200806123 九、發明說明： 【發明所屬之技術領域】 明係y有關於-種抑制晶鬚(whisker)發生的佈線基板 。之’侧於在絕緣基板表面上，㈣銅摘合金所形 ^之多數佈齡以形成佈_型，且於該佈顏型的端子部 成含有錫的金屬鍍覆層之佈線基板中，自該佈線圖型端 卞：分之金屬鍍覆詹表面的晶鬚生成得以受抑制的佈線基板。 【先雨技術】 在絕緣基板表面上形成以由鋼所構成之多數佈線的佈線 確且裝電子構件之電氣連接，或爲使該佈線 ϋ之互相連、、Ό u係於其端子部分形成廉價的鑛錫般之鑛 覆層。 然而在鍍錫中’已知會發生所謂的晶鬚，而有 晶鬚導致電路短路的問題叢生。 惟有關晶鬚的發生機制’雖經種種研究， 完全防止晶鬚發生的目的。 逆风付乂 即使於日本特開2005-340434號公報(專利文獻 於由電解銅箱形成之底層銅電路表面覆蓋純銅鑛覆層，而 ，形成的純雛覆層表面形成錫鑛覆層後，再經騎處理= 處理，filing) ’藉由將錫鍍覆層之全部或一部分形 &、 層及Cu3Sn層等，而防止錫晶鬚發生，然而，雖如上^般5 由以純銅鍍覆層被覆底層銅電路之表面，即使藉她理糟 可獲得於錫鐘覆層(Ci^Sn層)與純鋼鍍覆層間不發隙 TAB膠帶的記載。也就是説，習用之TAB膠 ; 晶鬚的發生’係在底層電絲面’直接形成錫鍍覆層 由 炫融處理(加熱處理），在該錫鍍覆層上擴散銅者，^ $ 熔融處理之底層電路與錫鍍覆層之界面由於卡肯 9 ^寻 -雜應而容易發生空隙，因而’記载以純鋼層覆底(厗= 路表面，降低其表®粗糖度(使之平滑），即使以溶融處^可 IP0702I5/SF-1609f 5 200806123 ^。因此，在製造上述專 刻以形成底層鋼電路後，將電解銅舒崎擇祕 鍍而形成純銅層的必要，以鋼電路表面再進行電解電 錫鍍覆層，轴桃彳切成純_後再予以形成 帶的製造工程複雜化的門^之^要，因而’有使tab膠 的3過。又，猎由熔融處理，銅在該鍍錫 ^中痛散’而可於形成的錫鍍覆層中含有相當量』 ο二壯有關所形成之銅落的金顧之結晶粒徑，於專利文獻 =體=::7之號:::，_光滑面至》 !=ίϊ膜等。通常’以上述方式控制表面附近的二，係 私與絕緣層的緊雌，惟這種金觸的粒徑與形成 在該銅治上之金屬鍍覆層之晶鬚的關係未明。 宙在日本特開2006_52441號公報(專敝獻3)之申請 專利辄囲弟1項中，有所謂「未處理薄落中之C1含有量小於 3〇 ppm爲其特徵的銅箔」之記载，具體例中，爲使電解液中 的C1離子濃度成爲ι·5 mg/公升而予轉加濃鹽酸的實 2所獲得的銅箔中C1濃度爲10ppm以下，且即使使（：1-離子濃 度成爲25 mg/公升而添加濃鹽酸的實施例4，所得銅箔中之 C1濃度亦爲10ppm以下。又於該專利文獻2之比較例〗即 示，除了使電解液中Cr離子濃度爲1·5 mg/公升而同時添加 濃鹽酸及明膠(gelatin) 3.6 mg/公升之量以外，使用電計液對 所製造的銅箔測量之Cl—濃度爲40ppm。如此之電解銅箱通常 將Cl_濃度抑制在低濃度。然而，在該比較例1中使用的電解 液係含有C1離子及明膠’若依該等之C1-離子與明膠之γ幷用系 統，不易形成柱狀之銅結晶，一般係形成爲粒狀結晶。也就^ 説，若依該種cr離子及明膠併用系，由於不容易形成爲較$ P070215/SF-1609f 6 200806123 晶’且多爲粒狀結晶，故鱗無電解錫鑛覆層 度致使摘與無電觸賴層_界面部，由 於級^cascade)效應而有容易發生空隙的問題。又，因專利文 農度小於3〇 ’的銅fl ’記載有通常以通 匕友 / m左右的較大電流進行銅的析出作業，故於使 用風離子濃度較高之電鍍浴析出銅時，即使以如例文、 以有效地析出形狀安定的柱狀粒=造的 層擴散之速:ϊ的=微細粒子’故有較難抑制銅向無電解鍵錫 [專利文獻1]日本特開2005-340434號公報 [專利文獻2]日本特開2〇〇5_ 1S3357號公報 [專利文獻3]曰本特開2006-52441號公報 【發明内容】 [發明所需解決的問題] 本發明係提供-種於金屬銅形成的佈線表面，形 金 丰f之金f電鍍層的佈線基板的該含有金屬錫之金屬電鍍層 表面’不谷易發生晶鬚的佈線基板爲目的。 [解決問題的手段] 士本發明的佈線基板，其特徵為：其係於絕緣基板的至一 缘=擇^刻鋪而予以形成佈、_型，且於上述佈 含有_金屬賴層予以被覆之佈線 基板者，上述佈線圖型係以主要為粒徑3 :所形成’且上述柱_銅之氯濃度在μ5〜 上述佈線圖型之金屬鑛覆層係以主要含有錫之結晶 粒仫為〇.7叫以上的金屬所形成，且於上述佈線難中 上不含來自有機化合物之碳原子者。 ^亦即，本發明之構成佈線基板之佈線圖型，雖係含 f氯離子，但係藉由將於不含有明谬或膠類等有機化合物的 銅电鍍液中析出而獲得之銅箔予以蝕刻而成者。 IP〇7〇215/SF-1609f 7 200806123 ιίΐΐ述之被覆佈線圖型表面而形成之金屬鑛覆層，通常 舄十勻厚度0·02〜1·5μηι之無電解錫鍵覆層。 女於本發明之佈線基板上形成之佈線圖型之大部分係由且 ，二晶粒徑3pm以上的柱狀結晶構造的銅所形成，且具有^ j絲子形絲_的柱狀結晶構造。於含有該柱狀粒 +含有氯濃度為5〜5()’之較高含量，如上述欲提 氯濃度之情況下，通f係將使用之電鑛銅液内 、離子/辰度，持於50〜80mg/公升，且較好爲5〇〜7〇 mg/ 公升左右的，濃度，而於銅析出之際，電流密度通常設定爲工 二3^A/dm，且較好設定在範圍内，而以較低 =岔度析_。若社絲件析_，可使減度如上述般 =尚’ 2獲得由大部分爲粒徑3μιη以上的柱狀粒子所形成的 ^解銅4。又’製造如此高氯濃度的電解銅荡時，在電鑛銅液 中不添加郷、膠類等的有機化合物。假若添加师、膠類等 之有機化合物(蛋自質），將使形成的鋼結晶易成為粒狀結晶， 因此’極不容易形成在本發明所使用之粒徑3叫以上的柱狀 結晶。如此，由於以明膠、膠類等之有機化合物與氯併用系 獲得的電解銅箱中大多爲小粒徑的粒狀結晶銅，因而，加速銅 向佈線圖型表面上形成的錫鍍覆層擴散之速度。 如上述，藉由使用含有特定高氯含量且係大粒徑的柱狀结 晶銅所形成的佈線_表社，形成由大粒徑騎成之鑛^ 層，即可銅向該錫鍍覆層擴散之速度變得非常緩慢。 已知一般金屬錫係採用具有正方晶系結晶構造且a=b= 5.831埃、c=3.182埃、α=ρ=γ=9〇之結晶構造’而銅擴散 至錫中後之金屬間化合物（其代表的金屬間化合物爲Cu6Sn5) 係採用通常為a=lL033埃、b=7 294埃、c=9 83埃、α=γ =90、ρ=98.82之單斜結晶系的結晶構造。且由此，得知錫與 金屬間化合物(CugSii5)的格子常數有極大差異。因此，若形成 Cu原子擴散於錫鍍覆層之金屬間化合物(以％)，則在形成擴 IP070215/SF-1609f 8 200806123 服’而锡鐘覆層發生壓縮應力，認為該壓 縮應力成局錫晶鬚發生的驅動力。 门 、在本發明的佈線基板，藉由形成佈線圖型的 範爲形成粒徑較大之柱狀結晶銅予以控制3 μ再使，、上形成之鍚鍍覆層之粒徑加大，即以 5 ί纖紐。如找，齡·_子之^ ίί:3ΐ屬曰Ϊ之生成而發生的壓縮應力減低，而ί 粒徑，即得以抑制晶鬚的發生。 猎机大銅粒子的 [發明的效果] 依本發明的舰基板，#可抑制稀線表面之含有錫的今 H 生錫晶鬚。也就是説，形成本發明之、 織則奸顯概大陳練子，且亦使形 ΐϊϊίϊΐΓί錫鍍覆層之錫析出結晶加大，如此由於銅结 =得==i層 忐锶曰彩々跡心丄 4 u通！細應力乃係用以形 力3可減少錫晶鬚發生的驅動力。因此，於本發^佈3 發生。若如上述方式於錫雛層中不累積成ί 域與錫嫂覆層間之界面，不會形成^質 【實施方式】 接著，就本發明的佈線基板予以具體説明。 本發明的佈線基板，係於絕緣基板的至少一 箔以選擇性_辭_成佈、_型，且係於該佈^型= IP070215/SF-1609f 9 200806123 少一部分係以含有錫的金屬鍍覆層予以覆蓋者。 構成本發明佈線基板之佈線圖型，係藉由對銅 性蝕刻而形成。 丁乂 k擇200806123 IX. Description of the invention: [Technical field to which the invention pertains] The system y has a wiring substrate for suppressing the occurrence of whiskers. 'on the surface of the insulating substrate, (4) the majority of the age of the copper-cut alloy to form a cloth-type, and in the wiring-type terminal portion of the wiring portion of the metal-plated layer containing tin, The wiring pattern end: a metal wiring plated on the surface of the Zhan whisker to suppress the formation of the wiring substrate. [Pre-Rain Technology] The electrical connection of the electronic components is formed on the surface of the insulating substrate by a plurality of wirings made of steel, or the wiring is connected to each other, and the wiring is formed in the terminal portion. The tin-like mineral coating. However, in tin plating, it is known that so-called whiskers occur, and there is a problem that whiskers cause short circuits. However, the mechanism of occurrence of whiskers has been completely prevented from the occurrence of whiskers. In addition, it is disclosed in Japanese Laid-Open Patent Publication No. 2005-340434 (the patent document covers a pure copper ore coating on the surface of a bottom copper circuit formed by an electrolytic copper box, and then forms a tin ore coating on the surface of the formed pure green coating layer, and then By riding treatment = processing, "filing" prevents the occurrence of tin whiskers by forming all or part of the tin plating layer & layer, Cu3Sn layer, etc., however, although it is as above, 5 is coated with pure copper. The surface of the underlying copper circuit is covered, and the TAB tape can be obtained from the tin-bell coating (Ci^Sn layer) and the pure steel plating layer. That is to say, the conventional TAB glue; the occurrence of whiskers 'being on the bottom wire surface' directly forms a tin plating layer by the smelting treatment (heat treatment), and the copper is diffused on the tin plating layer, ^ $ melting The interface between the underlying circuit and the tin-plated layer is easily creased due to the Karken 9^---there is a description of the pure steel layer covering the bottom (厗=road surface, lowering its surface® coarse sugar content (making it smooth) ), even if it is molten, it can be IP0702I5/SF-1609f 5 200806123 ^. Therefore, after manufacturing the above-mentioned special order to form the bottom steel circuit, it is necessary to plate the electrolytic copper to form a pure copper layer, to the surface of the steel circuit. Then, the electroplated electroplated layer is electroplated, and the shaft peach is cut into pure _, and then the door of the manufacturing process of the belt is complicated, so that there is a 3 of the tab glue. Copper can be painfully dispersed in the tin plating, and can contain a considerable amount of crystallized grain in the tin plating layer formed by the two crystals, in the patent document = body =:: 7 No.:::, _ smooth surface to ” != ϊ ϊ film, etc. Usually 'control the two near the surface in the above way, The relationship between the size of the gold contact and the whisker of the metal plating layer formed on the copper layer is unknown. In the case of the patent application, there is a description of the "copper foil characterized by a C1 content of less than 3 〇ppm in an untreated smear". In the specific example, the C1 ion concentration in the electrolytic solution is changed. In the copper foil obtained by the actual addition of 5 mg/liter to the concentrated hydrochloric acid, the C1 concentration is 10 ppm or less, and even in Example 4 in which (1: 1-ion concentration is 25 mg/liter and concentrated hydrochloric acid is added, The concentration of C1 in the obtained copper foil is also 10 ppm or less. In addition, the comparative example of Patent Document 2 shows that in addition to the concentration of Cr ions in the electrolytic solution of 1.5 mg/liter, concentrated hydrochloric acid and gelatin are simultaneously added. In addition to the amount of 3.6 mg/liter, the Cl-concentration measured on the copper foil produced using the electrometer solution was 40 ppm. Such an electrolytic copper box generally suppressed the Cl_ concentration at a low concentration. However, it was used in the comparative example 1. The electrolyte contains C1 ions and gelatin's γ幷 according to the C1-ion and gelatin. In the system, it is difficult to form columnar copper crystals, which are generally formed into granular crystals. That is to say, if the type of cr ion and gelatin are used in combination, it is not easy to form crystals as compared with $P070215/SF-1609f 6 200806123' Most of them are granular crystals, so the scale of the electroless tin deposits causes the problem of easy voids due to the effect of the cascade and the electroless contact layer. Moreover, since the patented degree is less than 3铜's copper fl' is described as a copper precipitating operation usually performed at a large current of about 匕友友/m. Therefore, when copper is deposited using an electroplating bath having a high wind ion concentration, it is effectively precipitated as in the example. The shape of the columnar granules of the shape of the granules is as follows: ϊ = = 细 细 细 细 细 细 [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [Patent Document 3] JP-A-2006-52441 SUMMARY OF INVENTION [Problems to be Solved by the Invention] The present invention provides a wiring surface formed by metal copper. Jinfeng f's gold f plating layer of the wiring substrate Metal of the metal surface of the tin plated layer 'valley does not occur easily the wiring board for the purpose of whiskers. [Means for Solving the Problem] The wiring board of the present invention is characterized in that it is formed on the edge of the insulating substrate to be etched, and is formed into a cloth, a _ type, and is covered with the _ metal layer. In the wiring substrate, the wiring pattern is formed mainly by the particle size 3: and the column-copper has a chlorine concentration of μ5 to the metal pattern of the wiring pattern, and the crystal grain mainly containing tin is 〇.7 is formed by the above metal, and does not contain carbon atoms derived from organic compounds in the above-mentioned wiring difficulty. That is, the wiring pattern constituting the wiring board of the present invention is a copper foil obtained by depositing a copper plating solution which does not contain an organic compound such as an alum or a gel, although it contains f-chloride ions. Etched to the original. IP〇7〇215/SF-1609f 7 200806123 金属 The metal ore coating formed by covering the surface of the wiring pattern is usually an electroless tin bond coating with a thickness of 0·02~1·5μηι. Most of the wiring patterns formed on the wiring substrate of the present invention are formed of copper having a columnar crystal structure having a crystal grain size of 3 pm or more, and having a columnar crystal structure of the wire shape of the wire. . In the case of containing the columnar particles + containing a higher concentration of chlorine concentration of 5 to 5 () ', as in the case of the above-mentioned chlorine concentration to be extracted, the use of the electro- ore copper liquid, ion / Chen, will be used The concentration is 50 to 80 mg / liter, and preferably about 5 〇 to 7 〇 mg / liter, and when copper is precipitated, the current density is usually set to 2 ^ A / dm, and is preferably set in the range Inside, and at a lower = 岔 degree _. If the silk fabric is analyzed, the degree of reduction can be as described above = still 2 to obtain copper which is formed by columnar particles having a particle diameter of 3 μm or more. Further, when electrolytic copper having such a high chlorine concentration is produced, an organic compound such as ruthenium or gum is not added to the molten copper liquid. If an organic compound such as a teacher or a gel (such as an egg) is added, the formed steel crystal is likely to be a granular crystal. Therefore, it is extremely difficult to form a columnar crystal having a particle diameter of 3 or more used in the present invention. In this way, since the electrolytic copper case obtained by using an organic compound such as gelatin or a gel and a chlorine-based system is mostly a granular copper crystal having a small particle diameter, the copper is spread on the surface of the wiring pattern to accelerate the diffusion of the tin plating layer. Speed. As described above, by using a wiring formed by a columnar crystal copper having a specific high chlorine content and a large particle diameter, a layer formed by a large particle size is formed, that is, copper is applied to the tin plating layer. The speed of diffusion becomes very slow. It is known that a general metal tin is an intermetallic compound having a tetragonal crystal structure and having a crystal structure of a = b = 5.831 angstroms, c = 3.182 angstroms, and α = ρ = γ = 9 而 and copper is diffused into the tin ( The intermetallic compound represented by the formula is Cu6Sn5). A monoclinic crystal structure having a ratio of a = lL033 Å, b = 7 294 angstroms, c = 9 83 angstroms, α = γ = 90, and ρ = 98.82 is used. From this, it was found that the lattice constant of tin and the intermetallic compound (CugSii5) was greatly different. Therefore, if an intermetallic compound (in %) in which Cu atoms are diffused in the tin plating layer is formed, a compressive stress is generated in the coating of the tin bell in the formation of the expanded IP070215/SF-1609f 8 200806123, and the compressive stress is considered to be a tin. The driving force of whiskers. In the wiring board of the present invention, by forming a wiring pattern, the columnar crystal copper having a large particle diameter is controlled to be 3 μm, and the particle size of the ruthenium plating layer formed thereon is increased, that is, Take 5 ί fiber button. If you look for it, age _子之^ ίί: The compressive stress that occurs when the 3 genus is formed is reduced, and the λ particle size, that is, the occurrence of whiskers is suppressed. [Effect of the Invention] According to the ship substrate of the present invention, # can suppress the tin-containing tin whisker on the surface of the thin line. That is to say, the formation of the invention is woven by the singularity of the singer, and the crystallization of the tin-plated layer of the tin-plated layer is increased, so that the copper knot is ==i layer Heart 丄 4 u pass! The fine stress is used to reduce the driving force of tin whiskers. Therefore, it occurs in this hair cloth. If the interface between the ί region and the tin-bismuth layer is not accumulated in the tin layer as described above, the film is not formed. [Embodiment] Next, the wiring board of the present invention will be specifically described. The wiring substrate of the present invention is based on at least one foil of the insulating substrate to be selectively patterned, and is attached to the type of the package = IP070215/SF-1609f 9 200806123. The cover is covered. The wiring pattern constituting the wiring board of the present invention is formed by etching copper. Ding Wei
本發明所用的銅箔係使用電解銅箔。而於本發明 細㈣含有特定量的氯濃度且大部分由她結晶銅所電 本發明之佈線基板中，於構成佈線圖型的銅中含有5^5〇 ppm，較好為5〜40ppm範圍内的氯。藉由本發明之佈 上形成之佈線圖型的銅中含有上述量的氯，即能安定地予 ，粒徑3μπι以上，較好爲3〜1〇μπι範圍内的柱狀結晶銅。^ 舄了安定地析出該等大粒徑之柱狀結晶銅，所形成的銅 含有來自明膠或膠類等之蛋白質即有機化合物的碳原子。 而於本發明使用的電解銅箔，係使用銅離子濃度 30，150g/公升，較好為4G〜13G g/公升範圍内的鑛鋼液^ 以形，。而於上述鍍銅液中，通常含有游離硫酸離子，惟於 f明係使用游離的硫酸離子(SO，)濃度爲75〜25〇 公升， 較好80〜220 g/公升範圍内之鍍銅液。再者，本發明 的鍍銅溶液中含有氯離子(Cr)，而該cr離子濃度通常爲5〇〜 8〇 mg/公升，較好為50〜7〇 mg/公升之範圍内，係表示較 -般使用之細液巾的練爲高。此魏料储由於錢銅液 中添加鹽酸予以導入。 雖然在本發明使用的鍍銅液中，含有如上述之比較高濃戶 的氯離子，但不含有明膠、膠類等的蛋白質所成之有^化ς 物。若添加該蛋白質等之有機化合物予以製造，則銅不容易; 成柱狀結晶，通常其粒狀結晶較多，且其粒徑亦大多至多 3μαι 〇 ’、、 使用上述氯離子濃度高的鑛銅液，以獲得可能形成本發明 之佈線基板中之佈線圖型的電解銅箔，其銅的析出條件至爲重 要’，常係將温度維持於20〜6〇。〇，設定電流密度爲3〜7 a /dm2(300〜700A/m2)之範圍内，以較低電流密度、<且温和的 IP070215/SF-1609f 10 200806123 析出銅。如上述自鍍銅液以該等條件析出鋼，可得到氯含 y ’且主要係以粒徑為3μιη以上的柱狀結晶所成的電解^ 又’於製造本發明使用的電解銅箔之鍍銅液，除上述成分 以外、，雖不特別需要其他成分，惟於具亦如上述之基本組成之 鍍^液t，除上述銅離子及硫酸離子以外，在不損害本發明目 的範圍内，亦可添加螯合劑、界面活性劑等。 x • 構成本發明佈線基板之佈線圖型，係以具有上述氯濃度在 5〜50^>pm、較好在5〜4〇ppm的高濃度且主要為粒徑3师以 上、，好主要為3〜ΙΟμιη的柱狀結晶之銅所形成。 爲製造具有該等大粒徑柱狀結晶的銅箔，於含有上述般濃 度的銅離子及硫酸離子之鍍銅液中氯離子之作用具有重要 性。:般S造電鞠狀情況下，細整所獲·電/解銅絲 面狀f或其，張力等，已知有添加少量膠類、明膠等蛋白質， ^及氯離子等，例如於使用明膠之情況下，該明膠的添加量通 二係調整爲。.1〜2〇 ppm/公升左右。又例如在含有氯離子之 t月況的電鑛液中之氯離子(cr)濃度，通常係調整爲1〇〜4〇鹏 念右。^如，使用添加明膠的鑛銅液製造電解銅箔時，所得之 電解銅箔表面之粗化面受到抑制。然而，僅使用明膠時，對上 • 述般的電解銅箱的粗面化抑制效果不大，故有爲引發具有明膠 的粗面化抑制效果而有必要存在氯化物離子之説(例如参照曰 本特開2002一322586號公報第陶2段落）。因此，於如此般 添加明膠予?調整之電解銅箱的表面粗度較低，故適於佈線基 板之製造，得以作爲以微影蝕刻⑽oto卿hic)法進行選擇性餘 刻製造佈線圖型時之電解銅n n乏地被使用。 然而，以上述方式製造的低表面粗度之電解銅箔，爲抑低 表面粗度，有必要將個個銅粒子的粒徑予以變小，例如，單獨 添加50 pp^ig的日^膠所製造之電解銅箔係形成粒徑約〇· 3μιη左 右之粒狀結晶。若使用由上述銅的微細粒狀結晶所成的電解銅 IP070215/SF-I609f 200806123 箔予以形成之佈線圖型表面上形成錫鑛覆層時，因該銅落中的 致銅原子對錫鍍覆層的高速擴散，急速形 ，銅之金屬剛b合物，更縣翻軒觸鍍覆層之 高速擴散，而麵層與錫鍍覆層之界面部分，由似以卡肯道爾 (方-m -雜應形成錄雜。藉由上述_子之擴散而生成 金屬間化合物，使於錫鍍覆射之歸應力增冑，而以該麵 應力爲驅動力，發生多數的錫晶鬚，且亦將隨著_的經過， 急速增加該晶鬚之發生根數。The copper foil used in the present invention is an electrolytic copper foil. In the wiring substrate of the present invention, which contains a specific amount of chlorine concentration and most of which is crystallized by copper, the present invention contains 5^5 ppm, preferably 5 to 40 ppm in the copper constituting the wiring pattern. Chlorine inside. The copper of the wiring pattern formed on the cloth of the present invention contains the above-mentioned amount of chlorine, that is, the columnar crystal copper having a particle diameter of 3 μm or more, preferably 3 to 1 μm. ^ The columnar crystal copper of such a large particle size is precipitated in a stable manner, and the copper formed contains a carbon atom derived from a protein such as gelatin or a gel, that is, an organic compound. Further, in the electrolytic copper foil used in the present invention, a molten steel having a copper ion concentration of 30, 150 g/liter, preferably 4 G to 13 G g/liter, is used. In the above copper plating solution, usually contains free sulfuric acid ions, but the concentration of free sulfuric acid ions (SO,) is 75 to 25 liters, preferably 80 to 220 g / liter of copper plating solution. . Furthermore, the copper plating solution of the present invention contains chloride ions (Cr), and the concentration of the cr ions is usually in the range of 5 〇 8 〇 mg / liter, preferably 50 to 7 〇 mg / liter, which means The use of the fine liquid towel is high. This Wei material storage is introduced by adding hydrochloric acid to the copper liquid. Although the copper plating solution used in the present invention contains chloride ions of relatively high-concentration as described above, it does not contain proteins such as gelatin or gelatin. When an organic compound such as this protein is added and manufactured, copper is not easy; in the case of columnar crystals, usually, there are many granular crystals, and the particle diameter thereof is usually at most 3 μαι 〇 ', and the use of the above-mentioned copper chloride having a high concentration of chloride ions The liquid is obtained to obtain an electrolytic copper foil which may form a wiring pattern in the wiring substrate of the present invention, and the precipitation conditions of copper are important, and the temperature is usually maintained at 20 to 6 Torr. 〇, set the current density in the range of 3~7 a / dm2 (300~700A/m2), and precipitate copper at a lower current density, & and mild IP070215/SF-1609f 10 200806123. When the steel is precipitated from the copper plating solution under the above conditions, the electrolysis of the electrolytic copper foil used in the production of the present invention can be obtained by electrolysis of the columnar crystal having a chlorine content of y' and mainly having a particle diameter of 3 μm or more. The copper liquid, other than the above-mentioned components, does not particularly require other components, but the plating liquid t having the basic composition as described above, in addition to the above-mentioned copper ions and sulfate ions, does not impair the object of the present invention. A chelating agent, a surfactant, and the like may be added. x The wiring pattern constituting the wiring substrate of the present invention has a chlorine concentration of 5 to 50 Å pm, preferably 5 to 4 〇 ppm, and a particle size of 3 or more. It is formed of copper of columnar crystals of 3 to ΙΟμιη. In order to produce a copper foil having such a large-sized columnar crystal, the action of chloride ions in the copper plating solution containing copper ions and sulfate ions having the above-mentioned concentrations is important. In the case of the S-electricity, it is known that a small amount of a gel, a gelatin or the like is added, and a chloride or the like is added, for example, in use. In the case of gelatin, the amount of gelatin added is adjusted to be two. .1~2〇 ppm/liter. For example, the concentration of chloride ion (cr) in an electric ore containing t-months of chloride ions is usually adjusted to 1 〇 to 4 〇 right. For example, when an electrolytic copper foil is produced using a gelatin-added ore-forming copper liquid, the roughened surface of the surface of the obtained electrolytic copper foil is suppressed. However, when only gelatin is used, the effect of suppressing the roughening of the above-mentioned electrolytic copper box is not large, and therefore it is necessary to have chloride ions in order to suppress the effect of suppressing the surface roughness of gelatin (for example, see 曰Japanese Patent Laid-Open Publication No. 2002-322586, paragraph 2, paragraph 2). Therefore, since the surface of the electrolytic copper box to which the gelatin is added is adjusted to have a low surface roughness, it is suitable for the manufacture of the wiring substrate, and the wiring pattern can be selectively produced by the lithography etching (10) otoqing method. The electrolytic copper is used boringly. However, in the case of the low-surface-thickness electrolytic copper foil manufactured in the above manner, in order to suppress the surface roughness, it is necessary to reduce the particle diameter of each of the copper particles, for example, adding 50 pp^ig of the day alone. The produced electrolytic copper foil is formed into a granular crystal having a particle diameter of about 〇·3 μm. When a tin ore coating is formed on the surface of a wiring pattern formed by using the electrolytic copper IP070215/SF-I609f 200806123 foil formed of the fine granular crystal of copper described above, the copper atom in the copper falling is plated with tin. The high-speed diffusion of the layer, the rapid shape, the copper metal b-compound, the high-speed diffusion of the plated coating of the county, and the interface between the surface layer and the tin-plated layer, which is like the Kaken Doyle (square - M-hybrid should form a recording impurity. The intermetallic compound is formed by the diffusion of the above-mentioned _ sub-particles, so that the stress of the tin plating is increased, and a large amount of tin whiskers are generated by the surface stress as a driving force, and It will also increase the number of occurrences of the whiskers rapidly as _ passes.
以本發明使用的具有主要為粒徑3μηι以上之柱狀結晶、 ，好主要為3〜陳狀結晶之銅，與製造上述佈線基 = 不同’係不使卿類、明膠等蛋白f，氯濃度維 ，在通每A 50〜80 mg/公升、較好5〇〜7〇 mg/公升左右的 高濃度’崎㈣之電雜度設爲通常之丨〜撤/如2、且 ^設定爲1〜15A/dm2範圍内之較低電流密度使銅析出 造。 ^將鑛銅溶液中的上述氯離子濃度與一般電鍍液中之氯 辰度味，7H鱗常高練値，個該賴液以温和 慢慢析出，金屬，即可轉辦所含有之紐度在上述之5〜 =fpm細内。❿且具有該氯濃度晴出綱結晶形狀爲柱 狀、、、口 _，其粒徑大部分爲3μπι以上的粒子，更好爲粒徑3〜 的柱狀結晶的銅粒子佔有其大部分者。文中所謂的『佔 有/、大部分』或『主要形成之』係指形成佈線之銅箔中至少 50容積％，較好至少8〇容積％由粒徑爲恤以上、較好 〜ΙΟμηι的柱狀結晶銅所佔有者。 … ，以第圖顯示上述適用於本發明的高氯含量的析出 之曰形狀爲柱狀結晶，且其粒子大部分爲粒徑3哗以上，進 而争乂好大部分由粒徑冑3〜1〇μπι的柱狀結晶之銅粒子所佔 之電〒銅，剖面的電子顯微鏡照片_^_讀像”又嗜第〕 圖顯不作爲比較㈣使㈣膠予⑽絲徑約3()μιη粒狀結晶 IP070215/SF-1609f 12 200806123 之電，銅落剖面的電子顯微鏡照片卿_瓣像）。 粒子之電解銅箱，若係析出上述結晶構造的大 二f 極使用鋼板而在陰極使用鈦電極，以攪液 ㈣。此時的鑛銅液温度係如上述設定ίThe column crystal having a particle diameter of mainly 3 μm or more, which is mainly used for the columnar crystal having a particle diameter of 3 μm or more, which is mainly composed of the above-mentioned wiring base = is different from the above-mentioned wiring base, and does not cause the protein f, such as qing, gelatin, etc., chlorine concentration Dimensions, in the high concentration of 50 to 80 mg / liter per A, preferably 5 〇 ~ 7 〇 mg / liter, 'saki (four) electrical noise is set to normal 丨 ~ withdrawal / such as 2, and ^ set to 1 A lower current density in the range of ~15 A/dm2 causes copper to precipitate out. ^ The concentration of the above chloride ion in the ore solution is the same as that of the chlorine in the general plating solution. The 7H scale is often high, and the liquid is slowly and gradually precipitated. The metal can be transferred to the Within the above 5~=fpm fine. Further, the chlorine crystal having a clear crystal structure of the chlorine concentration is a columnar shape, a port, a particle having a particle diameter of mostly 3 μm or more, and more preferably a copper particle having a columnar crystal diameter of 3 to a large portion. . The term "occupied/mostly" or "mainly formed" as used herein means at least 50% by volume of the copper foil forming the wiring, preferably at least 8% by volume. The columnar shape is larger than the size of the shirt, preferably ~ΙΟηηι The possession of crystalline copper. The figure shows that the above-mentioned high-chlorine-containing precipitation type which is suitable for the present invention is a columnar crystal, and most of the particles have a particle diameter of 3 哗 or more, and further contends that most of the particle diameter 胄 3 〜 1 〇μπι columnar crystal of copper particles accounted for the electron 〒 copper, the electron micrograph of the cross section _ ^ _ read image "has the second" map not as a comparison (four) make (four) glue to (10) wire diameter about 3 () μιη grain Crystalline IP070215/SF-1609f 12 200806123 Electricity, electron micrograph of copper drop profile _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ To stir the liquid (4). The temperature of the ore solution at this time is as set above.
St^ ^^之財，藉蚊電流電解，以電流密度1 杜批φ加^、缺1〜15A/dm2細_電流紅較温和條 $析出銅’含於鍍銅液中的氯離子亦隨著銅析出而導入析出銅St^ ^^之财, by mosquito current electrolysis, with current density 1 Du batch φ plus ^, lack of 1~15A/dm2 fine _ current red milder strips $ precipitated copper 'chloride ions contained in the copper plating solution also Leading out copper and introducing precipitated copper
ΐ ϋ範肋的氯係於銅結晶成長時可決定其結晶構造 較切結晶粒徑。而且’由該極微量的氯對 護錫)等没有任何的不良影響’且在環境保 且在形絲本卿佈驗板之壯，不 $膠類等之形油糾通常朗之蛋白質之綠子或氮原 ϊξι基板’細制上紐之鋪、較好為電解 銅泊形成佈義型’惟做為形成_、_型魏絲板，一般 係使用聚酿亞胺。 又於本發明的佈線基板，以作為軟性印刷佈線基板使用較 有利，但亦得以使用硬質絕緣基板作爲剛性佈線基板使用。 、在本發明的佈線基板中，若將上述電解銅箔與絕緣基板予 以牙貝層Η守，可介由黏著劑使電解銅箔與絕緣基板予以黏貼、或 可不必介由黏著劑而黏貼。 ' ’ 形成由上述般之絕緣基板與電解銅箔所成的基材薄膜 後，可利用微影蝕刻法之蝕刻法，將電解銅箔選擇性钱 所需形狀之佈線圖型。 帝又’於本發明使用之絕緣基板得視需要，可穿設用以組裝 電子構件之裝置孔(device hole)、進行佈線基板定位的定位 IP0702l5/SF-1609f 13 200806123 賴之扣鍵纽(spiOeket hGle)、確認佈線基板 二:之二ί ί性的貫穿孔(thr〇ughh〇le)、折疊該佈線基板使 用枯之佈線折曲縫(sHt)等。 ^上述方式於絕緣基板表面上配置之銅箔表面上塗敷 像而开曰由t形成之感光性樹脂層進行所需圖型的曝光·‘ 董編性樹腊所成之圖型後，以該圖型作爲遮罩材， 子銅v白^讀性_，即可獲得由銅絲成之佈線圖型。 传以ΐΐΪΪίϊ銅11予以選擇性侧形成之佈線圖型，通常 林錄抗觸㈣細re_而形成 抗十分:：===:塗敷 或覆蓋形層後’在自抗銲劑 方法解，或無電解電鑛法之任何一種 隹：本么明中，以無電解電鍍法爲宜。 好為彡成之錫鍍覆層厚度通常爲G.G2〜吻111，較 _ 子的^f ’娜紅鍍錫層中錫粒 化。形成於本發_奸大小而變 =分爲上的柱W銅粒子’二$其:虽 大部分靠1而於_大粒彳 1之柱狀結晶銅 覆層時，則在嗜錫^費展击，右形成例如上述般之無電解錫鍍 上的ί晶ϋ 锡f子ΐ晶具有主要為0·_以 層的錫粒子粒徑增大/、有〜3μιη的粒徑，因此形成錫鍍覆 表面第與3藉圖由顯上么以上的銅柱狀結晶所成之佈線 分之剖面的電子=，解鍍錫法所形成之錫鍍覆層界面部 电子顯雜則。㈣3®卿之町I為形成無電 IP〇7〇2l5/SF.l609f 200806123 片、。又覆層3〇天後之界面部分之暗視野及明視野的顯微鏡照 大部’第^顯示_製造鋪時採用娜所製造之 表面上Γ藉由二上晶鋼所成之銅猪所形成之佈線 部分的電子顯微2二解鍵錫法形成的鍍錫層’其界面 覆声30夭^!ΐ鏡Α片。弟圖所示之照片係形成無電解錫鍍 a由卜、^之界面部分之暗視野及明視野的顯微鏡照片。 綾的論圖及第4圖之比較可知，若形成作爲底層之伟 的=形果成= ZZT-t 之益、時’形成於其表面 之…、電解?賴射稿平均錄無法賴。加。 盈雷iii=及第4圖所示，形成佈線的銅與被覆其表面之 軸_散_職㈣(錫鍍 “，政頃域係由金屬間化合物所成的粒子所 =成。於弟3圖所示之金屬間化合物幾乎為以Cu6Sn5爲主成 ^之粒狀物，且自f觸細(刊⑽ ，銅金屬濃度連續降低之方式形成濃度梯度。該金&化3 的粒徑，相對於其初期階段之大約為〇·1μπι±0·5μιη左右，於 由添加明膠使粒徑變小的粒狀結晶的銅所成之佈線上的 金屬間化合物的粒徑大約為〇〇3μιη士〇〇2μιη左右，且於其初 期階段，該金屬間化合物的粒徑，有形成佈線之銅粒徑愈大之 愈來愈變大的傾向。然而，因該金屬間化合物隨其經過時間而 變化’在經過30天後’金屬間化合物粒徑，相對於在第3圖 中變化停止於0·18μιη±0·05μιη左右，在第4圖所示的銅粒子 較小之情況下，其經過30天後的金屬間化合物粒徑即可達 0·56μπι〇 IP070215/SF-1609f 15 200806123 而以此方式構成佈線的銅粒子爲大粒徑柱狀結晶之 明佈線基板中，銅自該構成佈線之銅向無電解錫鍍 速度較慢，因此’金屬間化合物之經時形成速度亦較f賴政 如上述之金屬間化合物，係藉由於錫中擴散銅離子又 之化合物’且關麵的比率獨，故其域分應爲Cu^或 且亦含有αι4η等之中間成分。由於銅對錫之擴散 5斜 銅之擴散速度爲快，故銅擴散至錫之以Cu6sn5成爲主 擴散領域係形成自銅所成的佈線表面向無電解錫鑛芦 方向之擴散領域。於該擴散領域中之銅擴散並不相同，^ 情況下，形成由銅金屬所成的佈線表面向無電解 而 方向其銅濃度依序降低的銅濃度梯度。 X復層表面 在本發日月的佈線基板’因構成佈線的銅爲柱狀 徑較大，更因其表面之錫結晶亦較大，故銅 = t度變薄。剖系銅離子對錫織層之擴散速度加速時員3土 層發生魏應力，顧馳力觀域成為無電 解錫鐘覆層表面上發生晶鬚之驅動力。 之揭鍍覆層之擴散速度加耕，在形成佈線圖型 線圖型的金屬鍍覆層之間’或於形成佈 該擴散領域之間，發生伴隨銅擴散之卡肯 多個應，形成 因銅料觸鍍纖侧’該鑛細空隙係 徑較月的依線基板，因構成祕的鋼金屬粒 之擴者，若依本發明’因銅離子對錫鍍覆層 '、&銅邊擴散，同時引起錫鍍覆層内的壓縮應力 IP070215/SF-1609f 16 200806123 缓和，因而’不容易在錫鍍覆層中累積成為産生錫晶鬚之驅動 力之壓縮應力。 因此，在本發明的佈線基板中，形成鍍錫層時之錫晶鬚產 生程度，與習用者幾乎相同而無變化，但隨著時間經過，由本 發明固有的構成，因銅離子向錫鍍覆層進行擴散的速度缓慢而 顯示所發生之晶鬚的發生根數並無顯著增加之特異傾向。 弟5圖顯示係將如上述般採用明膠製造較小粒徑之粒狀 粒子所成之銅箔所製造的印刷電路基板在室温下，其經時晶鬚 發生根數以光顯微鏡測定之例中，晶鬚發生根數以「△」符號 標示，且滿足本發明要件之佈線基板上發生的晶鬚根數，以「」 響 符號予以標示。 由第5圖可知，在形成無電解錫鍍覆層後之〇〜1〇天左左 右’本發明的佈線基板與比較例之佈線基板所發生的晶鬚根數 量一般没有太大差別。然而，於該期間，在比較例i之^線基 板中’銅離子向錫鐘覆層中急速擴散，相對地，以本發明之實 施例1製造的佈線基板’因構成佈線的銅粒徑較大且係具有柱 狀結晶之關係’銅離子向錫鑛覆層的擴散緩慢，故於無電解錫 鏡覆層中銅離子的擴散，將停留在銅與無電解錫鍍覆層界面附 近，故其擴散前端部未到達無電解锡鍍覆層表面附近。爲此， • 在無電解錫鍍覆層中因銅離子擴散而產生的壓縮應力累積極 少’故形成無電解錫鍍覆層後超過10天起的錫晶鬚發生根數 有顯著的差別。 ^ 也就是説，形成佈線之銅結晶粒徑小的情況下，隨著銅向 錫鍍覆層進行擴散而經時發生的錫晶鬚根數增多，且於形成無 電解錫鍍覆層後之10天左右開始轉爲晶鬚根數急速增加。& 如本發明之佈線基板般形成配線之銅成為大粒徑柱狀结晶，即 可使經時的錫晶鬚發生量的增加減少。如第5圖所示Γ本發明 之佈線基板經過30天後的錫晶鬚發生根數通常爲2〇〇榍/rm2 以下，其《祕板巾錫發錄 IP070215/SF-1609f 17 200806123 如上述，因鋼的擴散、缓慢’故麵與錫界面部，實 男上/又有由銅急速擴散而產生之卡肯道爾(力_欠蚪、、_ 且在無電解錫鍍覆層中(或界面部分），没有: 急遠擴散導致之應力集中。 ] 又上述说明中，僅係爲説明構成佈線 曰 解錫鍍覆層界面部中錫 鍍覆層被覆之佈、線進行熱處理等的銅 mm，惟只魏行用於使銅離子擴 僅能在絲面介由擴散領域形絲電解錫 散領域、雜之形麟各項，賴上仍健战 擴 於所明的銅離子擴散領域，係在無電解 ^ ^ CueSn^ Cu3Sn；i 銅的擴散領域能到達無電解錫鍍覆層表 ic 為Ϊ他實施方式，替代純鍚電鍍而進行Sn_Ag、 效果。η ”。之^有％的金屬電鍍者，可獲得與上述同様 [實施例] τ，m?*本發明的佈線基板’以實施例予以具體説明如 下仁本發明不限於實例所提示者。 [實施例1] 游離时料:、 該嫂銅液作域準鍍。該基準鍵銅“不含氣i子及有ϊ BP070215/SF-1609f 18 200806123 物質 添加巾使C1離子4成爲5G吨/公升的方式 中含膠之鑛銅液⑴。又該物。 温度=爲=二屬方，極，調整鍍， 以製造平均厚度25师的電解銅y。邊在鈦金屬板面析出_， 箱中^== 進行氯之精_結果，在該電解鋼 ΪΪΓ分為練為5/zm雜狀結晶。 忐而F泠敁造的電解銅箔（厚度爲25叫η)之銅析出办 分餘1基轉_崎_酸，^ 4體〇〒加熱而獲仵聚酿亞胺薄膜(厚度:4。㈣/電職的J層 _ ，層體之冑軸絲面錄感紐樹脂形 成Ϊ姐树月曰層’再將該感光性樹脂層予以曝光•顯像而侃、 由感光性樹脂之硬化物所成之^ (_ldngH 成 列。使用上述方式形成之遮蔽材料對電解銅箔進行選擇性韻 形成^3淨去除上述遮蔽材料後，以露出端子部分之方式再 其次’在露㈣端子部分以市料無電解顯覆液形 度0·5μπι的錫鐘覆層，而製成佈線基板。 以該方式製造的佈線基板端子部分的剖面示於第 3圖係形成顯覆層後，在室温經過3G天後之同處剖。 在其初期階段既有之金屬間化合物（主成分爲Cue 徑在室溫下於30天内成長爲粒徑。 ’ 然而，於形成佈線之銅與錫鍍覆層的界面部並未觀察到因 BP0702I5/SF-1609f 19 200806123 卡肯這爾.竹卜、、喝效應而形成的所謂空隙。 自如此所得之佈線基板產生之錫晶鬚根數示於第5圖。 [實施例2] 於只施例1中，改變所添加的濃鹽酸量，調製氯含有率爲 3了 ppm的電解銅箔。除使用該電解銅箔以外，以同様條件， 形成佈線圖型，且在該佈線圖型表面形成厚度〇·5μιη之無電解 ，鍍覆層。而對該佈線基板進行與實施例1同様的晶鬚根數測 疋的結果’其測出根數係略同以實施例1製造之佈線基板中的 晶鬚發生根數。 [比較例1] 在實施例1中，取代形成該電解銅箔時所使用之鍍銅液 (1) ’不添加鹽酸，而代之添加50 mg/公升之量的明膠量，此 外以同様操作條件調製鍍銅液(2)，除使用該鍍銅液(2)以外， 以同樣操作製造佈線基板。惟該鑛銅液(2)中不含有氯離子。 所传之佈線基板端子部分剖面示於第4圖。在其初期階段 形成既有之金屬間化合物，其主要成分爲Cu6Sn5且粒徑爲 〇·〇3μιη。該等錫鐘覆層剛开》成後的金屬間化合物之粒徑較小， 故形成佈線的銅粒徑小，且係粒狀結晶的關係，銅對錫鍍覆層 的擴散速度快速，其在室温經過30天後之金屬間化合物粒徑 成長至0.560μιη。 隨著上述金屬間化合物的生成，在銅與錫鍍覆層之界面部 分’多數發生因卡肯道爾效應而形成之空隙，亦可由光學顯微 鏡看出多個晶鬚。 自如此所得的佈線基板發生之錫晶鬚根數示於第5圖。 若在以銅所成之端子表面上被覆錫鍍覆層，因銅離子向錫 鑛覆層擴散，藉由該擴散在錫鍍覆層發生壓縮應力。因而認為 於錫鍍覆層表面產生之錫晶鬚形成，係成為因銅擴散而在錫鍍 覆層上發生壓縮應力之驅動力，如上述比較例1，若對該錫鍍 覆層以穩定提供銅的形態形成佈線，則對錫鐘覆層連續不斷地 IP070215/SF-1609f 20 200806123 應力，且时肯韻絲而發生錄雜。 _ _ίί 5圖所示，於形成贿覆層後，在初期階段，雖|法 小及結日日日構造對於發生晶鬚的較大影響，但隨著 ’具體上，自形祕鍍覆層後經歷 m 4 發生Βθ讀數的差別開始較爲明顯，故於經過20天、 天時’可發覺發生晶迦數能大差別。 在^表面上形成錫鍍覆層時，在錫紐層内擴散銅，惟於 ϋ除因伴隨銅擴散作用產生之應力而生成錫晶鬚現 彼與、±由、？；、、、而’如上述詳述，得以了解銅離子對錫鍍覆層之 二晶鬚形成帶來極大影響。因此，在本發明，藉由限 二ίί佈ί®^_粒徑及其結晶形狀，和限_離子之擴 政速度’得以實現使錫晶鬚發生根數減少。 、 [比較例2] ρ 2+ί實施例1中，除使用將硫酸及硫酸銅五水合物調製爲 曲U f為8Gg/公升、游離时為15Gg/公升、氯離子 ^為1.5 mg/公升、明膠3 6 mg/公升之細液以外，係與 j列1同様方式形成電解銅落，除使用該電解銅猪以外 樣衣造佈線基板。 广曲所得的佈線基板予以檢視結果，雖形成佈線圖型的銅中之 爲JO ppm，但確認在該銅中有氯及起因於明膠的碳原 子存在。爲此’該銅具有不爲柱狀結晶的粒狀結晶，且因該牡 控較小’而輯無電觸層之概瞬絲，故於^ 與無電解錫鑛覆層之界面發現多數空隙。 [産業上的利用可能性] 本發明的佈線基板，於構成在該佈線基板上形成的佈線圖 型之佈線’由主要為粒徑3 〇μηι的拄狀結晶所形成，因而，較 構一般佈線基板上所形成之佈線之銅粒子粒徑顯著更 大。右在自該大粒徑之柱狀結晶形成的佈線表面形成無電解錫 IP070215/SF-1609f 21 200806123 鍍覆層時，則形成該無電解錫鍍覆層之錫粒子的粒徑亦大。於 ^有，雜子構成的鑛線及無t解難覆層所成的佈線 中，在無電解錫鍍覆層内的銅擴散速度顯著降低， ，乎不發生_離子擴翻起之讨顧效應而 隙’且於無電解錫鍍覆層内因銅離子擴散而產生的壓縮應力不 ^累積在無電解錫織層中。錫晶鬚之發生‘騎力為錫^覆層 =之上述壓縮應力，於本發明的佈線基板中，由於銅的擴散較 忮，故其擴散而在無電解錫鍍覆層中累積的壓縮應力，故 不容易發生錫晶鬚。 口此本發明付以在製造微細的細線化佈線基板時，使端 子間距、端子間的距離狹窄化要求的佈線 晶鬚發生所致之短路現象，故其實用性極高。乍為防止口 【圖式簡單說明】 第1圖係適用於本發明的析出銅結晶形狀爲柱狀結晶，且 二大部分粒子的粒徑爲恤以上之電解銅細面的電子臟 鏡照片（FIB-SIM像）。 ，第2圖係採用明膠予以形成之粒徑爲約〇·3μιη之粒狀結晶 所形，之電解銅箔的電子顯微鏡照片斤迅名服像）。 第3圖為在大部分係由3μηι以上的銅之柱狀結晶所成之 佈線表面，與藉由上述無電解鍍錫法形成之錫鍍覆層的界面部 分之電子顯微鏡照片（STEM像)。 第4圖為製造銅箔時採用明膠，於使用大部分爲〇·3μιη左 右的粒狀結晶銅所成的銅箱所形成之佈線表面，與上述同様藉 由無電解鍍錫法形成的錫鍍覆層之界面部分的電子顯微鏡^ 片(STEM像）。 、 … 第5圖係表示以如上述般採用明膠製造較小粒徑之粒狀 粒子所成銅、冶所製造的印刷佈線基板之經時晶鬚發生數量的 圖表例，及由本發明之較大粒子之柱狀結晶所成/的佈線基板之 經時晶鬚發生數量的圖表例。 IP070215/SF-1609f 22 200806123 【主要元件符號說明】 23 IP070215/SF-1609fThe chlorine of the 肋 ϋ rib can determine the crystal structure and the crystal grain size when the copper crystal grows. Moreover, there is no adverse effect on 'the trace amount of chlorine on the tin), and it is in the environment and is strong in the shape of the silk. It is not the shape of the oil. Sub- or Nitrogen ϊξ ι substrate 'finely laid on the shop, preferably electrolytic copper to form a cloth type 'only as a form _, _ type Wei wire plate, generally using poly-imine. Further, the wiring board of the present invention is preferably used as a flexible printed wiring board, but a rigid insulating board is also used as the rigid wiring board. In the wiring board of the present invention, when the electrodeposited copper foil and the insulating substrate are adhered to the gutta-percha layer, the electrodeposited copper foil and the insulating substrate can be adhered via an adhesive or can be adhered without an adhesive. After forming a base film formed of the above-described insulating substrate and electrolytic copper foil, the electrolytic copper foil can be selectively used in a wiring pattern of a desired shape by an etching method using a photolithography method. Emperor's insulative substrate used in the present invention can be worn as needed to assemble a device hole for assembling an electronic component, and to position the wiring substrate. IP0702l5/SF-1609f 13 200806123 Lai Zhikou Key (spiOeket hGle), confirming the wiring board 2: the two through holes (thr〇ughh〇le), and folding the wiring board using the dry wiring bending seam (sHt). ^In the above-mentioned manner, after applying a pattern on the surface of the copper foil disposed on the surface of the insulating substrate and opening the photosensitive resin layer formed of t to perform the exposure of the desired pattern, the pattern formed by the Dongbian tree wax, The pattern is used as a masking material, and the copper is white and the reading is _, and the wiring pattern formed by the copper wire can be obtained. Passing 布线ίϊ copper 11 to selectively form the wiring pattern, usually Lin recorded anti-touch (four) fine re_ and formed anti-million::===: after coating or covering the layer 'in the self-resistance method solution, or Any type of electroless ore method: In this case, electroless plating is preferred. Fortunately, the thickness of the tin plating layer is usually G.G2~ kiss 111, which is tinned in the tin plating layer of the ^f ’ Na red. Formed in this hair _ traits change = divided on the column W copper particles 'two $. It: Although most of the 1 to the _ large grain 彳 1 columnar crystal copper coating, then in the tin The right-handed, for example, electroless tin plating on the above-mentioned electroless tin plating, tin tin sub-twisted crystal has a particle size of mainly 0·_ layer of tin particles increased, and has a particle size of 〜3 μm, thus forming tin plating The electrons of the cross section of the wiring formed by the copper columnar crystals having the above-mentioned surface and the above-mentioned graph are the electrons of the tin plating layer formed by the anti-tinning method. (4) 3® Qingzhi Town I is formed without electricity IP〇7〇2l5/SF.l609f 200806123 piece. The dark field of the interface part of the coating after 3 days and the microscope of the bright field of the most part of the 'the first display _ the shop was made by the copper pig formed by the two upper crystal steel. The electron microscopy of the wiring part 2 is formed by the tin-plated layer formed by the tin-solution method. The interface is covered with sound 30 夭 ^! The photograph shown in the figure shows the dark field of the interface portion of the electroless tin plating and the microscopic photograph of the bright field. A comparison between the map of 绫 and the map of Fig. 4 shows that if the formation of the bottom layer is = the benefit of ZZT-t, the time is formed on the surface of it, and the electrolysis? plus. Yinglei iii= and Fig. 4 show that the copper forming the wiring and the axis covering the surface thereof are scattered (4) (tin plating), and the political domain is composed of particles made of intermetallic compounds. The intermetallic compound shown in the figure is almost a granular material of Cu6Sn5, and a concentration gradient is formed from the f-contact (10), the concentration of copper metal is continuously decreased. The particle size of the gold & The particle size of the intermetallic compound on the wiring formed by the copper of the granular crystal which is reduced in particle size by adding gelatin is about 〇〇3μιη relative to the initial stage of about 1·1μπι±0·5μιη. 〇〇2μηη, and in the initial stage, the particle size of the intermetallic compound tends to become larger as the particle size of the copper forming the wiring becomes larger. However, the intermetallic compound varies with the elapsed time. 'After 30 days, the particle size of the intermetallic compound stopped at about 0.18μηη±0·05μιη relative to the change in Fig. 3, and the copper particle shown in Fig. 4 was smaller than 30. The particle size of the intermetallic compound in the day can reach 0.56μπι〇IP070215/SF -1609f 15 200806123 In the case where the copper particles constituting the wiring in this manner are large-sized columnar crystals, the copper is plated from the copper constituting the wiring to the electroless tin plating rate, so that the intermetallic compound has a warp time. The formation rate is also higher than that of the above-mentioned intermetallic compound, because the compound which diffuses copper ions in tin and the ratio of the closing surface is unique, the domain should be Cu^ or also contain intermediate components such as αι4η. Due to the diffusion of copper to tin, the diffusion rate of oblique copper is fast, so copper diffuses to tin. Cu6sn5 becomes the main diffusion field, and the wiring surface formed from copper forms a diffusion field toward the electroless tin ore. The diffusion of copper in the diffusion field is not the same. In the case of the copper, the copper concentration gradient is gradually reduced in the direction of the electrolessness of the wiring surface formed by the copper metal. The substrate 'is a large columnar diameter due to the copper constituting the wiring, and the tin crystal on the surface is also larger, so the copper = t degree becomes thinner. The diffusion rate of the copper ion to the woven layer is accelerated when the diffusion speed of the woven layer is 3 Wei stress occurs, Gu The self-powered field becomes the driving force for whiskers on the surface of the electroless tin-tin coating. The diffusion speed of the plating layer is increased and the ploughing is formed between the metal plating layers forming the wiring pattern pattern. Between the diffusion areas of the cloth, a multiple of Kaken with the copper diffusion occurs, and the copper substrate is formed on the side of the plating side of the copper material. According to the present invention, the "copper ion-to-tin plating layer", & copper edge diffusion, and at the same time cause the compression stress in the tin plating layer IP070215/SF-1609f 16 200806123 to be moderated, thus 'not easy to tin plating layer It is accumulated as a compressive stress that generates the driving force of tin whiskers. Therefore, in the wiring board of the present invention, the degree of generation of tin whiskers in forming the tin-plated layer is almost the same as that of the conventional one, but does not change with time, but with the passage of time, the copper ion is plated to tin by the structure inherent to the present invention. The rate at which the layer diffuses is slow and shows a specific tendency that the number of generated whiskers does not increase significantly. FIG. 5 shows an example in which a printed circuit board made of a copper foil made of gelatin particles having a smaller particle size as described above is subjected to light microscopy at room temperature at room temperature. The number of whiskers generated is indicated by the symbol "△", and the number of whiskers occurring on the wiring substrate satisfying the requirements of the present invention is indicated by a "" symbol. As is apparent from Fig. 5, the number of whiskers generated in the wiring substrate of the present invention and the wiring substrate of the comparative example is generally not greatly different after the formation of the electroless tin plating layer. However, during this period, in the wire substrate of Comparative Example i, 'copper ions rapidly diffused into the tin-bell cladding layer, and the wiring substrate manufactured by the first embodiment of the present invention was relatively smaller in the copper particle diameter of the wiring. The large relationship has the relationship of columnar crystals. 'The diffusion of copper ions into the tin ore coating is slow, so the diffusion of copper ions in the electroless tin mirror coating will stay near the interface between copper and electroless tin plating. The diffusion front end portion does not reach the vicinity of the surface of the electroless tin plating layer. For this reason, • The accumulation of compressive stress due to the diffusion of copper ions in the electroless tin plating layer is extremely small. Therefore, there is a significant difference in the number of tin whiskers generated after 10 days from the formation of the electroless tin plating layer. ^ In other words, when the copper crystal grain size of the wiring is small, the number of tin whiskers that occur over time as the copper diffuses into the tin plating layer increases, and 10 after the formation of the electroless tin plating layer The number of whisker roots increased rapidly around the day. & The copper in which the wiring is formed as in the wiring board of the present invention becomes a columnar crystal having a large particle diameter, that is, the increase in the amount of tin whisker which is formed over time is reduced. As shown in Fig. 5, the number of tin whiskers generated after 30 days of the wiring substrate of the present invention is usually 2 〇〇榍 / rm 2 or less, and the "small sheet of tin foil is issued by IP070215/SF-1609f 17 200806123 as described above. Due to the diffusion of steel, the slow 'face and tin interface, the real male / there is a rapid diffusion of copper generated by the Karken Doyle (force _ 蚪, _ and in the electroless tin plating layer (or In the above-mentioned description, only the copper and mm which are used for the heat treatment of the cloth and the wire covered with the tin plating layer in the interface portion of the wiring tin-plated layer are described. However, only Wei Xing is used to expand the copper ion only in the field of filaments in the field of diffusion of filaments, and in the field of miscellaneous shape, and it is still in the field of copper ion diffusion. In the field of electroless ^ ^ CueSn ^ Cu3Sn; i copper diffusion can reach the electroless tin plating layer table ic is the implementation method, instead of pure germanium plating for Sn_Ag, effect. η ”. The same as the above [Embodiment] τ, m? * The wiring substrate of the present invention is The embodiment will be specifically described as follows. The present invention is not limited to the examples. [Example 1] Free time material: The copper bismuth solution is used as a quasi-plating layer. The reference key copper "does not contain gas i and has ϊ BP070215/ SF-1609f 18 200806123 Substance-added towel makes C1 ion 4 into a 5G ton / liter-containing colloidal copper liquid (1). This product is also temperature. = Temperature = = two, square, adjusted plating, to produce an average thickness of 25 The electrolytic copper y of the division is deposited on the surface of the titanium metal plate, and the ^^= in the box is subjected to the fineness of chlorine. The result is that the electrolytic steel is divided into 5/zm heteromorphic crystals. Electrolytic copper foil (thickness 25 is called η), copper precipitation office, 1 basis, _ _ _ acid, ^ 4 body 〇〒 heating to obtain 仵 酿 酿 亚 ( ( 厚度 厚度 厚度 厚度 厚度 厚度 厚度 厚度 厚度 厚度 厚度 厚度 厚度 厚度 厚度 厚度 厚度 厚度 厚度 厚度 厚度 厚度 厚度 厚度_ , the layer of the 胄 丝 丝 丝 纽 纽 纽 纽 纽 纽 ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光Column. The selective forming of the electrolytic copper foil by using the masking material formed in the above manner is performed to remove the above-mentioned shielding material to expose the terminal portion. Next, a wiring board is formed by coating a tin-bus with a liquid crystal of 0. 5 μm in the terminal portion of the exposed (four) terminal portion. A cross section of the terminal portion of the wiring substrate manufactured in this manner is shown in FIG. After the coating is over, it is cut at the same time after 3G days at room temperature. In the initial stage, there are intermetallic compounds (the main component is Cue diameter which grows to the particle size within 30 days at room temperature. ' However, in the formation of wiring The so-called void formed by the effect of BP0702I5/SF-1609f 19 200806123 Kaken, and the effect of drinking was not observed at the interface between the copper and the tin plating layer. The number of tin whiskers generated from the thus obtained wiring substrate is shown in Fig. 5. [Example 2] In Example 1 alone, the amount of concentrated hydrochloric acid added was changed to prepare an electrolytic copper foil having a chlorine content of 3 ppm. In addition to the use of the electrolytic copper foil, a wiring pattern was formed under the same conditions, and an electroless plating layer having a thickness of 〇·5 μm was formed on the surface of the wiring pattern. On the other hand, the result of the measurement of the number of whiskers in the same manner as in the first embodiment was as follows. The number of detected whiskers was slightly the same as the number of whiskers in the wiring substrate produced in the first embodiment. [Comparative Example 1] In Example 1, instead of adding hydrochloric acid, the copper plating solution (1) used when forming the electrolytic copper foil was added, and the amount of gelatin in an amount of 50 mg/liter was added instead, and the operation was performed in the same manner. The copper plating solution (2) was prepared in the same manner, except that the copper plating solution (2) was used, and the wiring substrate was produced in the same manner. However, the ore solution (2) does not contain chloride ions. A cross section of the terminal portion of the wiring board to be transferred is shown in Fig. 4. In the initial stage, an existing intermetallic compound is formed, the main component of which is Cu6Sn5 and the particle size is 〇·〇3μιη. Since the particle size of the intermetallic compound immediately after the formation of the tin-bell coating is small, the copper particle diameter of the wiring is small, and the relationship between the granular crystal and the diffusion speed of the copper-tin plating layer is rapid. The intermetallic compound particle size was increased to 0.560 μm after 30 days at room temperature. With the formation of the above intermetallic compound, a large number of voids formed by the Karkendorf effect occur at the interface portion between the copper and the tin plating layer, and a plurality of whiskers can be seen by an optical microscope. The number of tin whiskers generated from the thus obtained wiring substrate is shown in Fig. 5. When a tin plating layer is coated on the surface of a terminal made of copper, copper ions are diffused into the tin ore deposit, and compressive stress is generated in the tin plating layer by the diffusion. Therefore, it is considered that the tin whisker generated on the surface of the tin plating layer is a driving force for generating a compressive stress on the tin plating layer due to copper diffusion, and as in the above Comparative Example 1, if the tin plating layer is stably provided In the form of copper, the wiring is formed, and the tin-bell coating is continuously subjected to IP070215/SF-1609f 20 200806123 stress, and the recording occurs when the wire is twisted. _ _ίί 5 shows that after the formation of the bribe cover, in the initial stage, although the structure of the small and the day of the day has a greater impact on the occurrence of whiskers, but with the 'specifically, the self-formed plating layer After the occurrence of the m 4 occurrence Β θ reading difference is more obvious, so after 20 days, the day can be found to have a large difference in the number of crystals. When a tin plating layer is formed on the surface of the ^, copper is diffused in the tin-nuclear layer, but the tin whiskers generated by the stress accompanying the diffusion of copper are removed, and the ? ; , , and ' As detailed above, it is understood that copper ions have a great influence on the formation of the whisker of the tin plating layer. Therefore, in the present invention, the number of tin whiskers is reduced by limiting the particle size and its crystal shape, and the rate of expansion of the ion-limited ion. [Comparative Example 2] ρ 2+ί In Example 1, except that sulfuric acid and copper sulfate pentahydrate were used to prepare a curve of U G of 8 Gg / liter, 15 Gg / liter when free, and 1.5 mg / liter of chloride ion ^ In addition to the fine liquid of gelatin of 3 6 mg/liter, an electrolytic copper drop is formed in the same manner as in the first column, and a wiring substrate is prepared in addition to the electrolytic copper pig. As a result of the inspection of the wiring board obtained by the koji, it was confirmed that JO-25 was formed in the copper of the wiring pattern, but it was confirmed that chlorine was present in the copper and carbon atoms due to gelatin were present. For this reason, the copper has a granular crystal which is not columnar crystal, and since the kiln is small, and the electro-contact layer is not integrated, a large number of voids are found at the interface between the electroless tin ore coating. [Industrial Applicability] The wiring board of the present invention is formed of a meandering crystal having a particle diameter of 3 〇μηι in a wiring pattern formed on the wiring board, and thus a general wiring is formed. The copper particles of the wiring formed on the substrate have a significantly larger particle size. When the electroless tin IP070215/SF-1609f 21 200806123 plating layer is formed on the surface of the wiring formed of the large-sized columnar crystal, the particle size of the tin particles forming the electroless tin plating layer is also large. In the wiring formed by the heterogeneous ore and the uncoated layer, the copper diffusion rate in the electroless tin plating layer is remarkably lowered, and the effect of the _ ion expansion is not observed. The compressive stress generated by the diffusion of copper ions in the electroless tin plating layer does not accumulate in the electroless tin layer. The occurrence of tin whiskers is the above-mentioned compressive stress of the tin-cladding layer. In the wiring substrate of the present invention, since the diffusion of copper is relatively high, the compressive stress accumulated in the electroless tin plating layer is diffused. Therefore, tin whiskers are not prone to occur. In the present invention, the short-circuit phenomenon caused by the occurrence of wiring whiskers required to narrow the terminal pitch and the distance between the terminals when manufacturing a fine thin wiring substrate is extremely practical.乍 防止 防止 【 【 【 【 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 FI FI FI FI FI FI FI FI FI FI FI FI FI FI FI FI FI FI FI FI -SIM like). The second figure is a granular crystal formed by gelatin and having a particle size of about 〇·3μιη, and an electron micrograph of the electrolytic copper foil is taken as an image. Fig. 3 is an electron micrograph (STEM image) of an interface portion between a wiring surface formed of a columnar crystal of copper of 3 μη or more and a tin plating layer formed by the electroless tin plating method. Fig. 4 is a view showing a wiring surface formed by using a gelatin in a copper foil to form a copper box made of a granular crystal copper which is mostly about 3 μm, and a tin plating formed by electroless tin plating. Electron microscopy (STEM image) of the interface portion of the coating. Fig. 5 is a diagram showing an example of the number of occurrences of the time-dependent whiskers in the printed wiring board produced by using the gelatin particles having a smaller particle size by gelatin as described above, and larger by the present invention. An example of the number of occurrences of the time-dependent whiskers of the wiring substrate formed by the columnar crystals of the particles. IP070215/SF-1609f 22 200806123 [Explanation of main component symbols] 23 IP070215/SF-1609f