1380750 九、發明說明： 【發明所屬之技術領域】 近年來在電子機器用配線基板的領域，隨著高密度封 裝化，銅配線的細線化正急速地進行，配線寬度及配線間 顯著地逐漸變窄。又，在晶圓級晶片尺寸封裝（Wafer-level Chip Size Package)的領域’藉由半加法來形成細線銅配 線、或是形成突起[Bump:爲了連接基板與封裝而設置的小 節結狀導體突起]成爲主流。 【先前技術】 半加法係使用無電解鍍敷或是濺鍍法等物理方法在基 板上設置金屬薄膜層（以下稱「種晶層」），藉由微影在其 上面形成配形成用或突起形成用光阻圖案。形成銅配線時 更施行電鍍銅，最後蝕刻去除剝離光阻後不需要的種晶層 而形成銅配線。形成突起時，係施行構成突起的金屬，例 如鍍敷焊料’最後蝕刻去除剝離光阻後不需要的種晶層而 形成突起。 本發明者等提案揭示一種在過氧化氫-硫酸中添加唑 類的系統’作爲在該半加法之晶種層的銅蝕刻液（參照專利 文獻1) °雖然種晶係無電解鍍敷銅時，該蝕刻液能夠具有 0 @ f虫刻’但是種晶層係藉由濺鍍法所形成的銅時，則 無'法完全纟虫刻去除。因爲濺鍍銅係在絕緣層上以微粒子的 狀態緻密、物理性地形成，所以比更無電解鍍敷銅更不容 進行飽刻去除。因此爲了完全蝕刻去除而進行過度蝕刻時 會減少銅配線寬度。又，有提案揭示一種在銅配線側面或 1380750 表面上形成銅以外的金屬皮膜而進行蝕刻種晶層的銅之方 法’但是上述的藥液時同樣地，種晶層係濺鍍銅時亦無法 完全蝕刻去除（參照專利文獻2、3 )。 關於使用半加法之種晶層的鎳蝕刻液，有提案揭示一 種過氧化物-硝酸-硫酸系統，但是種晶層係以濺鍍法所形 成的鎳（濺鍍鎳）時，則無法完全蝕刻去除（參照專利文獻 4)。因此，在藉由半加法來形成細線銅配線時，要求一種 蝕刻去除種晶層的濺鍍銅或濺鍍鎳之實用化的方法，能夠 抑制銅配線的配線寬度減少。 [專利文獻1 ]特開2 0 0 5 - 5 3 4 1號公報 [專利文獻2]特開平9-162523號公報 [專利文獻3]特開2003-78234號公報 [專利文獻4]特開2001-14〇〇84號公報 【發明內容】 本發明之課題係提供一種製造基板的方法，係使用具 有藉由濺鍍法所形成的金屬薄膜層之基板，以半加法形成 細線銅配線突起，其特徵爲，能夠迅速去蝕刻去除種晶層 的金屬、特別是濺鍍銅或濺鍍鎳，能夠抑制銅配線的配線 寬度減少、沒有斷線、短路等不良、不會侵蝕突起構成金 屬、可靠性高。 爲了解決上述課題，本發明者反覆地專心檢討結果， 發現半加法其使用具有藉由濺鍍法所形成的金屬薄膜層之 基板，藉由使用以特定的濃度及比率含有過氧化氫及磷酸 之蝕刻液作爲金屬薄膜層的蝕刻液，能夠解決上述課題， 1380750 又，在蝕刻液之過氧化氫與磷酸的重量比（過氧化氫/ 磷酸）爲0.02〜0.3。過氧化氫與磷酸的重量比小於〇.〇2時 及大於0.3時種晶層的蝕去除性不充分，特別是銅配線形 成時因爲減少銅配線的配線寬度變爲顯著，乃是不佳。 基板有Ti、Si、Sn、Cr及其合金，其中可以舉出有由 Ti、TiN、TiW、Si、Si02、SiN、Sn ' SnPb、SnAg、Cr、 CrNi等金屬所構成之主要使用於晶圓級晶片尺寸封裝所使 用的基板、及使用聚醯亞胺作基材之軟性基板等。 在本發明，作爲蝕刻對象之種晶層金屬係藉由濺鍍法 所形成的銅、鎳金屬。 在本發明，蝕刻液與對象物的接觸方法沒有特別限 制，可以藉由浸漬處理、噴霧處理等來進行。蝕刻處理溫 度以20〜60 °C爲佳。處理溫度大於60 °C時，因爲會促進過 氧化氣的分解，乃是不佳。關於触刻處理時間，依配合對 象物的表面狀態或形狀來選擇最適合的時間，實用上以30 秒〜1 2 0秒爲佳。因爲在蝕刻處理後，在蝕刻液附著於對 象物狀態下放置時，銅表面會氧化變色而產生不均’所以 蝕刻處理後以迅速地進行水洗爲佳。 本發明所使用的蝕刻液的管理’因爲伴隨者金屬的溶 解各成分的濃度會降低’所以必須分析各成分濃度來補充 不足的成分。又，因爲隨著金屬溶解量的增加，蝕刻速度 會降低，若金屬溶解量大於1 5克/升的階段時更新蝕刻液 爲佳。 [實施例] 1380750 以下，依照實施例及比較例，具體地說明本發明，但 是本發明不限定於以下的實施例。 實施例1 調配含有1重量％過氧化氫、10重量％磷酸（過氧化氬/ 磷酸重量比=G. 1 0)之蝕刻液。接著，在矽晶圓基板上形成 0.5微米厚度之濺鍍銅膜，藉由微影在其上面形成光阻圖 案’進而施行6微米厚度之電鍍銅，最後剝離光阻，製成 銅配線寬度/配線間隔爲1 5微米/1 0微米的試驗基板。 以3 0 °C的蝕刻液浸漬處理該基板，測定配線間隔部分 之種晶層的濺鍍銅完全被蝕刻去除的時間。而且，使用光 學顯微鏡測定蝕刻處理前後的銅配線寬度，算出配線寬度 減少量。結果如表1所示。 實施例2 在實施例1除了蝕刻液使用含有0.5重量％過氧化氫、 8重量％磷酸（過氧化氫/磷酸重量比=〇.〇6)之蝕刻液以外， 與實施例1同樣地進行，測定算出去除時間與配線寬度減 少量。結果如表1所示。 比較例1 在實施例1除了蝕刻液使用含有1重量％過氧化氫、4 重量％磷酸' 0.0 1重量％ 1 Η -四唑之蝕刻液以外，與實施例 1同樣地進行，測定算出去除時間與配線寬度減少量。結 果如表1所示。 比較例2 在實施例1除了蝕刻液使用含有3重量％過氧化氫' 31380750 IX. EMBODIMENT OF THE INVENTION [Technical Fields of the Invention] In recent years, in the field of wiring boards for electronic devices, with high-density packaging, the thinning of copper wiring is rapidly progressing, and the wiring width and wiring are significantly changed. narrow. In addition, in the field of Wafer-level Chip Size Package, thin wire copper wiring is formed by semi-addition, or protrusions are formed [Bump: a small-junction conductor protrusion provided for connecting a substrate and a package) ] Become the mainstream. [Prior Art] A semi-additive system is provided with a metal thin film layer (hereinafter referred to as a "seed layer") on a substrate by a physical method such as electroless plating or sputtering, and a formation or protrusion is formed thereon by lithography. A photoresist pattern is formed. When copper wiring is formed, electroplating copper is further applied, and finally, a seed layer which is unnecessary after stripping the photoresist is removed by etching to form a copper wiring. When the protrusions are formed, a metal constituting the protrusions, for example, a plating solder is applied, and finally, a seed layer which is not required after the stripping of the photoresist is removed to form a protrusion. The inventors of the present invention have proposed a system in which an azole is added to hydrogen peroxide-sulfuric acid as a copper etching solution in the seed layer of the half-addition (see Patent Document 1). When the etching solution can have 0 @ f insects, but the seed layer is formed by sputtering, the copper is not completely removed. Since the sputtered copper is densely and physically formed on the insulating layer in the state of fine particles, it is less likely to be saturably removed than the electroless copper plating. Therefore, the copper wiring width is reduced when over etching is performed for complete etching removal. Further, there has been proposed a method of forming a metal film other than copper on the side surface of a copper wiring or a surface of 1380750 to etch a seed layer of copper. However, in the case of the above-mentioned chemical liquid, the seed layer cannot be sputtered with copper. Complete etching removal (refer to Patent Documents 2 and 3). Regarding the nickel etching solution using the semi-additive seed layer, it is proposed to disclose a peroxide-nitric acid-sulfuric acid system, but when the seed layer is formed by sputtering (nickel plating), it cannot be completely etched. Removal (refer to Patent Document 4). Therefore, when the thin-line copper wiring is formed by the half-addition, a method of etching off the sputtered copper or the sputtered nickel of the seed layer is required, and the wiring width of the copper wiring can be suppressed from being reduced. [Patent Document 1] JP-A-2003-78234 [Patent Document 3] JP-A-2003-78234 [Patent Document 4] JP-A-2001 SUMMARY OF THE INVENTION The object of the present invention is to provide a method for producing a substrate by forming a thin copper wiring protrusion by semi-addition using a substrate having a metal thin film layer formed by a sputtering method. It is characterized in that it is possible to quickly etch and remove the metal of the seed layer, in particular, by sputtering copper or sputtering nickel, and it is possible to suppress the wiring width of the copper wiring from being reduced, such as no wire breakage, short circuit, etc., which does not erode the protruding metal, reliability high. In order to solve the above problems, the inventors have repeatedly focused on reviewing the results and found that a semi-additive uses a substrate having a metal thin film layer formed by a sputtering method, and contains hydrogen peroxide and phosphoric acid at a specific concentration and ratio. The etching solution can be used as an etching solution for the metal thin film layer, and the above problem can be solved. 1380750 Further, the weight ratio of hydrogen peroxide to phosphoric acid in the etching solution (hydrogen peroxide/phosphoric acid) is 0.02 to 0.3. When the weight ratio of hydrogen peroxide to phosphoric acid is less than 〇.〇2 and more than 0.3, the etching property of the seed layer is insufficient, and in particular, when the copper wiring is formed, it is not preferable because the wiring width of the copper wiring is made remarkable. The substrate includes Ti, Si, Sn, Cr and alloys thereof, and examples thereof include a material consisting of Ti, TiN, TiW, Si, SiO 2 , SiN, Sn 'SnPb, SnAg, Cr, CrNi, etc., which are mainly used for wafers. A substrate used for a chip size package, a flexible substrate using polyimide as a substrate, and the like. In the present invention, the seed layer metal to be etched is copper or nickel metal formed by sputtering. In the present invention, the method of contacting the etching liquid with the object is not particularly limited, and it can be carried out by immersion treatment, spray treatment or the like. The etching treatment temperature is preferably 20 to 60 °C. When the treatment temperature is higher than 60 °C, it is not preferable because it promotes decomposition of the peroxidation gas. Regarding the etch processing time, the most suitable time is selected depending on the surface state or shape of the object, and it is preferably 30 seconds to 120 seconds. Since the copper surface is oxidized and discolored to cause unevenness after the etching liquid adheres to the object after the etching treatment, it is preferable to perform water washing immediately after the etching treatment. The management of the etching liquid used in the present invention is lowered by the concentration of each component in the dissolution of the accompanying metal. Therefore, it is necessary to analyze the concentration of each component to supplement the insufficient component. Further, since the etching rate is lowered as the amount of dissolved metal increases, it is preferable to update the etching liquid if the amount of metal dissolved is more than 15 g/liter. [Embodiment] 1380750 Hereinafter, the present invention will be specifically described based on examples and comparative examples, but the present invention is not limited to the following examples. Example 1 An etching solution containing 1% by weight of hydrogen peroxide and 10% by weight of phosphoric acid (argon peroxide/phosphoric acid weight ratio = G.10) was prepared. Next, a 0.5 μm thick sputtered copper film is formed on the germanium wafer substrate, and a photoresist pattern is formed thereon by the lithography to perform electroplating of a thickness of 6 μm, and finally the photoresist is stripped to obtain a copper wiring width/ A test substrate having a wiring interval of 15 μm / 10 μm. The substrate was immersed in an etching solution at 30 ° C, and the time during which the sputtered copper of the seed layer of the wiring interval portion was completely removed by etching was measured. Further, the width of the copper wiring before and after the etching treatment was measured using an optical microscope, and the amount of decrease in the wiring width was calculated. The results are shown in Table 1. Example 2 In the same manner as in Example 1, except that an etching liquid containing 0.5% by weight of hydrogen peroxide and 8% by weight of phosphoric acid (hydrogen peroxide/phosphoric acid weight ratio = 〇.〇6) was used as the etching solution. The removal time and the wiring width reduction amount were calculated and measured. The results are shown in Table 1. Comparative Example 1 In the same manner as in Example 1, except that an etching solution containing 1% by weight of hydrogen peroxide and 4% by weight of phosphoric acid '0.0 1% by weight of 1 fluorene-tetrazole was used as the etching solution, the removal time was measured and measured. Reduced amount of wiring width. The results are shown in Table 1. Comparative Example 2 In Example 1, except that the etching solution was used, it contained 3% by weight of hydrogen peroxide '3
1380750 重里°/〇磷酸（過氧化氫/隣酸重量比=1·〇〇)之蝕刻液以外，與 實施例1同樣地進行，測定算出去除時間與配線寬度減少 里·。結果如表1所示。 實施例3 調配含有1 5重量％過氧化氫' 1 5重量％磷酸（過氧化 氫/磷酸重量比=〇 · 1 〇)之蝕刻液。接著，在矽晶圓基板上形 成0.3微米厚度之濺鍍鎳膜’藉由微影在其上面形成光阻 圖案，進而施行6微米厚度之電鍍銅，最後剝離光阻，製 成銅配線寬度/配線間隔爲1 5微米/1 0微米的試驗基板。 以 3 0 °C的蝕刻液噴霧處理該基板（噴霧壓力 0 · 0 3 Μ P a)’測定配線間隔部分之種晶層的濺鑛鎳完全被蝕 刻去除的時間。而且，使用光學顯微鏡測定蝕刻處理前後 的銅配線寬度，算出配線寬度減少量。結果如表1所示。 比較例3 在實施例3除了蝕刻液使用含有0.3重量％過氧化氫、 3 0重量％硝酸、6重量％硫酸、0 · 0 1重量％氯化鈉、1重量 %2-氯-吡啶之蝕刻液以外，與實施例3同樣地進行，測定 算出去除時間與配線寬度減少量。結果如表1所示。 比較例4 在實施例1除了蝕刻液使用含有1 5重量％過氧化氫、 1 5重量％磷酸、2ppm氯離子之蝕刻液以外，與實施例3同 樣地進行，測定算出去除時間與配線寬度減少量。結果如 表1所示。In the same manner as in Example 1, except that the etching liquid of 1380 750 liter/phosphoric acid (hydrogen peroxide/o-acid weight ratio = 1 〇〇) was used, the measurement of the removal time and the wiring width was measured. The results are shown in Table 1. Example 3 An etching solution containing 15% by weight of hydrogen peroxide '15 wt% phosphoric acid (hydrogen peroxide / phosphoric acid weight ratio = 〇 · 1 Torr) was formulated. Next, a 0.3 micron thick sputtered nickel film is formed on the germanium wafer substrate. A photoresist pattern is formed thereon by lithography, and then a copper plating thickness of 6 micrometers is applied, and finally the photoresist is stripped to obtain a copper wiring width/ A test substrate having a wiring interval of 15 μm / 10 μm. The substrate (spray pressure 0 · 0 3 Μ P a) was spray-treated with an etching solution at 30 ° C to measure the time during which the splashed nickel of the seed layer of the wiring interval portion was completely etched away. Further, the width of the copper wiring before and after the etching treatment was measured using an optical microscope, and the amount of decrease in the wiring width was calculated. The results are shown in Table 1. Comparative Example 3 In Example 3, except for the etching solution, etching using 0.3% by weight of hydrogen peroxide, 30% by weight of nitric acid, 6% by weight of sulfuric acid, 0.01% by weight of sodium chloride, and 1% by weight of 2-chloro-pyridine was used. The liquid removal was measured in the same manner as in Example 3 except that the removal time and the wiring width reduction amount were measured. The results are shown in Table 1. Comparative Example 4 In the same manner as in Example 3, except that an etching solution containing 15% by weight of hydrogen peroxide, 15% by weight of phosphoric acid, and 2 ppm of chloride ions was used as the etching solution, the measurement of the removal time and the wiring width was measured. the amount. The results are shown in Table 1.
I 1380750 [表i] 去除時間（秒） 配線寬度減少量（微米） 實施例1 40 <1 實施例2 50 <1 實施例3 45 <1 比較例1 300 5 比較例2 180 8 比較例3 600 8 比較例4 600 8I 1380750 [Table i] Removal time (seconds) Wiring width reduction amount (micrometer) Example 1 40 <1 Example 2 50 <1 Example 3 45 <1 Comparative Example 1 300 5 Comparative Example 2 180 8 Comparison Example 3 600 8 Comparative Example 4 600 8
如表1所示，依據本發明的蝕刻方法以半加法形成細 線銅配線時，能夠抑制銅配線的配線寬度減少、蝕刻去除 種晶層的濺鍍銅或濺鍍鎳。 實施例4 調配含有1重量％過氧化氫、1 2重量％磷酸（過氧化氫/ 磷酸重量比=0.08)之飩刻液。 使用已施行濺鍍銅的基板及已施行電鑛銅的基板，對 各基板以3 0 °C、搖動處理6 0秒，算出各銅的蝕刻速度。 蝕刻速度的計算，濺鍍銅係使用登光X線測定處理前後的 膜厚、電鍍銅係測定處理前後的重量差，來算出各銅的蝕 刻量。 實施例5 除了蝕刻液使用含有1重量％過氧化氫、4重量％磷酸 (過氧化氫/磷酸重量比=0.2 5)之蝕刻液以外，與實施例4同 樣地進行、算出蝕刻量。 -11- 1380750 比較例5 調配含有1重量％過氧化氫、2重量％憐酸（過氧化氫/ 磷酸重量比=0.5)之蝕刻液。 使用已施行濺鍍銅的基板及已施行電鏡銅的基板’對 各基板以301、搖動處理60秒’算出各銅的蝕刻速度。 蝕刻速度的計算’濺鍍銅係使用螢光X線測定處理前後的 膜厚、電鍍銅係測定處理前後的重量差’來算出各銅的蝕 刻量。 比較例6 除了餘刻液使用含有5重量％過氧化氫、1重量％憐酸 (過氧化氫/磷酸重量比=5 · 0 )之蝕刻液以外’與實施例5同 樣地進行、算出蝕刻量。 比較例7 除了使用將以過氧化氫、硫酸作爲主成分之三菱瓦斯 化學股份公司製的蝕刻液CPE-700調整爲】重量％過氧化 氫的蝕刻液以外，與比較例5同樣地進行' 算出蝕刻量。 結果如表2所示。 [表2] 蝕刻速度濺鍍銅 微米/分鐘 蝕刻速度電鍍銅 微米/分鐘 蝕刻速度比 擺鑛銅/電鍵銅 實施例4 0.70 0.60 1.17 實施例5 0.60 0.58 1.03 比較例5 0.54 0.71 0.76 比較例6 0.33 0.70 0.47 比較例7 0.50 1.40 0.36 1380750 實施例6 調配含有0.9重量％過氧化氫、1〇重量％磷酸（過氧化 氫/磷酸重量比=0.09)之蝕刻液。 使用已施行SnAg焊料鍍敷過之試片，對各試片以30 °C、以浸漬處理1 〇分鐘，測定處理前後的重量，來算出蝕 刻速度。又，觀察表面狀態。 比較例8 調配含有1重量％過氧化氫、5重量％磷酸之蝕刻液。 使用已施行SnAg焊料鍍敷過之試片’對各試片以30 °C、以浸漬處理1 〇分鐘，測定處理前後的重量，來算出蝕 刻速度。又，觀察表面狀態。 結果如表3所示。 [表3] 金屬種晶 蝕刻速度 A/分鐘 表面觀察 實施例6 SnAg <10 無變化 比較例8 SnAg 560 變白模糊 【圖式簡單說明】 jfff 〇 j t w 【元件符號說明】 無。As shown in Table 1, according to the etching method of the present invention, when the thin copper wiring is formed by the half addition, it is possible to suppress the reduction in the wiring width of the copper wiring, and to remove the sputtered copper or the sputtered nickel of the seed layer. Example 4 An etchant containing 1% by weight of hydrogen peroxide and 12% by weight of phosphoric acid (hydrogen peroxide/phosphoric acid weight ratio = 0.08) was prepared. Using a substrate on which sputtering copper was applied and a substrate on which copper ore was applied, each substrate was subjected to shaking treatment at 30 ° C for 60 seconds to calculate the etching rate of each copper. In the calculation of the etching rate, the copper plating was used to calculate the etching amount of each copper before and after the film thickness before and after the X-ray measurement treatment and the difference in weight before and after the electroplating copper measurement treatment. (Example 5) The etching amount was calculated in the same manner as in Example 4, except that an etching liquid containing 1% by weight of hydrogen peroxide and 4% by weight of phosphoric acid (hydrogen peroxide/phosphoric acid weight ratio = 0.25) was used. -11- 1380750 Comparative Example 5 An etching solution containing 1% by weight of hydrogen peroxide and 2% by weight of pity acid (hydrogen peroxide / phosphoric acid weight ratio = 0.5) was prepared. The etching rate of each copper was calculated by using a substrate on which copper plating was applied and a substrate on which electron microscopy copper was applied, 301 and shaking treatment for each substrate for 60 seconds. Calculation of etching rate The thickness of each copper was calculated by using the thickness of the sputtering copper before and after the measurement by the X-ray measurement and the difference in weight before and after the copper plating measurement process. Comparative Example 6 The etching amount was calculated in the same manner as in Example 5 except that the etching liquid containing 5% by weight of hydrogen peroxide and 1% by weight of pity acid (hydrogen peroxide / phosphoric acid weight ratio = 5 · 0) was used. . Comparative Example 7 The calculation was carried out in the same manner as in Comparative Example 5 except that the etching liquid CPE-700 manufactured by Mitsubishi Gas Chemical Co., Ltd., which has hydrogen peroxide and sulfuric acid as a main component, was adjusted to have an etchant of wt% hydrogen peroxide. The amount of etching. The results are shown in Table 2. [Table 2] Etching Rate Sputtering Copper Micron/min Etching Speed Electroplating Copper Micron/Min Etching Speed Ratio Pendulum Copper/Electric Bond Copper Example 4 0.70 0.60 1.17 Example 5 0.60 0.58 1.03 Comparative Example 5 0.54 0.71 0.76 Comparative Example 6 0.33 0.70 0.47 Comparative Example 7 0.50 1.40 0.36 1380750 Example 6 An etching solution containing 0.9% by weight of hydrogen peroxide and 1% by weight of phosphoric acid (hydrogen peroxide/phosphoric acid weight ratio = 0.09) was prepared. Using the test piece which had been subjected to SnAg solder plating, each test piece was immersed at 30 ° C for 1 〇 minute, and the weight before and after the treatment was measured to calculate the etching rate. Also, observe the surface state. Comparative Example 8 An etching solution containing 1% by weight of hydrogen peroxide and 5% by weight of phosphoric acid was prepared. Using a test piece which had been subjected to SnAg solder plating, each test piece was subjected to immersion treatment at 30 ° C for 1 〇 minute, and the weight before and after the treatment was measured to calculate the etching rate. Also, observe the surface state. The results are shown in Table 3. [Table 3] Metal seed crystal etching rate A/min Surface observation Example 6 SnAg < 10 No change Comparative example 8 SnAg 560 whitening blur [Simple description of the drawing] jfff 〇 j t w [Description of component symbols] None.