電路基板之斷面圖。圖9是顯示本發明的第7實施形態的可撓性電路基板之斷面圖。圖1 〇是顯示濺鍍環裝置之構成圖。圖11是顯示本發明的其他實施形態的可撓性電路基板之斷面圖。【主要元件符號說明】 1 :樹脂薄膜 la，具有種晶層之薄膜 2a :氮化矽層 2b :氧氮化矽層 3 :銅系金屬層 3 a :銅膜 -40- 200836609 4 :銅濺鍍膜 5 :鍍銅層 6 :可撓性電路基板 7 :金屬膜Table 9 Sample No. Gas pressure composition DC voltage High-frequency power film composition Film thickness Metal film thickness adhesion (N/mm) (Pa) (Ar: N2) (V) (W/cm2) (nm) (nm) Initial 180 〇C-1 曰Experimental Example 1-1 0.5 8:2 385 0.098 SiN1.2 3 矽2 0.9 0.3 Experimental Example 1-2 0.5 7:3 430 0.15 SiNl.l 20 矽2 0.3 0.6 Experimental Example 1·3 0.5 9 :1 400 0.01 SiN0.3 10 矽2 0.3 0.2 Experimental Example 1-4 0.6 5:5 415 0.25 SiN1.4 10 矽2 0.9 03 Experimental Example 2-1 0.5 7:3 410 0.098 SiN1.2 10 矽0.3 0.4 0.5 Experimental Example 2-2 0.5 7:3 410 0.098 SiN1.2 10 矽6 0.4 0.7 [Evaluation Result] In the specification, the initial enthalpy becomes 〇.5 N/mm or more, and after storage for high temperature, there is no special regulation, but it is generally 0.4. N/mm or more. It can be seen from the evaluation results that good results can be obtained after the initial adhesion and high-temperature storage, and since it is an insulator, there is no problem of etching, and a flexible circuit substrate capable of obtaining a fine pattern can be obtained. . [Brief Description of the Drawings] -39-200836609 Fig. 1 is a cross-sectional view showing a flexible circuit board according to a first embodiment of the present invention. Fig. 2 is a cross-sectional view showing a flexible circuit board according to a second embodiment of the present invention. Fig. 3 is a view showing the configuration of a sputtering ring device. Fig. 4 is a view showing the configuration of a plating apparatus. Fig. 5 is a view showing a configuration of a second example of the sputtering ring device. Fig. 6 is a view showing the configuration of a third example of the sputtering ring device. Fig. 7 is a view showing the configuration of a fourth example of the sputtering ring device. Fig. 8 is a cross-sectional view showing a flexible circuit board according to another embodiment of the present invention. Fig. 9 is a cross-sectional view showing a flexible circuit board according to a seventh embodiment of the present invention. Figure 1 shows the composition of the sputter ring device. Figure 11 is a cross-sectional view showing a flexible circuit board according to another embodiment of the present invention. [Description of main component symbols] 1 : Resin film la, film 2a with seed layer 2: tantalum nitride layer 2b: hafnium oxynitride layer 3: copper-based metal layer 3 a : copper film -40 - 200836609 4 : copper splash Coating 5: Copper plating layer 6 : Flexible circuit substrate 7 : Metal film

1 0 :電漿室 1 1 :第1濺鍍室 12 :第2濺鍍室 1 3 :供給滾子 1 4 :捲取滾子 1 5 :電漿處理裝置 16 :第1滾子 17 :第2滾子 18 :矽標靶 1 9 :銅標靶 20 :高頻電源 21 :直流電源 2 1 a :直流電源 21b :直流電源 2 2 :咼頻電源 23 :共通滾子 24 :金屬標靶 25 :鍍裝槽 2 6 :水洗槽 2 7 :乾燥槽 2 8 :供給滾子 -41 200836609 :捲取滾子 =直流電源 :陽極 =陰極滾子 =銅供給部 :銅線 ••坩堝 z加熱器 :蒸鍍室 -421 0 : plasma chamber 1 1 : first sputtering chamber 12 : second sputtering chamber 1 3 : supply roller 1 4 : winding roller 1 5 : plasma processing device 16 : first roller 17 : 2roller 18: 矽 target 1 9 : copper target 20 : high frequency power supply 21 : DC power supply 2 1 a : DC power supply 21b : DC power supply 2 2 : 咼 frequency power supply 23 : common roller 24 : metal target 25 : plating tank 2 6 : washing tank 2 7 : drying tank 2 8 : supply roller -41 200836609 : coiling roller = DC power supply: anode = cathode roller = copper supply: copper wire ••坩埚z heater : evaporation chamber -42

Claims

200836609 X. Patent application No. 1 A flexible circuit substrate characterized in that a tantalum nitride layer formed by sputtering is formed on the surface of a resin film with an equivalent of 0.5 to 1.33 of nitrogen. Further, a copper-based metal layer is formed. A flexible circuit board characterized in that a yttrium oxynitride layer formed by sputtering is formed on the surface of the resin film in an equivalent amount of nitrogen of 0.3 to 1.1, and further A copper-based metal layer is formed. 3. A flexible circuit board characterized in that a tantalum nitride layer or a hafnium oxynitride layer formed by a sputtering method is formed on a surface of a resin film, and is formed of tantalum, aluminum, and nickel. A metal film having a thickness of 0.5 to 5 nm is selected, and a copper-based metal layer is further formed. A method of producing a flexible circuit board, comprising: forming a tantalum nitride sputtering process on a surface of a resin film to form a tantalum nitride layer having a nitrogen content of 0.5 to 1.3% equivalent And a copper-based metal forming process for further forming a copper-based metal layer. The method of manufacturing a flexible circuit board according to the fourth aspect of the invention, wherein the tantalum nitride sputtering process is applied to an electrode roller that transports a resin film on a side opposite to the target. The high frequency is biased toward the voltage side. 6. A method of producing a flexible circuit board, comprising: forming a yttrium oxynitride sputtering process on a surface of a resin film to form a lanthanum oxynitride layer having an equivalent of 0.3 to 1.1 nitrogen And a copper-based metal forming process for further forming a copper-based metal layer. 7. The method of manufacturing a flexible circuit board according to claim 6, wherein the above-mentioned yttrium oxynitride sputtering process is an electrode roll for transporting a resin film in a field opposite to the target. The sub-side is applied while applying a high-frequency bias voltage. 8. A method of producing a flexible circuit board, comprising: forming a first sputtering of a tantalum nitride layer or a hafnium oxynitride layer formed on a surface of a resin film by a sputtering method; Process; further forming a second sputtering process of a φ metal film having a thickness of 0.5 to 5 nm selected from ruthenium, aluminum, and nickel; and a copper-based metal formation process for further forming a copper-based metal layer. The method of manufacturing a flexible circuit board according to the eighth aspect of the invention, wherein the second sputtering process applies a high-frequency bias voltage to an electrode roller that transports a resin film in a region opposite to the target surface. , while doing.

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