201247946 六、發明說明: 【潑^明戶斤屬之·技:彳标$貝域^】 發明領域 本發明係關於一電鍍方法,且更特別地,係關於一電 鑛方法’其有利於用於裝填諸如銅之金屬進入在該基板之 製造中的該等通孔中,諸如一半導體基板或其等之類,該 基板在其内部具有許多垂直穿透的通孔柱(孔栓塞),且可使 用於所謂半導體晶片之三維封裝中。 【先前技術3 發明背景 形成諸如銅之一金屬通孔柱,垂直穿透過一半導體基 板,之技術係知悉為電連接半導體基板多層堆疊之該等層 的方法。 第1A至1C圖顯示一示範性方法,用於製造在其中具有 銅通孔柱之一基板。首先’如第1A圖中所顯示,一基 板W係藉由在一基底1〇,諸如一矽晶圓,中形成數個向上 開口之通孔而製備的,例如藉由使用該光刻/蝕刻技術;在 該基底10之表面上,包括通孔12之側壁,形成一介電薄膜 (未顯示的),例如藉由PVD ;在該基底10之整個表面上,包 括通孔12之内部表面,形成諸如Ti(鈦)之一金屬障蔽層14, 且然後在該障蔽層14表面上形成一銅種子層16。該通孔12 之直徑,,d”係為,舉例而言,2至50μιη,特別是1〇至2〇μηι, 且該通孔12之深度”h”係為,舉例而言,20至150μηι。 接者’銅電鑛係使用該銅種子層16做為一陰極在該基 201247946 板W表面上實行,從而裝填一電鍍金屬(銅)18至該通孔中, 並沈積該電鍍金屬18至該銅種子層16之表面上,如第1B圖 中所顯示。在藉由銅電鍍嵌入銅至該通孔12之此一事例 中,一硫酸銅電鍍溶液係廣泛地使用做為一電鍍溶液,該 者相對地係不昂貴且相對地係容易控制的,包括其廢物處 理〇 其後,如第1C圖中所顯示,在該基底10上之額外的電 鍵金屬18、銅種子層16與障蔽層14係移除的,例如,藉由 化學機械拋光(CMP)。進一步的,該基底10之後表面側係拋 光掉,例如,至由第1C圖中兩點鏈線所顯示之該位置,從 而曝露嵌入於該通孔12中之該電鍍金屬18的底部面。該基 板W在其中具有銅(電鍍金屬18)通孔柱,垂直穿經由該基板 W,可以在此方式中製造。 該通孔12—般地具有一高的高寬比,意即,深度對直 徑比,並具有一大的深度。為了徹底地裝填銅(電鍍金屬) 至此種通孔12中,具有一高的高寬比及一大的深度,藉由 電鍵而不製造諸如在該嵌入金屬中的孔隙的缺陷,其係通 常必要在一底部-向上方式中執行該電鍍,以容許該電鍍金 屬優先地從該通孔12之底部生長。 此種底部-向上電鑛一般地係藉由使用一硫酸銅電鍍 溶液而實行,該者含有各種添加劑,諸如sps(二硫化(雙 石《丙基))(bis (3-sulf〇pr〇pyi) disulfide)做為一電鑛加速劑、 PEG(聚⑽乙二醇)做為—抑㈣、及pm(聚乙烯亞胺)做為 一均勻劑。這些添加劑在其吸收至一基板表面之後發揮它 201247946 們的效果。 PVD —般地具有一低的階梯覆蓋性(step coverage)。所 以’假若該連續的銅種子層16係藉由PVD在該障蔽層14表 面上形成’然後該連續的銅種子層16需要具有一頗大的厚 度,舉例而言,在從800 nm至1000 nm之該範圍中。必然地, 對較小厚度之種子層係有一需求。 如第2圖中所顯示,其已為可理解的是藉由一同形 (conformal)CVD製程在基底10之整個表面上,包括該等通 孔12之表面,形成一鈷薄膜20做為一種子層,該者兼做為 一障蔽層。然後’一銅電鍍製程係於做為陰極之該鈷薄膜 20上實行,以一電鍍金屬,意即銅,嵌入該通孔12。 C發明内容3 發明概要 然而’以諸如銅或其等之類的金屬依據一電鍍製程徹 底地裝填該等通孔12而不產生未裝填的地帶係頗為困難 的,該等通孔具有由該鈷薄膜20覆蓋之表面且具有一高的 南寬比與一大的深度。 舉例而言,如第3圖中所顯示,一基板w係製備的▲ 者之表面係由一鈷薄膜覆蓋,並具有數個具有1〇叫^直彳承嶽 約ΙΟΟμιη深度之通孔12a。當此基板|之表面係使用含^各 種添加劑之一硫酸銅電鍍溶液電鍍,以一電鍍金屬Μ納 入該等通孔12a時,未裝填地帶22a其具備頗粗糙表面者^ 向於在該等通孔12a之大的底部部分形成。 鈷薄骐覆 第4圖顯示另一基板W,該者之表面係以 201247946 蓋且具備數個具有20μηι直徑與約120μηι深度之通孔12b。 當此基板Wq面係❹含有各種添加 劑之一硫酸銅電鍍 溶液電嫂’以—電鍍金屬18銅嵌入該等通孔l2b時未裝填 地帶22b其具備頗粗糙表面者傾向於在該等通孔12b之大的 底部部7刀形成’且裝填在該等通孔12b中之銅易具有不同的 長度。 第5圖顯不還一基板w,該者之表面係以一鈷薄膜覆 蓋且具有數個具有3〇μηι直徑與約130μηι深度之通孔12c。 备此基板W之表面係使用含有各種添加劑之一硫酸銅電鍍 '、液電鑛以電鑛金屬18銅嵌入該等通孔12c時,該電鍵 金屬18銅係僅僅在料通孔12。之上部内表面上生長。該生 長的電鑛金屬18不會封閉該等通孔12c之開口端 ,未能以該 電鍍金屬18徹底地嵌入該等通孔12〇。 如上文所描述,以一銅電鍍金屬,依據使用硫酸銅電 鍍洛液之一電鍍製程完全地嵌入通孔而不產生未裝填地帶 係非谷易的,该等通孔之表面係以一鈷薄膜覆蓋且具有一 高的高宽比與-大的深度。針對未能完全地獻該等通孔 之理由’係為相信的是,在該電鍵製誠間減薄膜係 溶解於該錢銅電鑛溶液中,該者储由與該酸性硫酸銅 電鑛溶液直接賴。具體地,假若難子狀金屬係為較 不惰㈣金;| ’諸如Μ ’意即假若該種子層之金屬具有較 氫大的離子化趨勢’然後該種子層係溶解於―酸性電鑛溶 液。 忒鈷溥膜,意即,該種子層,溶解於電鍍溶液中之該 201247946 門題’4路了其本身’尤其是在該基板外部㈣表面的接觸 區域,該等區域接觸—密封構件其防止或密封該外部周圍 表面’與其鄰近地帶,免受該錢溶液傷害。具體地,該 、4膜在與4基板外部周圍表面的接觸區域與其鄰近地帶 -較高速率溶解’因為—電鑛薄膜係較不可能沈積於 這些局部區域上’歸因於在這些局部區域中該電場係被封 鎖的。該基板—般係從與藉由該密封構件免受該電鑛溶液 傷害之錄板2G的外部卵表面接_而供應電流。假若 在邊基板與其之鄰近地帶之該外關表面的接觸地帶上之 3亥錄薄膜係被溶解掉,驗該電流係被防止在沒有該種子 層存在下’意即’該料膜,流動至該基板。 『:驗性焦魏鋼電鍵溶液將為-可使用的溶液。然 而’該焦璘__溶液較該硫_電舰㈣更昂貴 的’且使得該電鍍溶液管理更為複雜,包括廢物處置。貝 ^種子層轉於酸性f麟液之該問題㈣# —姑薄膜 〈表面係、以銅魏時出現,還有當具有-較氫大之離子化 趨勢的金屬表面係電鍍以另-金屬時出現。 L於上文情況,本發明已經製作。所以本發明之—目 的係為提供1鍍料,該方法當具備具有-較氫大之離 』(勢之金屬種子層的基板係使用諸如硫酸銅電鑛溶液 Μ·生電鑛溶液電鍍時,能夠確實地以諸如 電錢金屬嵌人通孔。 的 了貫現上文目的,本發明提供一電 包含製備-基板,在其表面具有以一第一金屬覆;之= 201247946 孔,該第一金屬具有一較氫大的離子化趨勢,藉由在一前 處理溶液中浸入該基板來前處理該基板,而在該前處理溶 液中,較該第一金屬更為惰性之一第二金屬或其等之鹽類 係溶解的,且然後電鍍該基板之表面以在該通孔中嵌入該 第二金屬或一第三金屬。 由於該基板,在其表面具備以具有較氫大之離子化趨 勢之第一金屬覆蓋之通孔,係藉由在一前處理溶液中浸入 該基板來前處理,在該前處理溶液中,較該第一金屬更為 惰性之第二金屬或其等之鹽類係溶解的,較該第一金屬更 為惰性之第二金屬的金屬薄膜係藉助於代換在該第一金屬 之表面上形成。當該基板之表面係電鍍時,該第一金屬係 被防止與一酸性電鍍溶液直接地接觸且被溶解於該酸性電 鍍溶液中,從而確實地嵌入該電鍍金屬於該等通孔中。 該前處理溶液較佳地應於從略微酸性程度至略微鹼性 程度之該範圍中,從而以防止該第一薄膜,諸如一鈷薄膜, 一旦與該前處理溶液接觸便溶解於其中。 較佳地,先於藉由在該前處理溶液中浸入該基板來前 處理該基板之前,該基板應藉由在該脫氣水中浸入該基板 來前處理,其中在該前處理溶液中,該第二金屬或其之鹽 類係為溶解的。 此可以提升該基板表面的親水性,且在該滲透脫氣水 進入該通孔之後,在該等通孔中之滲透脫氣水可以以該前 處理溶液代換,該者因此確實地進入該等通孔中。 該第一金屬可能為鈷,舉例而言,且較諸鈷更為惰性 201247946 之該第二金屬可能為銅。在轉例巾,該前處理溶液較佳 地應具有從1至70g/L之範圍的銅濃度。 隨著-銅金屬薄膜係藉助於代換在該鈷薄膜表面上形 成’即使-雜硫_溶液錢驗為—f鍍溶液,紐 缚膜係被防止溶解於該㈣溶液中。含有銅之該前處理溶 液可藉由將硫義溶解至純水中而製備,舉例而言,且在 該前處理溶液中之銅濃㈣取決於料通孔的大小而設定 至一所欲值。 _該第二金屬可能為1巴、金、翻或銀,且該第三金厲可 為銅在此事例中’ 一酸性硫酸銅電鍍溶液較佳地係使 用做為該電鍍溶液。 依據本發明,當該第一金屬,例如其具有較氫 1 的離子化趨勢,係❹做為-種子層,且該基板係使用 諸如硫酸銅钱麵之酸性電麟絲紐,,該第一金 屬係藉由該第二金屬之金屬薄㈣受該電麟液之傷害, ,中該第二金屬較該第—金屬較為舰的,且該薄膜係 精助於代換在料—金屬表面上形成。㈣第—金屬覆蓋 之该等通孔因細_料之_钱金屬確實地搬入。 圆式簡單說明 第1A至1C®係為橫截面圖其顯示製作具有垂直延伸 經由該基板之數個鋼通孔柱之一基板的方法,· 第2圖係為-橫截面圖其顯示表面覆蓋以一姑薄膜且 具有通孔之一基板; 第3圖係為—橫截面圖其顯示一基板,該者之表面係覆 201247946 蓋以一鈷薄膜,且具有數個通孔其具有ΙΟμπι之一直徑與 ΙΟΟμίΉ之一深度,在使用一硫酸銅電鍍溶液電鍍該基板 時,以銅電鍍金屬嵌入該等通孔; 第4圖係為一橫截面圖其顯示一基板,該者之表面係覆 蓋以一鈷薄膜,且具有數個通孔其具有20μηι之一直徑與 120μηι之一深度,在使用一硫酸銅電鍍溶液電鍍該基板 時,以銅電鍍金屬嵌入該等通孔; 第5圖係為一橫截面圖其顯示一基板,該者之表面係覆 蓋以一鈷薄膜,且具有數個通孔其具有30μιη之一直徑與 130μηι之一深度,在使用一硫酸銅電鍍溶液電鍍該基板 時,以銅電鍍金屬嵌入該等通孔; 第6圖係為一示意平面圖,其顯示使用於實行本發明之 一電鍍方法之一電鍍設施的整體排列; 第7圖係為在第6圖顯示之該電鍍設施中所採用之一輸 送機械手臂的示意立面圖; 第8圖係為在第6圖顯示之該電鍍設施中所採用之一電 鍍裝置的示意橫截面圖; 第9圖係為在第8圖顯示之該電鍍裝置之一攪拌槳(攪 拌工具)的平面圖; 第10圖係為沿第9圖之線Α-Α所取之一橫截面圖;201247946 VI. DESCRIPTION OF THE INVENTION: [Spraying of the genus of the genus: 彳 $ 贝 贝 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 Loading such a metal such as copper into the vias in the fabrication of the substrate, such as a semiconductor substrate or the like, the substrate having a plurality of vertically penetrating via posts (hole plugs) therein, and It can be used in a three-dimensional package of so-called semiconductor wafers. [Prior Art 3] Background of the Invention The formation of a metal via post such as copper, which vertically penetrates a semiconductor substrate, is known as a method of electrically connecting the layers of a multilayer stack of semiconductor substrates. Figures 1A through 1C show an exemplary method for fabricating a substrate having a copper via post therein. First, as shown in FIG. 1A, a substrate W is prepared by forming a plurality of upwardly open vias in a substrate, such as a germanium wafer, for example by using the lithography/etching. a technique; on the surface of the substrate 10, including a sidewall of the via 12, forming a dielectric film (not shown), such as by PVD; on the entire surface of the substrate 10, including the inner surface of the via 12, A metal barrier layer 14 such as Ti (titanium) is formed, and then a copper seed layer 16 is formed on the surface of the barrier layer 14. The diameter of the through hole 12, d" is, for example, 2 to 50 μm, especially 1 〇 to 2 〇 μηι, and the depth "h" of the through hole 12 is, for example, 20 to 150 μm The copper electroplating system uses the copper seed layer 16 as a cathode on the surface of the substrate 201247946, so as to fill a plating metal (copper) 18 into the through hole, and deposit the plating metal 18 to The surface of the copper seed layer 16 is as shown in FIG. 1B. In the case of embedding copper into the via hole 12 by copper plating, a copper sulfate plating solution is widely used as a plating solution. The person is relatively inexpensive and relatively easy to control, including its waste treatment, thereafter, as shown in Figure 1C, additional bond metal 18, copper seed layer 16 and barrier layer on the substrate 10. The 14-series is removed, for example, by chemical mechanical polishing (CMP). Further, the surface side of the substrate 10 is polished off, for example, to the position indicated by the two-dot chain line in Figure 1C, thereby exposing a bottom surface of the plating metal 18 embedded in the through hole 12. W having a copper (electroplated metal 18) via post therein, vertically penetrating through the substrate W, can be fabricated in this manner. The via 12 generally has a high aspect ratio, that is, a depth to diameter ratio And has a large depth. In order to thoroughly fill the copper (electroplated metal) into the through hole 12, it has a high aspect ratio and a large depth, and is not manufactured by an electric key such as in the embedded metal. The defect of the void, which is usually necessary to perform the electroplating in a bottom-up manner to allow the electroplated metal to preferentially grow from the bottom of the via 12. This bottom-up electrowinning is generally performed by using a sulfuric acid. It is carried out by a copper plating solution containing various additives such as sps (bissulfide (disulfide)) (bis (3-sulf〇pr〇pyi) disulfide) as an electric ore accelerator, PEG (poly(10) Ethylene glycol) acts as a homogenizer—(iv) and pm (polyethyleneimine). These additives exert their effects on 201247946 after they are absorbed onto a substrate surface. PVD generally has a low ladder. Cover coverage. So 'if that The continuous copper seed layer 16 is formed on the surface of the barrier layer 14 by PVD. Then the continuous copper seed layer 16 needs to have a considerable thickness, for example, in the range from 800 nm to 1000 nm. Inevitably, there is a need for a smaller thickness seed layer. As shown in Figure 2, it is already understood that a conformal CVD process is performed on the entire surface of the substrate 10, including such The surface of the through hole 12 forms a cobalt film 20 as a sublayer, which serves as a barrier layer. Then a 'copper plating process is performed on the cobalt film 20 as a cathode to electroplate metal. That is, copper is embedded in the through hole 12. C SUMMARY OF THE INVENTION 3 SUMMARY OF THE INVENTION However, it is difficult to completely fill the through holes 12 in accordance with an electroplating process with a metal such as copper or the like without generating an unfilled land. The cobalt film 20 covers the surface and has a high south width ratio and a large depth. For example, as shown in Fig. 3, the surface of a substrate prepared by a substrate w is covered by a cobalt film and has a plurality of through holes 12a having a depth of 1 ^ ^ 彳 岳 。 。 。 。 。 When the surface of the substrate is plated using a copper sulfate plating solution containing various additives, and an electroplated metal crucible is incorporated into the through holes 12a, the unfilled strip 22a has a rather rough surface. A large bottom portion of the hole 12a is formed. Cobalt thin coating Fig. 4 shows another substrate W which is covered with 201247946 and has a plurality of through holes 12b having a diameter of 20 μm and a depth of about 120 μm. When the substrate Wq surface ❹ contains one of various additives, a copper sulphate plating solution, the galvanic metal 18 copper is embedded in the through holes l2b, and the unfilled strip 22b has a rather rough surface. The large bottom portion 7 is formed into a blade and the copper filled in the through holes 12b is easily different in length. Fig. 5 shows a substrate w which is covered with a cobalt film and has a plurality of through holes 12c having a diameter of 3 μm and a depth of about 130 μm. The surface of the substrate W is plated with copper sulfate containing one of various additives. When the liquid ore is embedded in the through holes 12c with the electric ore metal 18, the copper metal is only in the through hole 12. It grows on the upper inner surface. The grown electric ore metal 18 does not close the open end of the through holes 12c, and the through holes 12 are not completely embedded in the plating metal 18. As described above, a copper plating metal is completely embedded in the through hole according to one of the electroplating processes using copper sulfate plating solution, and the unfilled land is non-volatile, and the surface of the through holes is a cobalt film. Covered and has a high aspect ratio and a large depth. For the reason that the through holes are not completely provided, it is believed that the thin film is dissolved in the copper copper ore solution, which is stored with the acidic copper sulfate electric ore solution. Directly. Specifically, if the difficult-to-like metal is less inert (four) gold; | 'such as Μ' means that if the metal of the seed layer has a larger ionization tendency than hydrogen' then the seed layer is dissolved in the "acidic ore solution" . a ruthenium cobalt ruthenium film, that is, the seed layer, which is dissolved in a plating solution, the 201247946 problem, '4 roads themselves', especially in the contact area of the outer surface of the substrate (four), the area contact-seal member prevents it Or sealing the outer surrounding surface 'with its adjacent zone from the money solution. Specifically, the contact area of the 4 film with the surrounding surface of the 4 substrate and its adjacent zone - a higher rate of dissolution 'because - the film of the ore film is less likely to deposit on these local areas' due to the local area The electric field is blocked. The substrate is generally supplied with current from the surface of the outer egg of the tablet 2G which is protected from the electroplating solution by the sealing member. If the film is dissolved in the contact zone of the outer substrate with the outer surface of the adjacent substrate, the current is prevented from flowing in the absence of the seed layer. The substrate. 『: The test pyrotechnic electro-key solution will be a usable solution. However, the solution is more expensive than the sulfur-electric ship (four) and makes the management of the plating solution more complicated, including waste disposal. The problem that the shell seed layer is transferred to the acidic f lin liquid (4) #—gu film <surface system, appearing in copper Wei, and when the metal surface having a tendency to ionize with hydrogen is electroplated with another metal appear. L In the above case, the present invention has been made. Therefore, the present invention is directed to providing a plating material which is provided with a substrate having a metal seed layer which is relatively large in hydrogen and which is electroplated with a copper sulfate electroplating solution, such as a copper sulfate electroplating solution. The present invention provides an electrical inclusion preparation substrate having a first metal cladding on its surface; = 201247946 hole, the first The metal has a tendency to ionize more hydrogen, pretreating the substrate by immersing the substrate in a pretreatment solution, and in the pretreatment solution, one of the second metals is more inert than the first metal or The salt is dissolved, and then the surface of the substrate is plated to embed the second metal or a third metal in the through hole. Since the substrate has a tendency to have a larger hydrogen ionization degree on the surface thereof The first metal-covered through hole is pretreated by immersing the substrate in a pretreatment solution, and the second metal or its salt which is more inert than the first metal in the pretreatment solution Is dissolved, compared to the first a metal film of a second metal which is more inert is formed on the surface of the first metal by substitution. When the surface of the substrate is plated, the first metal is prevented from directly contacting an acidic plating solution. Contacting and being dissolved in the acidic plating solution to positively embed the plating metal in the through holes. The pretreatment solution is preferably in a range from a slightly acidic degree to a slightly alkaline degree, thereby Preventing the first film, such as a cobalt film, from being dissolved therein upon contact with the pretreatment solution. Preferably, the substrate is prior to pretreatment of the substrate by immersing the substrate in the pretreatment solution. Pretreating by immersing the substrate in the deaerated water, wherein the second metal or a salt thereof is dissolved in the pretreatment solution. This can enhance the hydrophilicity of the surface of the substrate, and in the permeation After the deaerated water enters the through hole, the permeated deaerated water in the through holes may be replaced by the pretreatment solution, and the person thus surely enters the through holes. The first metal may be For example, and the second metal which is more inert than cobalt 201247946 may be copper. In the case of a recirculation towel, the pretreatment solution should preferably have a copper concentration ranging from 1 to 70 g/L. - the copper metal film is formed on the surface of the cobalt film by means of substitution, and the neotite film is prevented from being dissolved in the (iv) solution. The pretreatment containing copper The solution can be prepared by dissolving sulphur in pure water, for example, and the concentration of copper in the pretreatment solution (four) is set to a desired value depending on the size of the through hole. _ The second metal may be 1 bar, gold, turn or silver, and the third gold may be copper. In this case, an acidic copper sulfate plating solution is preferably used as the plating solution. According to the present invention, when the first metal, For example, it has a tendency to ionize more than hydrogen 1, the system is used as a seed layer, and the substrate is made of an acid electric wire, such as a copper sulfate surface, the first metal is made of a metal of the second metal. Thin (four) is damaged by the electric lining liquid, and the second metal is more than the first More metal ship, and the thin-film material in fine assist substitution - are formed on the metal surface. (4) The through-holes covered by the first metal are surely carried in due to the fine metal. Circular Simple Description 1A to 1C® is a cross-sectional view showing a method of fabricating a substrate having a plurality of steel through-hole posts extending vertically through the substrate, and FIG. 2 is a cross-sectional view showing surface coverage a substrate having a thin film and having a through hole; Fig. 3 is a cross-sectional view showing a substrate, the surface of which is covered with a cobalt film of 201247946, and having a plurality of through holes having one of ΙΟμπι a diameter and a depth of ΙΟΟμίΉ, when the substrate is plated with a copper sulfate plating solution, the through holes are embedded with copper plating metal; FIG. 4 is a cross-sectional view showing a substrate, the surface of which is covered with a cobalt film having a plurality of through holes having a diameter of one of 20 μm and a depth of 120 μm. When the substrate is electroplated using a copper sulfate plating solution, the through holes are embedded in the copper plating metal; FIG. 5 is a The cross-sectional view shows a substrate covered with a cobalt film and having a plurality of through holes having a diameter of 30 μm and a depth of 130 μm, which is electroplated using a copper sulfate plating solution. In the case of a plate, the through holes are embedded in a copper plated metal; Fig. 6 is a schematic plan view showing the overall arrangement of an electroplating facility for performing one of the electroplating methods of the present invention; Fig. 7 is in Fig. 6. A schematic elevational view of one of the transport robots used in the electroplating facility is shown; Fig. 8 is a schematic cross-sectional view of one of the electroplating devices employed in the electroplating facility shown in Fig. 6; a plan view of a stirring paddle (stirring tool) of one of the plating apparatuses shown in Fig. 8; Fig. 10 is a cross-sectional view taken along line Α-Α of Fig. 9;
第11圖係為一橫截面圖其顯示一基板,該者之表面係 覆蓋以一鈷薄膜,且具有數個通孔其具有ΙΟμιη之一直徑與 約ΙΟΟμιη之一深度,在使用一硫酸銅電鍍溶液電鍍該基板 時,以銅電鍍金屬嵌入該等通孔,在該基板使用具備10 g/L 10 201247946 銅濃度之一前處理溶液處理之後; 第12圖係為一橫截面圖其顯示一基板,該者之表面係 覆蓋以一鈷薄膜,且具有數個通孔其具有20μηι之一直徑與 約120μηι之一深度,在使用一硫酸銅電鍍溶液電鍍該基板 時,以銅電鍍金屬嵌入該等通孔,在該基板使用具備10 g/L 銅濃度之一前處理溶液處理之後; 第13圖係為一橫截面圖其顯示一基板,該者之表面係 覆蓋以一鈷薄膜,且具有數個通孔其具有30μπι之一直徑與 約130μηι之一深度,在使用一硫酸銅電鍍溶液電鍍該基板 時,以銅電鍍金屬嵌入該等通孔,在該基板使用具備10g/L 銅濃度之一前處理溶液處理之後; 第14圖係為一橫截面圖其顯示一基板,該者之表面係 覆蓋以一鈷薄膜,且具有數個通孔其具有ΙΟμηι之一直徑與 約ΙΟΟμιη之一深度,在使用一硫酸銅電鍍溶液電鍍該基板 時,以銅電鍍金屬嵌入該等通孔,在該基板使用具備30g/L 銅濃度之一前處理溶液處理之後; 第15圖係為一橫截面圖其顯示一基板,該者之表面係 覆蓋以一鈷薄膜,且具有數個通孔其具有20μιη之一直徑與 約120μηι之一深度,在使用一硫酸銅電鍍溶液電鍍該基板 時,以銅電鍍金屬嵌入該等通孔,在該基板使用具備30g/L 銅濃度之一前處理溶液處理之後; 第16圖係為一橫截面圖其顯示一基板,該者之表面係 覆蓋以一鈷薄膜,且具有數個通孔其具有ΙΟμιη之一直徑與 約ΙΟΟμιη之一深度,在使用一硫酸銅電鍍溶液電鍍該基板 11 201247946 時,以銅電鍍金屬嵌入該等通孔,在該基板使用具備60g/L 銅濃度之一前處理溶液處理之後; 第17圖係為一橫截面圖其顯示一基板,該者之表面係 覆蓋以一鈷薄膜,且具有數個通孔其具有20μηι之一直徑與 約120μπι之一深度,在使用一硫酸銅電鍍溶液電鍍該基板 時,以銅電鍍金屬嵌入該等通孔,在該基板使用具備60 g/L 銅濃度之一前處理溶液處理之後;且 第18圖係為一橫截面圖其顯示一基板,該者之表面係 覆蓋以一鈷薄膜,且具有數個通孔其具有30μηι之一直徑與 約130μηι之一深度,在使用一硫酸銅電鍍溶液電鍍該基板 時,以銅電鍍金屬嵌入該等通孔,在該基板使用具備60g/L 銅濃度之一前處理溶液處理之後。 I:實施方式3 較佳實施例之詳細說明 於此,參照該等圖式來說明本發明之較佳實施例。下 列說明例示一示範性事例,在該者中,如第2圖所顯示之一 基板W係製備的,該基板具備藉由一同形CVD製程、在其 等整個表面上形成,包括通孔12之表面,做為種子層之一 鈷薄膜,該者雙重做為一障蔽層。然後,一銅電鍍製程係 使用一硫酸銅電鍍溶液在該基板W之表面上實行,因此以 一電鍍金屬,意即銅,嵌入該等通孔12中,從而在該基板 W中形成銅通孔。 第6圖係為使用於實行本發明之一電鍍方法之一電鍍 設施的整體佈局平面圖。此電鑛設施係設計以為了在一相 12 201247946 繼方式中自動地執行所有的電鍍製程,包括基板之前處 理、電鍍、及電鍍之後處理。具有附著於其上之一裝曱面 板的設備框架110的内部係由一分隔板112劃分為一電鍍空 間116 ’該空間係用於執行一基板之電锻製程與被電鐘溶液 附著之該基板的處理,及用於執行其他製程之一清洗空間 114,意即,不直接涉及一電鍍溶液之製程者。兩個基板支 擇器160(見第7圖)係平行排列,而附著一基板至每一基板支 撐器160並從每一基板支撐器160分離一基板的基板附著/ 分離台162係在由該分隔板112所分隔之一分隔部分上提供 做為一基板遞送段,其中該分隔板1丨2將該電鑛空間116與 該清洗空間114劃分開來。裝載/卸載埠12〇,在該者上存放 基板之基板匣係安裝的,係連接至該清洗空間114。進一 步,該設備框架110具有設於其上之一操縱面板121。 在§亥清洗空間114中,其係配置用於對齊一基板之一定 向平板或-缺口於-預決定方向的—對準器122,兩個用於 清洗-電《板並於—高速下旋轉該基板以自旋乾燥該基 板的清洗/乾燥裝置124。進—步,—第—輸送機器手臂128 實質上係配置於這些加卫裝置之中心,意即該對準器a〕與 該清洗/乾縣置124之中心、,從而在該等加工裝置122、 124、該基板附著/分離台162,及安裝在該裝載/卸載淳12〇 丄之s玄基板匣之間輸送與遞送一基板。 配置於該清洗空間i 14中之該對準器m與該清洗/乾 燥裝置12顿設計以為了在—水平狀態下支樓並加工一基 板,在該狀態中,該基板之前面係面向上。該第-輸送機 13 201247946 器手臂128係設計以為了在—水平狀g巾輸送及遞送—基 板,在该狀態中,該基板之前面係面向上。 在該電鍵空間116中,在從該分隔板m的順序中,其 係配置有用於存放或暫時存放該基板支撐器⑽之一貯藏 庫(stocker)164;—用於實行-預濕潤處理(第-前處理)的 第-前處理裝£126,以藉由以該脫氣水,例如純水(_) 濕潤而提升該基板表面之親水性;一用於實行代換處理(第 二前處理)的第二前處理裝置166,用於以鋼代換在該姑薄 膜表面上之鈷,該者係藉由將該基板浸入在一略微酸性或 略微鹼性的前處理溶液中,其中該溶液含有較鈷更為惰性 的銅;一用於以純水清洗該基板表面之第一水清洗裝置 168a; —用於實行電鍍之電鍍裝置17〇:一第二水清洗裝置 168b,及一用於脫水該電艘基板之吹氣裝置172。兩個第二 輸送機器手臂174a、174b係配置於這些裝置旁邊,以為了 沿著一軌道176移動。該第二輸送機器手臂之一者17如在該 基板附著/分離台162與該貯藏庫164之間輸送該基板支撲 器160。該第二輸送機器手臂之另一者174b在該貯藏庫 164、該第一前處理裝置126、該第二前處理裝置166、該第 一水清洗裝置168a、該電鍍裝置17〇、該第二水清洗裝置 168b、及該吹氣裝置172之間輸送該基板支撐器16〇。 如第7圖所顯示,該第二輸送機器手臂174a、174b每一 者具有在一垂直方向中延伸之一主體178,及可沿著該主體 178垂直移動與可繞其軸旋轉之—臂18〇。該臂18〇具有兩個 平行提供之基板支撐器固定部份182,用於可分離地固定該 14 201247946 等基板支撐器160。該基板支撐器160係設計以為了支撐基 板W在一狀態,在該狀態中該基板之前面係曝露而該基板 之一周邊部分係密封,且係設計能夠附著該基板W至該基 板支撐器160並從該基板支撐器160分離該基板W。 該貯藏庫164、該第一前處理裝置126、該第二前處理 裝置166、該水清洗裝置168a、168b及該電鍍裝置170係設 計以為了與在每一基板支撐器160兩端設有之向外凸出部 分接合’因此以支持該基板支撐器160在如此一狀態中該基 板支撐器160係在一垂直方向中懸掛。 該第一前處理裝置126具有兩個前處理槽127,用於在 其中持有一脫氣水,諸如純水(脫氣DIW)其具有,例如,不 超過2 mg/L溶解氧濃度或之類者。如第7圖中所顯示,支撐 該等基板支撐器160的該第二輸送機器手臂174b之臂180係 下降以為了與該第一前處理槽127之上端接合,以在一懸掛 方式中支持該等基板支撐器160,其中該等基板支撐器160 係於一垂直狀態中裝載該等基板W。因此,該第一前處理 裝置126係設計,藉由此該等基板支撐器16〇係與該等基板 w —起浸入在該前處理槽127中之該脫氣水中,以實行該基 板表面之一預濕潤處理(第一前處理)。 該第二前處理裝置166具有兩個前處理槽183,用於在 其中持有一略微酸性或略微鹼性的前處理溶液,該者含有 較結更為惰性之銅。如第7圖中所顯示,支撐該等基板支撐 器160的該第二輸送機器手臂174b之臂180係下降以為了與 該前處理槽183之上端接合,以在一懸掛方式中支持該等基 15 201247946 板支撐器160,其中該等基板支撐器160係於一垂直狀態中 裝載該等基板W。因此,該第二前處理裝置166係設計,藉 由此該等基板支撐器160係與該等基板W—起浸入在該前 處理槽183中之該前處理液體中,以實行一鈷薄膜表面之一 代換處理(第二前處理)。 一前處理溶液,在該者中銅係溶解且該者係從一略微 酸性程度至一略微鹼性程度之該範圍中,意即,具有從2至 9該範圍中之一 pH,係藉由將硫酸銅溶解至純水中,舉例而 言,而製備。該前處理溶液之銅濃度可能在從1至70g/L之 一範圍中,且係取決於該通孔之大小或之類而設定至一所 欲之值。一用於pH調整之緩衝劑,諸如磷酸鹽、鈦酸鹽、 檸檬酸、琥珀酸或硼酸,可能添加至該前處理溶液以抑制 該前處理溶液的pH波動。 類似地,該等水清洗裝置168a、168b具有兩個水清洗 槽184a及兩個水清洗槽i84b,該等者分別地於其中持有純 水’且該電鍍裝置170具有數個於其中持有電鍍溶液的電鍍 槽186。該等水清洗裝置16仏、168b及該電鍍裝置170係設 計的’藉由此該等基板支撐器160係與該等基板W—起浸入 於在該水清洗槽184a、184b中之該純水中,或在該電鍍槽 186中之該電鍍溶液中,以在如上文所描述之相同方式中實 行水清洗或電鍍。支撐該基板支撐器160的該第二輸送機器 手臂174b之臂180係下降,且空氣或惰氣係朝向安裝於該等 基板支撐器160上之該等基板w注入以吹走附著於該等基 板支撐器160與該等基板w上之液體並將該等基板W脫 16 201247946 水,其中該等基板支撐器係於—垂直狀態中裝载基板w。 因此,該吹氣裝置i 7 2係設相為了實行吹氣處理。 如第8圖中所顯示,在該電鍍裝置17〇中設有的每一電 鑛槽186係設計以為了在其巾持有―預決定數量的電鍵溶 液Q。該等基板W,該等者係維持在_狀態中,藉由此該前 面(被電鍍之表面)係曝露而該基板之周邊部分係由該基板 支標器_水密密封,係於—垂直方向浸人該電鑛溶液Q 卜在此實;例中,—酸性硫電鑛溶液係使用做為該 電鏟溶液Q,該者除了銅離子、—支持電解f與鹵素離子之 外,含有各種添加劑’諸如SPS(二硫化(雙以柄基))做為 -電鍍加速劑、PEG(聚乙烯乙二醇)做為一抑制劑、及 PEI(聚乙烯亞胺)做為—均㈣,舉例而言。較佳地硫酸係 使用做為該支持電㈣,且較佳喊離子係❹做為該鹵 素離子。 用於接党已溢出該電鍵槽186邊緣之電鑛溶液q的溢 出槽200已設於該電鍍槽186之上端周圍。一循環管路2〇4之 —端,該管路係設有-幫浦202,係連接至該溢出槽2〇〇之 底部,而該循環管路204之另一端係連接至設於該電鍍槽 186底#之一電鍍溶液供應入口 186a。因此,在該溢出槽2〇〇 中之電鍍溶液係藉由該幫浦2〇2之驅動返回該電鍵槽186。 在該幫浦202下游,一用於控制該電鑛溶液Q溫度的值溫單 元206及用於過滤含於该電鑛溶液中之異物的過遽器208 係居於該循環管路2〇4中間的。 底。卩板210,该者在其中具有大量的電鍍溶液通洞, 17 201247946 係設置於該電鍍槽186之底部中。該電鍍槽186之内部因此 係由該底部板210分割為一上部基板加工室214及一下部電 鐘溶液分佈至212。進一步,一遮蔽板216,垂直向下延伸’ 係安裝於該底部板210之下表面。 依據此電鍍裝置170,該電鍍溶液Q係藉由該幫浦2〇2 之驅動引入至該電鍍槽186的電鍍溶液分佈室212,通經由 設於該底部板210中的電鍍溶液通洞流進該基板加工室 214 ’垂直流動近似平行於由該基板支撐器16〇所支撐之該 基板W表面,且然後流進該溢出槽2〇〇。 具有相應於該基板w形狀之一環狀形狀的一陽極22〇 係由一陽極支撐器222支撐的且係垂直設於該電鍍槽ι86 中。當該電鍍溶液Q係裝填於該電鍍槽186中時,由該陽極 支撐器222所支撐之該陽極220變成浸入於在該電錄槽186 中之該電鍍溶液Q ’且面向由該基板支撐器16〇支撐並配置 於該電鍍槽186中之該基板W。 進一步’在該電鍵槽186中,一調節板224,用於調節 在該電鍍槽186中之該電位分佈,係於該陽極220與配置於 該電鍍槽186中一預決定位置的該基板w之間配置的。在此 實施例中,該調節板224係包含一柱狀部分226與一長方形 凸緣部分228,且係由一介電材料聚氣乙烯製成。該柱狀部 分226具有如此一開口大小與轴長度以為了充分地限制電 %擴張。該調節板224之凸緣部分228之一下端碰到該底部 板 210 〇 進一步,在該電鍍槽186十,一調節板224,用於調節Figure 11 is a cross-sectional view showing a substrate covered with a cobalt film and having a plurality of through holes having a diameter of one of ΙΟμηη and a depth of about ΙΟΟμηη, using a copper sulfate plating When the solution is electroplated, the through holes are embedded in the copper plating metal after the substrate is treated with a pretreatment solution having a copper concentration of 10 g/L 10 201247946; and FIG. 12 is a cross-sectional view showing a substrate The surface of the person is covered with a cobalt film and has a plurality of through holes having a diameter of one of 20 μm and a depth of about 120 μm. When the substrate is electroplated using a copper sulfate plating solution, the copper plating metal is embedded therein. a through hole after the substrate is treated with a pretreatment solution having a copper concentration of 10 g/L; FIG. 13 is a cross-sectional view showing a substrate covered with a cobalt film and having a number The through holes have a diameter of one of 30 μm and a depth of about 130 μm. When the substrate is plated with a copper sulfate plating solution, the through holes are embedded in the copper plating metal, and the substrate is used. After treatment with a pretreatment solution of 10 g/L copper concentration; Fig. 14 is a cross-sectional view showing a substrate covered with a cobalt film and having a plurality of through holes having a diameter of ΙΟμηι And plating the substrate with a copper sulfate plating solution at a depth of about 之一μιη, the copper plating metal is embedded in the through holes, and the substrate is treated with a pretreatment solution having a copper concentration of 30 g/L; Is a cross-sectional view showing a substrate covered with a cobalt film and having a plurality of through holes having a diameter of 20 μm and a depth of about 120 μm, which is electroplated using a copper sulfate plating solution. In the case of a substrate, the through holes are embedded in a copper plating metal after the substrate is treated with a pretreatment solution having a copper concentration of 30 g/L; and FIG. 16 is a cross-sectional view showing a substrate, the surface of the substrate Covered with a cobalt film and having a plurality of through holes having a diameter of one of ΙΟμηη and a depth of about ΙΟΟμηη, when the substrate 11 201247946 is electroplated using a copper sulfate plating solution, The metal plating is embedded in the through holes after the substrate is treated with a pretreatment solution having a copper concentration of 60 g/L; and FIG. 17 is a cross-sectional view showing a substrate covered with a cobalt film. And having a plurality of through holes having a diameter of one of 20 μm and a depth of about 120 μm. When the substrate is plated with a copper sulfate plating solution, the through holes are embedded in the copper plating metal, and the substrate is used with 60 g/ One of the L copper concentrations is treated with the pretreatment solution; and the 18th is a cross-sectional view showing a substrate covered with a cobalt film and having a plurality of through holes having a diameter of 30 μm At a depth of about 130 μm, when the substrate was plated with a copper sulfate plating solution, the through holes were embedded with copper plating metal after the substrate was treated with a pretreatment solution having a copper concentration of 60 g/L. I. Embodiment 3 DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, preferred embodiments of the present invention will be described with reference to the drawings. The following description exemplifies an exemplary case in which, as shown in FIG. 2, a substrate W is provided, the substrate is formed by a homomorphic CVD process, formed on the entire surface thereof, and includes a via hole 12 The surface, as a cobalt film of the seed layer, doubles as a barrier layer. Then, a copper plating process is performed on the surface of the substrate W using a copper sulfate plating solution, so that a plating metal, that is, copper, is embedded in the through holes 12, thereby forming a copper via hole in the substrate W. . Fig. 6 is a plan view showing the overall layout of an electroplating facility used in the electroplating method of the present invention. This electro-mineral facility is designed to automatically perform all electroplating processes in a phase 12 201247946, including pre-substrate processing, electroplating, and post-plating processing. The interior of the equipment frame 110 having one of the mounting panels attached thereto is divided by a partitioning plate 112 into a plating space 116' for performing an electric forging process of a substrate and being attached to the electric clock solution. The processing of the substrate, and the cleaning space 114 used to perform one of the other processes, that is, the process that is not directly involved in a plating solution. Two substrate adjusters 160 (see FIG. 7) are arranged in parallel, and a substrate attaching/separating stage 162 to which a substrate is attached to each substrate support 160 and a substrate is separated from each substrate support 160 is One of the partitions separated by the partition plate 112 is provided as a substrate delivery section, wherein the partition plate 1丨2 divides the electric ore space 116 from the cleaning space 114. The loading/unloading port 12 is attached to the cleaning space 114 on the substrate on which the substrate is stored. Further, the equipment frame 110 has a manipulation panel 121 provided thereon. In the cleaning space 114, it is configured to align one of the directional plates of a substrate or - the aligner 122 of the pre-determined direction, two for cleaning - electric "plate and rotate at high speed" The substrate is spin-dried to the cleaning/drying device 124 of the substrate. The step-by-step-transport robotic arm 128 is substantially disposed in the center of the guarding device, that is, the aligner a] and the center of the cleaning/drying county 124, and thus in the processing device 122 124. The substrate attachment/detachment stage 162 and a substrate mounted and transported between the loading/unloading cassettes. The aligner m disposed in the cleaning space i 14 and the cleaning/drying device 12 are designed to support the substrate in a horizontal state and process a substrate in which the front surface of the substrate faces upward. The first conveyor 13 201247946 arm 128 is designed to transport and deliver the substrate in a horizontal manner, in which state the front surface of the substrate faces upward. In the key space 116, in the order from the partition plate m, it is provided with a stocker 164 for storing or temporarily storing the substrate holder (10); for performing-pre-wetting processing ( The first pre-treatment of the first-pretreatment) is 126 to enhance the hydrophilicity of the surface of the substrate by wetting with the deaerated water, such as pure water (_); one for performing the substitution process (second before a second pretreatment device 166 for treating the cobalt on the surface of the ruthenium film by immersing the substrate in a slightly acidic or slightly alkaline pretreatment solution, wherein The solution contains copper which is more inert than cobalt; a first water cleaning device 168a for cleaning the surface of the substrate with pure water; - a plating device for performing electroplating 17: a second water cleaning device 168b, and a The air blowing device 172 for dehydrating the electric boat substrate. Two second conveyor arms 174a, 174b are disposed beside these devices for movement along a track 176. One of the second transport robots 17 transports the substrate baffle 160 between the substrate attachment/detachment stage 162 and the reservoir 164. The other one of the second transfer robots 174b is in the storage 164, the first pre-processing device 126, the second pre-processing device 166, the first water cleaning device 168a, the plating device 17A, the second The substrate holder 16 is transported between the water cleaning device 168b and the air blowing device 172. As shown in Fig. 7, the second conveyor robots 174a, 174b each have a body 178 extending in a vertical direction and are vertically movable along the body 178 and rotatable about its axis - the arm 18 Hey. The arm 18 has two substrate holder fixing portions 182 provided in parallel for detachably fixing the substrate holder 160 such as the 2012 201247946. The substrate holder 160 is designed to support the substrate W in a state in which the front surface of the substrate is exposed and a peripheral portion of the substrate is sealed, and is designed to adhere the substrate W to the substrate holder 160. The substrate W is separated from the substrate holder 160. The storage 164, the first pretreatment device 126, the second pretreatment device 166, the water cleaning devices 168a, 168b, and the plating device 170 are designed to be disposed at both ends of each substrate supporter 160. The outwardly projecting portion engages 'and thus supports the substrate holder 160 in such a state that the substrate holder 160 is suspended in a vertical direction. The first pretreatment device 126 has two pretreatment tanks 127 for holding a deaerated water therein, such as pure water (degassed DIW) having, for example, a dissolved oxygen concentration of no more than 2 mg/L or Class. As shown in FIG. 7, the arm 180 of the second conveyor arm 174b supporting the substrate support 160 is lowered for engagement with the upper end of the first pretreatment tank 127 to support the suspension in a suspension manner. The substrate holder 160 is mounted, wherein the substrate holders 160 are loaded in a vertical state. Therefore, the first pre-processing device 126 is designed such that the substrate holders 16 are immersed in the degassed water in the pre-treatment tank 127 together with the substrates w to perform the surface of the substrate. A pre-wetting treatment (first pre-treatment). The second pretreatment unit 166 has two pretreatment tanks 183 for holding therein a slightly acidic or slightly alkaline pretreatment solution containing relatively more inert copper. As shown in FIG. 7, the arms 180 of the second conveyor arm 174b supporting the substrate holders 160 are lowered for engagement with the upper ends of the pretreatment tanks 183 to support the bases in a suspension manner. 15 201247946 A plate holder 160, wherein the substrate holders 160 are loaded with the substrates W in a vertical state. Therefore, the second pre-processing device 166 is designed such that the substrate holder 160 is immersed in the pre-treatment liquid in the pre-treatment tank 183 with the substrate W to perform a cobalt film surface. One of the substitution processes (second pre-processing). a pretreatment solution in which the copper system is dissolved and the person is in a range from a slightly acidic degree to a slightly alkaline degree, that is, having a pH from the range of 2 to 9 by Copper sulfate is dissolved in pure water, for example, prepared. The copper concentration of the pretreatment solution may be in the range of from 1 to 70 g/L, and is set to a desired value depending on the size or the like of the through hole. A buffer for pH adjustment, such as phosphate, titanate, citric acid, succinic acid or boric acid, may be added to the pretreatment solution to inhibit pH fluctuation of the pretreatment solution. Similarly, the water washing devices 168a, 168b have two water washing tanks 184a and two water washing tanks i84b, respectively, which hold pure water therein, and the plating apparatus 170 has a plurality of holdings therein. Electroplating bath 186 for the plating solution. The water cleaning devices 16A, 168b and the plating device 170 are designed such that the substrate holder 160 is immersed in the water cleaning tanks 184a, 184b with the substrate W. In the plating solution in the plating bath 186, water washing or plating is performed in the same manner as described above. The arm 180 of the second transfer robot arm 174b supporting the substrate supporter 160 is lowered, and air or inert gas is injected toward the substrates w mounted on the substrate supporters 160 to blow away the substrates attached thereto. The support 160 and the liquid on the substrates w and the substrates W are removed from the 20124794646 water, wherein the substrate holders are loaded with the substrate w in a vertical state. Therefore, the air blowing device i 7 2 is configured to perform a blowing process. As shown in Fig. 8, each of the electrowinning tanks 186 provided in the electroplating apparatus 17 is designed to hold a predetermined number of electric-key solutions Q in its napkin. The substrates W are maintained in the _ state, whereby the front surface (the surface to be plated) is exposed, and the peripheral portion of the substrate is sealed by the substrate holder _ watertight, in the vertical direction In this case, the acid sulfur solution is used as the electric shovel solution Q, which contains various additives in addition to copper ions, supporting electrolysis f and halogen ions. 'such as SPS (disulfide (double handle base)) as - electroplating accelerator, PEG (polyethylene glycol) as an inhibitor, and PEI (polyethyleneimine) as - (4), for example Words. Preferably, the sulfuric acid is used as the supporting electricity (4), and the ion system is preferably used as the halogen ion. An overflow tank 200 for receiving the electric ore solution q from which the party has overflowed the edge of the key slot 186 has been disposed around the upper end of the plating tank 186. a end of a circulation line 2〇4, the line is provided with a pump 202 connected to the bottom of the overflow tank 2〇〇, and the other end of the circulation line 204 is connected to the plating The plating solution supply port 186a is one of the grooves 186 bottom #. Therefore, the plating solution in the overflow tank 2 is returned to the key slot 186 by the driving of the pump 2〇2. Downstream of the pump 202, a temperature unit 206 for controlling the temperature of the electromineral solution Q and a filter 208 for filtering foreign matter contained in the electromineral solution are interposed in the middle of the circulation line 2〇4. of. bottom. The seesaw 210, which has a large number of plating solution through holes therein, 17 201247946 is disposed in the bottom of the plating bath 186. The interior of the plating bath 186 is thus divided by the bottom plate 210 into an upper substrate processing chamber 214 and a lower clock solution distributed to 212. Further, a shielding plate 216 extending vertically downward is mounted on the lower surface of the bottom plate 210. According to the plating apparatus 170, the plating solution Q is introduced into the plating solution distribution chamber 212 of the plating tank 186 by the driving of the pump 2〇2, and flows through the plating solution through the bottom plate 210. The substrate processing chamber 214' vertical flow is approximately parallel to the surface of the substrate W supported by the substrate holder 16A, and then flows into the overflow groove 2''. An anode 22 having an annular shape corresponding to the shape of the substrate w is supported by an anode holder 222 and vertically disposed in the plating tank ι86. When the plating solution Q is loaded in the plating tank 186, the anode 220 supported by the anode holder 222 becomes immersed in the plating solution Q' in the electric recording tank 186 and faces the substrate holder The substrate W supported and disposed in the plating bath 186. Further, in the key slot 186, an adjustment plate 224 for adjusting the potential distribution in the plating bath 186 is disposed between the anode 220 and the substrate w disposed at a predetermined position in the plating bath 186. Between configurations. In this embodiment, the adjustment plate 224 includes a cylindrical portion 226 and a rectangular flange portion 228 and is made of a dielectric material of polyethylene. The cylindrical portion 226 has such an opening size and shaft length as to substantially limit electrical expansion. The lower end of one of the flange portions 228 of the adjusting plate 224 hits the bottom plate 210. Further, in the plating tank 186, an adjusting plate 224 is used for adjustment.
18 201247946 在該電錢槽186中之該電位分佈,係於該陽極22〇與配置於 «鍵槽186中-預決定位置的該基板w之間配置的。在此 貧轭例中,該調節板224係包含一柱狀部分226與一長方形 =緣部分228 ’且係由一介電材料聚氯乙稀製成。該柱狀部 :226具有如此-㈣大小與軸長度以為了充分地限制電 場擴張。該㈣板224之凸緣部分228之—下制達該底部 板210。 在該調節板224與配置於電鍍槽186中一預決定位置之 «板w之間係配置一垂直延伸的攪拌柴232,做為一撥掉 工具’該者平躲往復於絲板r表面以攪拌介於該基 板W與該調節板224之間之該電鍍溶液Q。藉由在電鍵期間 以該攪拌紫232(攪拌工具)麟該電錢溶液Q,__充分數量 的銅離子可以均勻地供應至該基板W之表面。 如第9及第1〇圖所顯示,該攪拌槳232係由具有^至^ mm之-均勻厚度"t”之-長方形、板狀構件所組成,且具有 數個平行狹縫232a其界定垂直延伸的條狀部分23沘者。該 等攪拌槳232係由,舉例而言,諸如pvc、pp與pTFE之一 樹脂,及具有-織龍塗層的sus或輯形成的。其係較 佳的是,至少部分㈣拌紫m,接觸該電鍵溶液者,、係電 隔離的。該搜拌紫232之垂直長度Ll與該狹縫咖之垂直長 度L2較該基板W之垂直大小係充分大的。進一步,該攪拌 槳232係如此設計的,以致於其橫向長度之總和η與其往復 距離(衝程)較該基板W之橫向大小係充分較大的。 其係較佳的是,該狹縫232a之寬度與數目係決定的, 201247946 藉由此每一條狀部分232b係愈窄愈好’至其具有該必要剛 性的程度,以致於介於該等狭鏠232a之間之該等條狀部分 232b可以有效地槐拌該電鍵溶液,此外該電鍍溶液可以有 效通經由該等狹縫232a。 該電鍍裝置170係設有一電鍍電源250,該者之正極在 電鍍期間係經由一導線連接至該陽極220,且該負極係經由 一導線連接至該基板W的表面。該電鍍電源250係連接至一 控制段252’且該電鍍裝置170係基於源自該控制段252之信 號被控制的。 —系列的電鍍製程將於下文描述的,該者係由第6圖所 顯示之該電鍍設施實行的,用於電鍍基板W之表面,該基 板具備在其等之整個表面上形成之鈷薄膜2〇,包括該等通 孔12之表面,如第2圖中所顯示,使用一硫酸銅電鍍溶液, 因此以一電鍍金屬’意即銅,嵌入該等通孔12中。 首先,該基板W係放置於一基板匣中,伴隨其前表面(被 電鍍之表面)面向上,且該基板匣係安裝於該裝載/卸載埠 120上。該等基板W之一者係藉由該第一輸送機器手臂128 從安裝在《載/卸載埠12Q上的基板£巾取出,且放置於 該對準器12 2上以依-預決定方向對齊該基板w之一定向 平板或缺口。另-方面’兩個基板支撐器⑽,該二者已在 一垂直狀態存放於賴藏庫⑹中,係借由該第二輸送機器 手臂⑽取出’旋轉’藉由此該等基板支㈣16〇係處 於-水平狀態’且然後平行放置於該基板附著/分離台162 上0 20 201247946 在一預決定方向對齊其等之定向平板或缺口之該等基 板W係輸送並裝載至放置於該基板附著/分離台162上之該 基板支撑器160中,該者係在一狀態藉由此該等基板之周邊 部分係密封的。該二基板支撐器160,已經裝載該等基板w 者,係同時固定、抬升且然後藉由該第二輸送機器手臂丨74a 輸送至該貯藏庫164。該基板支撐器160係旋轉90。成垂直狀 態並下降,藉由此該二基板支撐器16〇係於一懸掛方式中維 持於該貯藏庫164(暫時存放)。上文之操作係在一相繼方式 中重複實行的,藉由此基板係相繼地裝載入存放在該貯藏 庫164中之該基板支撐器16〇内,且係相繼地在一懸掛方式 中於預決定位置維持於該貯藏庫164中(暫時存放)。 另一方面,該二基板支樓器160,已經裝載該等基板且 暫時存放於該貯藏庫164中者,係同時固定、抬升且然後藉 由°亥第一輸送機器手臂174b輸送至該第一前處理裝置 126在s亥第一前處理裝置126中,由該等基板支撐器16〇所 支撐之該等基板w係浸入於在該前處理槽127中之脫氣水 中,諸如純水(DIW),從而以實行該基板…表面上之一預濕 潤處理(第一前處理)。使用做為該脫氣水之純水藉由一真空 除氧器具有較佳地調整至2mg/L或更低的溶解氧濃度,因 此,藉由實行該基板W表面上之預濕潤處理(第一前處理), 該基板W表面之親水性可以提升的,容許高度滲透脫氣水 進入基板W中之該等通孔12。 在邊第一前處理之後,該二基板支撐器16〇,每一者裝 載°玄等基板,係如上文所描述在相同的方式中輸送至該第 21 201247946 二前處理H166,在該者中,料基板紐人於在 理槽183中之—前卢柿 j處理》谷液,該前處理溶液含有溶解於其中 之銅^係& %微酸性程度至—略微驗性程度,從而以在 «玄鈷:4膜2〇表面上實行-代域理(第二前處理)。在此代換 處理中(=二前處理),該職水,該者料執行該預濕潤處 理(第W處理)已進入在基板w中之該等通孔12,係由該前 處理溶液代換,且該料孔12侧猶裝填以簡處理溶 液。 該代換處理將於下文詳細的說明。當减薄膜2〇覆蓋 表面之騎基板〜每__者係、浸人於含有銅之前處理溶液中 時’在該㈣獅表面上之鈷,該者較銅係較不惰性的, 係由該前處理溶液巾之峨換,從㈣織蓋該鈷薄膜20 之表面。該#薄膜2G之表面,以銅覆蓋者,將免受一電錢 溶液之傷害。當銅覆蓋該鈷薄膜2〇之整個表面時,該代換 反應停止,且一非常薄的銅薄膜係沈積於該鈷薄膜2〇之表 面上。該鈷溥膜20之厚度本質上係不受該銅薄膜的影響, 藉由此該鈷溥膜20具有做為一障蔽層之功能依舊有效或未 損害的。 該前處理溶液較佳地應於從一略微酸性程度至一略微 鹼性程度該範圍中,以防止該鈷薄膜2〇一旦與該前處理溶 液接觸而溶解於其中。該前處理溶液可能具有調整至2 mg/L或更低之一溶解氧濃度,如該脫氣水。 在該第二前處理之後,該等基板支撐器160,每一者裴 載以該等基板W,係在如上文所描述之相同方式中輸送至 22 201247946 該第一水清洗裝置168a,在該處,該等基板w之表面係以 該第一水清洗槽184a中持有之純水清洗的。 在該水清洗之後,該二基板支撐器16〇,每—者裝載以 該等基板W,係在如上文所描述之相同方式中輸送至該電 鍍裝置170之電鍍槽186。該電鍍槽186已經裝填一預決定數 量之電鍍溶液Q其具有一預決定組成物者,該電鍍溶液係經 由s玄循系統擔。s亥專基板支樓器16〇然後係下降以將由 該等基板支撐器160所支撐之該等基板W浸入於在該電鍍 槽186中之该電鑛溶液Q。每一基板w係配置於電鑛溶液q 中之一位置其面向由該陽極支撲器222所支樓之該陽極220 者。 每一基板W係浸入於該電鍍溶液Q達一預決定時間,以 該電鍍溶液Q代換在該等通孔12中之該前處理溶液^在該預 決定時間期間,在該陽極220與該鈷薄膜之間係沒有施加電 壓,其中该钻薄膜係於每一基板W表面上、以銅薄膜覆蓋 的。在其後,一電壓係施加於該陽極22〇與每一基板w表面 上、以銅薄膜覆蓋的該鈷薄膜2〇之間,執行一電鍍製程以 在由該銅薄膜所覆蓋之該鈷薄膜20表面上沈積一銅的電鍍 薄膜,以該鋼的電鍍薄膜嵌入該等通孔12。 在該電鍍製程所使用之該電鍍溶液q係為一酸性硫酸 電鍵溶液’該者之管理係相對容易實行。假若該鈷薄膜2〇 係與該酸性硫酸銅電鍍溶液處於直接接觸,然後該鈷薄膜 20係溶解於該電鍍溶液。在此實施例中,然而,由於該鈷 薄膜20之表面係以一非常薄的銅薄膜覆蓋,該鈷薄膜2〇係 23 201247946 保持不與該酸性硫酸銅電鍍溶液直接接觸,且由此係防止 溶解於該電鍍溶液Q中。在該陽極22〇與在該基板w表面上 之5亥薄臈20之間的電壓已經施加達一預決定時間之後,該 電鍍製程係終止的。 在5亥基板W已浸入於該電鍵溶液Q中之後,且直至該電 鍍氣程係終止的,該等攪拌槳232係平行於該等基板w來回 移動,以攪拌介於該調節板224與該基板W之間之該電鍍溶 液Q。該等通孔12之嵌入係持續的,直至該等通孔12之高寬 比係降低至該電鍍溶液Q可以輕易地到達在該等通孔12中 之邊電鍍金屬之表面的限度。假若該電鍍溶液Q在此時仍然 由該等攪拌槳232激烈地攪拌,然後該電鍍金屬之生長可能 減緩的’要求一額外時間直至該等通孔12係完全地嵌入。 為了避免此缺點,係為所欲的是,當該電鍍製程已進行至 某些限度時,該電鍍溶液Q係攪拌較不強烈地。 在該電鍍製程終止之後,在該陽極220與每一基板…表 面上、以銅薄膜覆蓋的該鈷薄膜20之間施加之該電壓係關 閉的。在其後,該二基板支撐器160,每一者裝載以該基板 W ’係再次藉由該第二輸送機器手臂174b支撐並從該電鍵 槽186撤回。 該二基板支撐器16 0然後係在如上文所描述之相同方 式中輪送至該第二水清洗裝置168b,在該處,該等基板之 表面係藉由將該等基板浸入在該水清洗槽184b中所持有之 5亥純水而清洗的。在其後,該等基板支撐器160,每一者裝 載以該基板,係在如上文所描述之相同方式中輸送至該吹 24 201247946 氣裝置172’在其處,該電鑛溶液與水滴係藉由吹動空氣或 -惰氣至該基板支撑n16()上而從該基板支撐器16〇移除 的。在其後,該等基板支㈣⑽’每―料載以該基板, 係在如上文所描述之相同方式中返回該貯藏庫164中,且每 -者係在’蚊位置紐麟持於該貯藏庫⑹中。 該第二輸送機器手臂174b依序地重覆上文該等操作, 以依序地將該基板支撐H16G,每-者裝載以電錢之一基 板’返回至献藏庫164巾之-預決定位置並在該貯藏庫 164中懸掛該基板支撐器160。另一方面’二裝載以電鍍後 之基板的基板支樓器160 ’該二者已返回至該貯藏庫164, 係在如上文所描述之相同方式中由該第二輸送機器手臂 174a同時地抓取,並放置於該基板附著/分離台162上。 該第一輸送機器手臂128,配置於該清洗空間114中, 從放置於該基板附著/分離台162—者上之一基板支標器 160取出一基板並輸送該基板至該清洗/乾燥裝置丨24之一 者。在該等清洗/乾燥裝置124中,該等基板,維持在—水 平位置中伴隨該前表面面向上,係清洗的,例如以純水, 且然後藉由在一高速下旋轉而自旋乾燥。在其後,該等基 板係藉由料-輸送機时臂128返㈣錢在該裝载^ 载埠120上之該基板匣,從而完成該電鍍操作之程序。 -實驗係履行的,在該者巾數麵叙基板係製備, 該等基板之整個表面係以一鈷薄膜覆蓋,包括不同大小之 通孔的表面。該預賴處理(第—前處理)係實行以將該基= 浸入於脫氣水中’繼之以該代換處理(第二前處理),該者使 25 201247946 用具有不同銅濃度之數種類型的前處理溶液,用於代換該 姑薄膜。在其後,該等基板係電鍍以用銅電鍍金屬嵌入該 等通孔。該等通孔在實驗中之嵌入將於下文說明的。 第11圖顯示一基板w,該者表面係覆蓋以一鈷薄膜且 係具有數個通孔12a ’該等通孔na在該基板W使用一硫酸 銅電鍍溶液電鍍,以一銅電鍍金屬18嵌入該等通孔i2a時’ 在一預濕潤處理(第一前處理)係實行以將基板W浸入於脫 氣水達10分鐘且然後一代換處理(第二前處理)係實行以使 用具有10 g/L銅濃度之一前處理溶液代換該鈷薄膜之表面 達1分鐘之後’其具有1〇μηι之一直徑與約ΙΟΟμπι之一深度。 第12圖顯示一基板w,該者表面係覆蓋以一鈷薄膜且係具 有數個通孔12b,該等通孔12b在該基板W使用一硫酸銅電 鍍溶液電鍍’以一銅電鍍金屬18嵌入該等通孔12b時,在該 預濕潤處理與該代換處理係在如第U圖之相同方式中實行 之後’其具有20μηι之一直徑與約120μηι之一深度。第13圖 顯示一基板W,該者表面係覆蓋以一鈷薄膜且係具有數個 通孔12c ’該等通孔12c在該基板W使用一硫酸銅電鑛溶液 電鍍,以一銅電鍍金屬18嵌入該等通孔12c時,在該預濕潤 處理與該代換處理係在如第12圖之相同方式中實行之後, 其具有30μηι之一直徑與約130μηι之一深度。 從第11至第13圖可以看見的是,當該代換處理(第二前 處理)係使用10g/L銅濃度之一前處理溶液實行以代換該姑 薄膜之表面達1分鐘時,具有ΙΟμηι之一直徑及l〇(^m之—深 度的該等通孔12a,如第11圖所顯示,係嵌入至不同深产, 26 201247946 具有30μπι之一直徑及13〇μηι之一深度的該等通孔12c,如第 13圖所顯示’係於該等通孔12c深處產生未裝填地帶而嵌入 的’而具有20μιη之一直徑及12〇μιη之一深度的該等通孔 12b,如第12圖所顯示,係嵌入良好的。 具備1 Og/L鋼濃度之該前處理溶液係藉由將硫酸銅溶 解於純水中而製備。具備3〇g/L銅濃度之一前處理溶液及具 備60g/L銅濃度之一前處理溶液,於下文所描述的,亦係藉 由將硫酸銅溶解於純水中而製備。 第14圖顯示一基板W,該者表面係覆蓋以一鈷薄膜且 係具有數個通孔12a,該等通孔12a在該基板%使用一硫酸 銅電鍍溶液電鍍,以一銅電鍍金屬18嵌入該等通孔12a時, 在一預濕潤處理(第一前處理)係實行以將基板w浸入於脫 氣水達10分鐘且然後一代換處理(第二前處理)係實行以使 用具有30g/L銅濃度之一前處理溶液代換該鈷薄膜之表面 達1分鐘之後,其具有1〇μπι之一直徑與約1〇〇μιη之一深度。 第15圖顯示一基板W,該者表面係覆蓋以一鈷薄膜且係具 有數個通孔12b,該等通孔12b在該基板…使用一硫酸鋼電 鍍溶液電鍍,以一銅電鍍金屬18嵌入該等通孔12b時,在該 預濕潤處理與該代換處理係在如第丨4圖之相同方式中實行 之後’其具有20μηι之一直徑與約120μηι之一深度。 從第14至第15圖可以看見的是,當該代換處理(第二前 處理)係使用30g/L銅濃度之一前處理溶液實行以代換該鈷 薄膜之表面達1分鐘時,具有ΙΟμιη之一直徑及1〇〇μιη之—深 度的該等通孔12a,如第14圖所顯示,係均勻地嵌入至相當 27 201247946 深度且同時在該等通孔12a深處產生小的未裝填地帶’而具 有2〇μηι之一直徑及之一深度的該等通孔12b,如第15 圖所顯示’實質上係完全嵌入的。 第16圖顯示一基板w,該者表面係覆蓋以一鈷薄膜且 係具有數個通孔12a ’該等通孔12a在該基板W使用一硫酸 銅電鍍溶液電鍍,以一銅電鍍金屬18嵌入該等通孔12a時, 在一預濕潤處理(第一前處理)係實行以將基板W浸入於脫 氣水達10分鐘且然後一代換處理(第二前處理)係實行以使 用具有60g/L銅濃度之一前處理溶液代換該鈷薄膜之表面 達1分鐘之後,其具有ΙΟμιη之一直徑與約ΙΟΟμιη之一深度。 第17圖顯示一基板w,該者表面係覆蓋以一鈷薄膜且係具 有數個通孔12b,該等通孔12b在該基板W使用一硫酸銅電 鍍溶液電鍍’以一銅電鍍金屬18嵌入該等通孔12b時,在該 預濕潤處理與該代換處理係在如第16圖之相同方式中實行 之後’其具有20μηι之一直徑與約120μπι之一深度。第18圖 顯示一基板W,該者表面係覆蓋以一鈷薄膜且係具有數個 通孔12c ’該等通孔12c在該基板W使用一硫酸銅電鍵溶液 電鍍,以一銅電鍍金屬18嵌入該等通孔12c時,在該預濕湖 處理與該代換處理係在如第16圖之相同方式中實行之後, 其具有30μηι之一直徑與約130μιη之一深度。 從第16至第18圖可以看見的是’當該代換處理(第二前 處理)係使用60g/L銅濃度之一前處理溶液實行以代換該钻 薄膜之表面達1分鐘時’具有ΙΟμηι之一直徑及ι〇〇μιη之一深 度的該等通孔12a,如第16圖所顯示,係於該等通孔12a深 28 201247946 處產生小的未裝填地帶而嵌入的,具有20μηι之一直徑及 12〇μιη之一深度的該等通孔12b ’如第17圖所顯示,且具有 3〇μιη之一直徑及130μιη之一深度的該等通孔12c,如第18 圖所顯示,係嵌入良好的。 在上文該實施例中,在依據一電鍍製程將銅(第二金屬) 嵌入通孔中,鈷係使用做為一第一金屬其較氫具有一較大 的離子化趨勢,且銅係使用做為一第二金屬,該者較鈷係 更為惰性的。一含有銅的前處理溶液係藉由將在一電鍍溶 液中含有的硫酸銅溶解於純水中而製備。由於該前處理溶 液係使用在該電鍍溶液中含有之一成分製備的,其係沒有 必要顧及夾帶不想要的物質至後續製程。鈀、金、鉑或銀 可能使用做為一金屬(第二金屬)其較鈷(第—金屬)係更為 惰性者,而通孔可能依據一電鍍製程將銅(第三金屬)嵌入 的。 在上文該實施例中,該預濕潤處理(第_前處理)係用於 將一基板浸入於諸如純水(DIW)之脫氣水中,以提升該基板 表面的親水性,而該代換處理(第二前處理)制於將板 浸入於含有銅之-略微雜或略麟㈣前處理溶液中, 其中銅較鈷贼為舰的,以由銅代換在—料膜表面中 之姑,該二前處理係彼此分開來實行的。然而該預濕潤 處理(第一前處理)與該代換處理(第二前處理)可能藉由將 -基板浸人於-脫氣前處理溶液其在從_略微酸性^度至 -略微驗性程度該範圍中且具備溶解於其中之銅而同:實 29 201247946 、在上文該實施例中,鋼係藉助於在一钻薄膜表面上的 代換而沈積’其t贿軸係雙重地做為_障蔽層與一種 子層,且通孔係藉由1鍍製程嵌人銅。然而,本發明亦 可應用於依據-魏製程在具有較氫—較大離子化趨勢的 金屬表面沈賴。在此—事财,銅係藉助於使用具有溶 解於其中之銅的前處理溶液在該金屬表面上的代換而沈 積’且‘然後該表面係電鍍此實關之㈣膜作 用為-障蔽層’ -_膜可能使用做為-障蔽層。該金屬 (第金屬),覆蓋6亥等通孔者,可能不必要作用為一障蔽 層。本發财可應㈣形成另—障蔽狄製程,在該障蔽 層上沈積-金屬(第—金屬)其較氫具有—較大的離子化趨 勢者,且錢在該沈積金屬上電賴。該祕於代換而沈 積之金屬料限於銅’域㈣人於祕之金聽不限於 銅0 該金屬(第一金屬)之例子,該者依據本發明較氫具有一 較大的離子化趨勢,包括鎳,舉例而言,除了鈷之外。藉 助於代換沈積於該第一金屬表面上之該金屬(第二金屬)的 例子除了銅之外包括把、金及銀。在上文該實施例中,一 金屬係嵌入於通孔。然而,本發明之原理亦可應用於溝槽 内連線(trench interconnects)中金屬之嵌入或通洞之電鍵。 雖然本發明已藉由參照至較佳實施例而說明,其係不 言而明的是本發明係非限於該等實施例,而是能在於此所 描述之該一般發明概念中做各種修飾。 【圖式簡單説明】 201247946 第1A至1C圖係為橫截面圖其顯示製作具有垂直延伸 經由該基板之數個銅通孔柱之一基板的方法; 第2圖係為一橫截面圖其顯示表面覆蓋以一鈷薄膜且 具有通孔之一基板; 第3圖係為一橫截面圖其顯示一基板,該者之表面係覆 蓋以一鈷薄膜,且具有數個通孔其具有ΙΟμιη之一直徑與 1 ΟΟμιη之一深度,在使用一硫酸銅電鍍溶液電鍍該基板 時,以銅電鍍金屬嵌入該等通孔; 第4圖係為一橫截面圖其顯示一基板,該者之表面係覆 蓋以一鈷薄膜,且具有數個通孔其具有20μιη之一直徑與 120μιη之一深度,在使用一硫酸銅電鍍溶液電鍍該基板 時,以銅電鍍金屬嵌入該等通孔; 第5圖係為一橫截面圖其顯示一基板,該者之表面係覆 蓋以一鈷薄膜,且具有數個通孔其具有30μηι之一直徑與 130μηι之一深度,在使用一硫酸銅電鍍溶液電鍍該基板 時,以銅電鍍金屬嵌入該等通孔; 第6圖係為一示意平面圖,其顯示使用於實行本發明之 一電鍍方法之一電鍍設施的整體排列; 第7圖係為在第6圖顯示之該電鍍設施中所採用之一輸 送機械手臂的示意立面圖; 第8圖係為在第6圖顯示之該電鍍設施中所採用之一電 鍍裝置的示意橫截面圖; 第9圖係為在第8圖顯示之該電鍍裝置之一攪拌槳(攪 拌工具)的平面圖; 31 201247946 第10圖係為沿第9圖之線A-A所取之一橫截面圖; 第11圖係為一橫截面圖其顯示一基板,該者之表面係 覆蓋以一鈷薄膜,且具有數個通孔其具有ΙΟμηι之一直徑與 約ΙΟΟμιη之一深度,在使用一硫酸銅電鍍溶液電鍍該基板 時,以銅電鍍金屬嵌入該等通孔,在該基板使用具備10 g/L 銅濃度之一前處理溶液處理之後; 第12圖係為一橫截面圖其顯示一基板,該者之表面係 覆蓋以一鈷薄膜,且具有數個通孔其具有20μπι之一直徑與 約120μιτι之一深度,在使用一硫酸銅電鍍溶液電鍍該基板 時,以銅電鍍金屬嵌入該等通孔,在該基板使用具備10 g/L 銅濃度之一前處理溶液處理之後; 第13圖係為一橫截面圖其顯示一基板,該者之表面係 覆蓋以一鈷薄膜,且具有數個通孔其具有30μπι之一直徑與 約130μιη之一深度,在使用一硫酸銅電鍍溶液電鍍該基板 時,以銅電鍍金屬嵌入該等通孔,在該基板使用具備10g/L 銅濃度之一前處理溶液處理之後; 第14圖係為一橫截面圖其顯示一基板,該者之表面係 覆蓋以一鈷薄膜,且具有數個通孔其具有ΙΟμιη之一直徑與 約ΙΟΟμπι之一深度,在使用一硫酸銅電鍍溶液電鍍該基板 時,以銅電鍍金屬嵌入該等通孔,在該基板使用具備30g/L 銅濃度之一前處理溶液處理之後; 第15圖係為一橫截面圖其顯示一基板,該者之表面係 覆蓋以一鈷薄膜,且具有數個通孔其具有20μιη之一直徑與 約120μηι之一深度,在使用一硫酸銅電鍍溶液電鍍該基板 32 201247946 時,以銅電鍍金屬嵌入該等通孔,在該基板使用具備30g/L 鋼濃度之一前處理溶液處理之後; 第16圖係為一橫截面圖其顯示一基板,該者之表面係 覆蓋以一鈷薄膜,且具有數個通孔其具有ΙΟμίΉ之一直徑與 約ΙΟΟμιη之一深度,在使用一硫酸銅電鍍溶液電鍍該基板 時,以銅電鍍金屬嵌入該等通孔,在該基板使用具備60g/L 銅濃度之一前處理溶液處理之後; 第17圖係為一橫截面圖其顯示一基板,該者之表面係 覆蓋以一鈷薄膜,且具有數個通孔其具有20μηι之一直徑與 約120μπι之一深度,在使用一硫酸銅電鍍溶液電鍍該基板 時,以銅電鍍金屬嵌入該等通孔,在該基板使用具備60 g/L 銅濃度之一前處理溶液處理之後;且 第18圖係為一橫截面圖其顯示一基板,該者之表面係 覆蓋以一鈷薄膜,且具有數個通孔其具有30μηι之一直徑與 約130μηι之一深度,在使用一硫酸銅電鍍溶液電鍍該基板 時,以銅電鍍金屬嵌入該等通孔,在該基板使用具備60g/L 銅濃度之一前處理溶液處理之後。 【主要元件符號說明】 通孔 110.·· 10…基底 12、12a、12b、12c··· 14…障蔽層 16…種子層 18…電鑛金屬 .20…钻薄膜 22a、22b…未裝填地帶 設備框架 112···分隔板 114…清洗空間 116···電鍍空間 120···裝載/卸載埠 33 201247946 121···操縱面板 122···對準器 124···清洗/乾燥裝置 126···第一前處理裝置 127、183…前處理槽 128···第一輸送機器手臂 160···基板支撐器 162…基板附著/分離台 164...貯藏庫 166···第二前處理裝置 168a…第一水清洗裝置 168b…第二水清洗裝置 170···電鍍裝置 172···吹氣裝置 174a、174b...第二輸送機器手臂 176…軌道 178···主體, 180…臂 182···基板支撐器固定部份 184a、184b…水清洗槽 186···電鍍槽 186a…電鍍溶液供應入口 200···溢出槽 202…幫浦 204···循環管路 206···恆溫單元 208···過濾器 210···底部板 212···下部電鍍溶液分佈室 214···上部基板加工室 216"·遮蔽板 220…陽極 222···陽極支撐器 224…調節板 226···柱狀部分 228···長方形凸緣部分 232…攪拌槳 232a…狹縫 232b…條狀部分 250···電鍍電源 252…控制段 W…基板 Q…電鍍溶液 3418 201247946 This potential distribution in the money slot 186 is disposed between the anode 22 and the substrate w disposed in the keyway 186 at a predetermined position. In this yoke case, the adjustment plate 224 includes a cylindrical portion 226 and a rectangular = edge portion 228' and is made of a dielectric material polyvinyl chloride. The columnar portion: 226 has such a (four) size and shaft length in order to sufficiently limit the electric field expansion. The bottom plate 210 is formed by the flange portion 228 of the (four) plate 224. Between the adjusting plate 224 and a predetermined position of the plating plate 186, a vertically extending mixing wood 232 is disposed as a dialing tool, which is used to reciprocate the surface of the wire r The plating solution Q between the substrate W and the conditioning plate 224 is stirred. A sufficient amount of copper ions can be uniformly supplied to the surface of the substrate W by the stirring violet 232 (stirring tool) during the electric key. As shown in Figures 9 and 1 , the agitating paddle 232 is composed of a rectangular, plate-like member having a uniform thickness "t" of ^ to ^ mm, and having a plurality of parallel slits 232a defined The vertically extending strip portions 23 are formed by, for example, a resin such as pvc, pp, and pTFE, and a sus or a layer having a weave coating. At least part (4) mixed with purple m, contact with the key solution, is electrically isolated. The vertical length L1 of the search purple 232 and the vertical length L2 of the slit coffee are sufficiently larger than the vertical size of the substrate W. Further, the stirring paddle 232 is designed such that the sum η of its lateral lengths and its reciprocating distance (stroke) are sufficiently larger than the lateral dimension of the substrate W. Preferably, the slit is The width and number of 232a are determined by 201247946 by the fact that each strip portion 232b is narrower as far as possible to the extent that it has the necessary rigidity such that the strip portions between the narrow strips 232a 232b can effectively mix the key solution, and the plating solution can be The plating device 170 is provided with a plating power source 250. The positive electrode of the device is connected to the anode 220 via a wire during plating, and the negative electrode is connected to the substrate W via a wire. The plating power source 250 is coupled to a control section 252' and the plating apparatus 170 is controlled based on signals originating from the control section 252. The series of plating processes will be described below, which is by the sixth The electroplating apparatus shown in the figure is used for plating the surface of the substrate W. The substrate is provided with a cobalt film 2〇 formed on the entire surface thereof, including the surface of the through holes 12, as shown in FIG. It is shown that a copper sulphate plating solution is used, so that a plated metal 'meaning copper' is embedded in the through holes 12. First, the substrate W is placed in a substrate , with its front surface (the surface to be plated) Face up, and the substrate is mounted on the loading/unloading cassette 120. One of the substrates W is taken out from the substrate mounted on the loading/unloading cassette 12Q by the first conveying robot arm 128. And placed in The aligner 12 2 is aligned with one of the substrates w to align the flat plate or the notch in a pre-determined direction. Another aspect is 'two substrate supports (10) which are stored in a vertical state in the reservoir (6) By taking out the 'rotation' by the second transfer robot arm (10), whereby the substrate supports (four) 16 处于 in a - horizontal state ' and then placed in parallel on the substrate attachment/separation table 162 0 20 201247946 in a predetermined The substrates W that are aligned with their alignment plates or notches are transported and loaded into the substrate holder 160 placed on the substrate attachment/detachment stage 162, which is in a state by which the substrates are The peripheral part is sealed. The two substrate holders 160, which have been loaded with the substrates w, are simultaneously fixed, lifted, and then transported to the reservoir 164 by the second transfer robot arm 74a. The substrate support 160 is rotated 90. The vertical state is lowered and lowered, whereby the two substrate holders 16 are held in the suspension 164 in a hanging manner (temporary storage). The above operations are repeated in a sequential manner whereby the substrate is successively loaded into the substrate holder 16 存放 stored in the reservoir 164 and successively in a suspension mode The predetermined position is maintained in the storage 164 (temporary storage). On the other hand, the two substrate supporters 160, which have been loaded with the substrates and temporarily stored in the storage 164, are simultaneously fixed, lifted, and then transported to the first by the first conveyor arm 174b. The pre-processing device 126 is in the first pre-processing device 126, and the substrates w supported by the substrate holders 16 are immersed in degassed water in the pre-treatment tank 127, such as pure water (DIW). ) to thereby perform a pre-wetting treatment (first pre-treatment) on the surface of the substrate. The pure water used as the deaerated water is preferably adjusted to a dissolved oxygen concentration of 2 mg/L or less by a vacuum deaerator, and therefore, by performing pre-wetting treatment on the surface of the substrate W (the first) The pre-treatment), the hydrophilicity of the surface of the substrate W can be increased, allowing the highly permeable degassed water to enter the through holes 12 in the substrate W. After the first pre-processing, the two substrate holders 16 are each loaded with a substrate, which is transported to the 21st 201247946 pre-processing H166 in the same manner as described above, in which , the substrate substrate is in the treatment tank 183 - the former Lu persimmon j treatment "cold liquid, the pretreatment solution contains copper in the system ^ ° micro acidity to a slight degree of inspection, so as to «Mysterious cobalt: 4 membrane 2 〇 on the surface - generation domain (second pretreatment). In this substitution process (= two pre-treatments), the job water, the person performing the pre-wet treatment (the W-th treatment) has entered the through-holes 12 in the substrate w, by the pre-treatment solution Change, and the side of the hole 12 is still filled with a simple solution. This replacement process will be described in detail below. When reducing the film 2〇 covering the surface of the riding substrate ~ every __, when immersed in the treatment solution containing copper, 'cobalt on the surface of the (four) lion, which is less inert than the copper system, The pretreatment solution towel was changed, and the surface of the cobalt film 20 was woven from (4). The surface of the #2G film, covered with copper, will be protected from a money solution. When copper covers the entire surface of the cobalt film 2, the substitution reaction is stopped, and a very thin copper film is deposited on the surface of the cobalt film. The thickness of the cobalt ruthenium film 20 is not substantially affected by the copper film, whereby the function of the cobalt ruthenium film 20 as a barrier layer is still effective or not. The pretreatment solution is preferably in a range from a slightly acidic degree to a slightly alkaline degree to prevent the cobalt film 2 from being dissolved therein upon contact with the pretreatment solution. The pretreatment solution may have a dissolved oxygen concentration adjusted to 2 mg/L or less, such as the deaerated water. After the second pre-treatment, the substrate holders 160, each carrying the substrates W, are transported to 22 201247946, the first water cleaning device 168a, in the same manner as described above. The surface of the substrate w is cleaned with pure water held in the first water washing tank 184a. After the water cleaning, the two substrate holders 16 are loaded with the substrates W and transported to the plating bath 186 of the plating apparatus 170 in the same manner as described above. The plating bath 186 has been filled with a predetermined amount of plating solution Q having a predetermined composition which is carried by the sinusoidal system. The substrate board 16 is then lowered to immerse the substrates W supported by the substrate holders 160 in the electroplating solution Q in the plating bath 186. Each of the substrates w is disposed at one of the positions of the electric ore solution q facing the anode 220 of the building supported by the anode baffle 222. Each substrate W is immersed in the plating solution Q for a predetermined time, and the plating solution Q is substituted for the pre-treatment solution in the through holes 12 during the predetermined time period, at the anode 220 and the No voltage is applied between the cobalt films, wherein the drill film is attached to the surface of each substrate W and covered with a copper film. Thereafter, a voltage is applied between the anode 22 and the surface of each substrate w between the cobalt thin films covered with a copper film, and an electroplating process is performed to coat the cobalt film covered by the copper film. A copper plating film is deposited on the surface of the film 20, and the plating film of the steel is embedded in the through holes 12. The plating solution q used in the electroplating process is an acidic sulfuric acid bond solution. The management of the person is relatively easy to carry out. If the cobalt film 2 is in direct contact with the acidic copper sulfate plating solution, then the cobalt film 20 is dissolved in the plating solution. In this embodiment, however, since the surface of the cobalt film 20 is covered with a very thin copper film, the cobalt film 2 23 23 201247946 remains in direct contact with the acidic copper sulphate plating solution, and thereby prevents Dissolved in the plating solution Q. The plating process is terminated after the voltage between the anode 22 and the surface of the substrate w has been applied for a predetermined period of time. After the 5 well substrate W has been immersed in the key solution Q, and until the plating gyro system is terminated, the agitating paddles 232 are moved back and forth parallel to the substrate w to agitate between the adjusting plate 224 and the The plating solution Q between the substrates W. The embedding of the vias 12 continues until the aspect ratio of the vias 12 is reduced until the plating solution Q can easily reach the limit of the surface of the metal plated on the sides of the vias 12. If the plating solution Q is still vigorously stirred by the stirring paddles 232 at this time, then the growth of the plating metal may be slowed down, requiring an extra time until the through holes 12 are completely embedded. In order to avoid this disadvantage, it is desirable that the plating solution Q is less agitated when the plating process has been carried out to some extent. After the termination of the electroplating process, the voltage applied between the anode 220 and the surface of each substrate, the cobalt film 20 covered with a copper film, is closed. Thereafter, the two substrate holders 160, each loaded with the substrate W', are again supported by the second transfer robot arm 174b and withdrawn from the keyway 186. The two substrate holders 16 0 are then routed to the second water cleaning device 168b in the same manner as described above, where the surfaces of the substrates are immersed in the water by immersing the substrates It is cleaned by 5 liters of pure water held in the tank 184b. Thereafter, the substrate holders 160, each loaded with the substrate, are transported to the blow 24 201247946 gas device 172' at the same location as described above, the electromineral solution and the water droplet system The substrate holder 16 is removed from the substrate holder 16 by blowing air or inert gas onto the substrate support n16(). Thereafter, the substrate branches (4) (10) are loaded into the reservoir 164 in the same manner as described above, and each of the substrates is held in the storage. Library (6). The second transport robot arm 174b sequentially repeats the above operations to sequentially support the substrate to the H16G, and each of the substrates is loaded with a substrate to return to the library 164. The substrate holder 160 is suspended and suspended in the reservoir 164. On the other hand, 'two substrate holders 160 loaded with the plated substrate' have been returned to the reservoir 164, simultaneously grasped by the second conveyor robot 174a in the same manner as described above. It is taken and placed on the substrate attachment/detachment stage 162. The first transfer robot arm 128 is disposed in the cleaning space 114, and takes out a substrate from a substrate holder 160 placed on the substrate attachment/detachment table 162 and transports the substrate to the cleaning/drying device. One of the 24s. In the cleaning/drying devices 124, the substrates are maintained in a horizontal position with the front surface facing up, cleaned, for example, with pure water, and then spin dried by rotation at a high speed. Thereafter, the substrates are returned to the substrate on the loading cassette 120 by the material-conveyor arm 128 to complete the plating operation. - The experiment is performed on the surface of the substrate, and the entire surface of the substrate is covered with a cobalt film, including surfaces of different sizes of through holes. The pre-treatment (first-pre-treatment) is performed by immersing the base = immersed in deaerated water followed by the substitution process (second pre-treatment), which makes 25 201247946 use a number of different copper concentrations A type of pretreatment solution for substituting the film. Thereafter, the substrates are plated to embed the vias with copper plating metal. The embedding of these through holes in the experiment will be explained below. Figure 11 shows a substrate w which is covered with a cobalt film and has a plurality of through holes 12a. The through holes na are plated on the substrate W using a copper sulfate plating solution, embedded in a copper plated metal 18 The through holes i2a are performed in a pre-wet treatment (first pre-treatment) to immerse the substrate W in deaerated water for 10 minutes and then a one-generation process (second pre-treatment) is carried out to use 10 g. One of the /L copper concentrations of the pretreatment solution is substituted for the surface of the cobalt film for 1 minute after it has a diameter of 1 〇μηι and a depth of about ΙΟΟμπι. Figure 12 shows a substrate w which is covered with a cobalt film and has a plurality of through holes 12b which are plated with a copper sulfate plating solution on the substrate W. In the case of the through holes 12b, after the pre-wetting treatment and the substitution processing are carried out in the same manner as in the U-th image, it has a diameter of one of 20 μm and a depth of about 120 μm. Figure 13 shows a substrate W which is covered with a cobalt film and has a plurality of through holes 12c. The through holes 12c are plated on the substrate W using a copper sulfate electroplating solution to electroplate a metal 18 When the through holes 12c are embedded, after the pre-wetting treatment and the substitution processing are carried out in the same manner as in Fig. 12, they have a diameter of one of 30 μm and a depth of about 130 μm. It can be seen from the 11th to 13th that when the substitution treatment (second pretreatment) is performed by using one of the 10 g/L copper concentration pretreatment solutions to replace the surface of the ruthenium film for 1 minute, One of the diameters of the ΙΟμηι and the depth of the hole 12a, as shown in Fig. 11, is embedded in different deep production, 26 201247946 having a depth of one of 30 μπι and a depth of 13 〇 μη The through holes 12c, as shown in Fig. 13, are embedded in the depth of the through holes 12c to form an unfilled land, and have such a through hole 12b having a diameter of 20 μm and a depth of 12 μm. As shown in Fig. 12, it is well embedded. The pretreatment solution having a steel concentration of 1 Og/L is prepared by dissolving copper sulfate in pure water. The pretreatment solution having a concentration of 3 〇g/L copper And a pretreatment solution having a copper concentration of 60 g/L, as described below, is also prepared by dissolving copper sulfate in pure water. Figure 14 shows a substrate W which is covered with a cobalt. The film has a plurality of through holes 12a, and the through holes 12a use a sulfuric acid on the substrate The copper plating solution is electroplated, and when a copper plating metal 18 is embedded in the through holes 12a, a pre-wetting treatment (first pre-treatment) is performed to immerse the substrate w in the deaerated water for 10 minutes and then to replace the treatment ( The second pretreatment was carried out to replace the surface of the cobalt film with a pretreatment solution having a copper concentration of 30 g/L for 1 minute, which had a diameter of 1 μm and a depth of about 1 μm. Figure 15 shows a substrate W which is covered with a cobalt film and has a plurality of through holes 12b which are plated on the substrate using a sulfuric acid steel plating solution and embedded in a copper plating metal 18 In the case of the through holes 12b, after the pre-wetting treatment and the substitution processing are carried out in the same manner as in FIG. 4, it has a diameter of one of 20 μm and a depth of about 120 μm. From the 14th to the 15th. It can be seen that when the substitution treatment (second pretreatment) is carried out by using a pretreatment solution of 30 g/L copper concentration to replace the surface of the cobalt film for 1 minute, it has a diameter of ΙΟμιη and 1 〇〇μιη—the depth of these The hole 12a, as shown in Fig. 14, is uniformly embedded to a depth of 27 201247946 and at the same time produces a small unfilled zone at the depth of the through holes 12a and has a diameter of one 及μηι and one depth The through hole 12b, as shown in Fig. 15, is substantially completely embedded. Fig. 16 shows a substrate w which is covered with a cobalt film and has a plurality of through holes 12a' such through holes 12a. The substrate W is plated with a copper sulfate plating solution, and a copper plating metal 18 is embedded in the through holes 12a, and is subjected to a pre-wetting treatment (first pretreatment) to immerse the substrate W in the deaerated water up to 10 Minutes and then one-generation treatment (second pre-treatment) is carried out to replace the surface of the cobalt film with one of the pretreatment solutions having a copper concentration of 60 g/L for one minute, which has one diameter of ΙΟμιη and one of about ΙΟΟμιη depth. Figure 17 shows a substrate w which is covered with a cobalt film and has a plurality of through holes 12b which are plated with a copper sulfate plating solution on the substrate W. In the case of the through holes 12b, after the pre-wetting treatment and the substitution processing are carried out in the same manner as in Fig. 16, it has a diameter of one of 20 μm and a depth of about 120 μm. Figure 18 shows a substrate W which is covered with a cobalt film and has a plurality of through holes 12c. The through holes 12c are plated on the substrate W using a copper sulfate electroless solution, embedded in a copper plated metal 18 The through holes 12c have a diameter of one of 30 μm and a depth of about 130 μm after the pre-wet lake treatment and the replacement process are carried out in the same manner as in Fig. 16. It can be seen from Figures 16 to 18 that 'when this substitution process (second pretreatment) is performed using one of the 60 g/L copper concentrations to pretreat the surface of the drill film for 1 minute' The through holes 12a of one of the diameters of ΙΟμηι and one of the depths of ι〇〇μηη, as shown in Fig. 16, are embedded in the small unfilled zone at the depth 28 201247946 of the through holes 12a, and have a 20 μηι The through holes 12b' having a diameter and a depth of 12 〇μη as shown in FIG. 17, and having the diameter of one of 3 μm and one of the depths of 130 μm, as shown in FIG. 18, The system is well embedded. In the above embodiment, the copper (second metal) is embedded in the through hole according to an electroplating process, and the cobalt is used as a first metal, which has a larger ionization tendency than hydrogen, and the copper system is used. As a second metal, this is more inert than cobalt. A copper-containing pretreatment solution is prepared by dissolving copper sulfate contained in a plating solution in pure water. Since the pretreatment solution is prepared using one of the components in the plating solution, it is not necessary to take care of entraining the undesired material to the subsequent process. Palladium, gold, platinum or silver may be used as a metal (second metal) which is more inert than cobalt (metal), and vias may be embedded in copper (third metal) according to an electroplating process. In the above embodiment, the pre-wetting treatment (the first pre-treatment) is for immersing a substrate in degassed water such as pure water (DIW) to enhance the hydrophilicity of the surface of the substrate, and the substitution is performed. The treatment (second pretreatment) is carried out by immersing the plate in a copper-containing slightly slightly or slightly lining (four) pretreatment solution, wherein the copper is replaced by a cobalt thief, and the copper is substituted for the surface of the film. The two pre-treatments are implemented separately from each other. However, the pre-wetting treatment (first pre-treatment) and the substitution treatment (second pre-treatment) may be performed by immersing the substrate in the pre-degassing treatment solution from a slight acidity to a slightity. To the extent that it has the copper dissolved therein: the same as: 29 201247946. In the above embodiment, the steel system is deposited by means of substitution on the surface of a drilled film. It is a barrier layer and a sub-layer, and the through-hole is embedded with human copper by a plating process. However, the present invention can also be applied to the surface of a metal having a tendency to be more hydrogen-larger ionization according to the -Wei process. Herein, the copper system deposits 'and' by using a pretreatment solution having copper dissolved therein on the surface of the metal, and then the surface is electroplated (4) to act as a barrier layer. '-_ Membrane may be used as a barrier layer. The metal (metal), which covers the vias such as 6 hai, may not necessarily act as a barrier layer. The fortune can be used to form a further barrier process in which a metal (metal) is deposited on the barrier layer, which has a larger ionization tendency than hydrogen, and the money is electrically charged on the deposited metal. The metal material deposited by the substitution is limited to the copper 'domain (4). The person is not limited to copper 0. The metal (first metal) example has a larger ionization tendency than hydrogen according to the present invention. , including nickel, for example, in addition to cobalt. An example of the metal (second metal) deposited by substituting the first metal surface includes, in addition to copper, gold, silver, and silver. In the above embodiment, a metal system is embedded in the through hole. However, the principles of the present invention can also be applied to the embedding or through hole of a metal in trench interconnects. Although the present invention has been described with reference to the preferred embodiments thereof, it is to be understood that the invention is not limited to the embodiments, but various modifications can be made in the general inventive concept described herein. BRIEF DESCRIPTION OF THE DRAWINGS 201247946 Sections 1A to 1C are cross-sectional views showing a method of fabricating a substrate having a plurality of copper via posts extending vertically through the substrate; FIG. 2 is a cross-sectional view showing the same The surface is covered with a cobalt film and has a substrate of a through hole; FIG. 3 is a cross-sectional view showing a substrate covered with a cobalt film and having a plurality of through holes having one of ΙΟμιη a diameter of one of 1 ΟΟμιη, when the substrate is electroplated with a copper sulfate plating solution, the through holes are embedded with copper plating metal; FIG. 4 is a cross-sectional view showing a substrate, the surface of which is covered a cobalt film having a plurality of through holes having a diameter of one of 20 μm and a depth of 120 μm. When the substrate is plated with a copper sulfate plating solution, the through holes are embedded with copper plating metal; A cross-sectional view showing a substrate covered with a cobalt film and having a plurality of through holes having a diameter of one of 30 μm and a depth of 130 μm, using a copper sulfate plating solution In the case of the substrate, the through holes are embedded in the copper plating metal; FIG. 6 is a schematic plan view showing the overall arrangement of the electroplating facility used in the electroplating method of the present invention; FIG. 7 is in the sixth The figure shows a schematic elevational view of one of the transport robots used in the electroplating facility; Fig. 8 is a schematic cross-sectional view of one of the electroplating devices used in the electroplating facility shown in Fig. 6; A plan view of a stirring paddle (stirring tool) of the plating apparatus shown in Fig. 8; 31 201247946 Fig. 10 is a cross-sectional view taken along line AA of Fig. 9; Fig. 11 is a A cross-sectional view showing a substrate covered with a cobalt film and having a plurality of through holes having a diameter of one of ΙΟμηι and a depth of about ΙΟΟμηη, when the substrate is plated using a copper sulfate plating solution The through holes are embedded in the copper plating metal after the substrate is treated with a pretreatment solution having a copper concentration of 10 g/L; FIG. 12 is a cross-sectional view showing a substrate, the surface of which is covered with One cobalt film And having a plurality of through holes having a diameter of one of 20 μm and a depth of about 120 μm, and when the substrate is plated with a copper sulfate plating solution, the through holes are embedded in the copper plating metal, and the substrate is used with 10 g/ After the pretreatment solution is treated as one of the L copper concentrations; Fig. 13 is a cross-sectional view showing a substrate covered with a cobalt film and having a plurality of through holes having a diameter of about 30 μm and about At a depth of 130 μm, when the substrate is electroplated using a copper sulfate plating solution, the through holes are embedded in a copper plating metal, and the substrate is treated with a pretreatment solution having a copper concentration of 10 g/L; A cross-sectional view showing a substrate covered with a cobalt film and having a plurality of through holes having a diameter of one of ΙΟμηη and a depth of about ΙΟΟμπι, when the substrate is plated using a copper sulfate plating solution Inserting the through holes with copper plating metal after the substrate is treated with a pretreatment solution having a copper concentration of 30 g/L; FIG. 15 is a cross-sectional view showing a substrate, The surface of the person is covered with a cobalt film and has a plurality of through holes having a diameter of 20 μm and a depth of about 120 μm. When the substrate 32 201247946 is electroplated using a copper sulfate plating solution, the copper plating metal is embedded therein. The through hole is processed after the substrate is treated with a pretreatment solution having a steel concentration of 30 g/L; and FIG. 16 is a cross-sectional view showing a substrate covered with a cobalt film and having a number The through hole has a diameter of one of ΙΟμίΉ and a depth of about ΙΟΟμιη. When the substrate is plated with a copper sulfate plating solution, the through holes are embedded in the copper plating metal, and one of the copper concentrations of 60 g/L is used in the substrate. After the treatment of the pretreatment solution; Fig. 17 is a cross-sectional view showing a substrate covered with a cobalt film and having a plurality of through holes having a diameter of 20 μm and a depth of about 120 μm. When the substrate is electroplated using a copper sulfate plating solution, the through holes are embedded in the copper plating metal after the substrate is treated with a pretreatment solution having a copper concentration of 60 g/L; And Figure 18 is a cross-sectional view showing a substrate covered with a cobalt film and having a plurality of through holes having a diameter of 30 μm and a depth of about 130 μm, using copper sulfate When the plating solution is plated with the substrate, the through holes are embedded in the copper plating metal after the substrate is treated with a pretreatment solution having a copper concentration of 60 g/L. [Description of main component symbols] Via 110.·· 10... Substrate 12, 12a, 12b, 12c, ... 14... barrier layer 16... seed layer 18... electro-mineral metal. 20... drilled film 22a, 22b... unfilled zone Equipment frame 112··· partition plate 114...cleaning space 116···plating space 120···loading/unloading埠33 201247946 121···manipulation panel 122···aligner 124···cleaning/drying device 126···First pretreatment device 127, 183... pretreatment tank 128···first transport robot arm 160···substrate support 162...substrate attachment/separation table 164...storage 166··· Two pre-processing devices 168a...first water washing device 168b...second water washing device 170···plating device 172···air blowing device 174a, 174b...second conveying robot arm 176...track 178··· body , 180...arm 182···substrate holder fixing portion 184a, 184b...water cleaning tank 186···plating tank 186a...electroplating solution supply inlet 200···overflow tank 202...helper 204···circulation line 206···Thermal unit 208···Filter 210···Bottom plate 212···The lower plating solution distribution room 214··· Upper substrate processing chamber 216"·shield plate 220...anode 222···anode support 224...adjustment plate 226···column portion 228···rectangular flange portion 232...stirring paddle 232a...slit 232b... strip portion 250···plating power supply 252... control section W... substrate Q... plating solution 34