1292295 九、發明說明： 【發明所屬之技術領域】 本發明是有關於-種監控銅電錢液填孔能力的方 法’且特別是有關於-種可適用於監控長時間使用的電鑛 槽液之填孔能力的改變’並預測電鍍液填孔能力的定電流 量測法。 【先前技術】 現今的印刷電路板大多採用電鍍銅的方式來製作金 屬導線及填錢接上下層的導孔，在此钱銅賴液中須 加入多種添加劑，使盲孔底部_沉積速率加快而達到孔 底上移（b〇ttom up)的填充現象，故鍍液中添加劑濃度的分 析與控制是目前研究上的重要課題。 在盲孔電鍍銅沉積的過程中，隨著電鍍操作的情況不 同會產生不同的填充結果，而一般常見的填充結果可分為 均勾成長型（C〇nformal)、非均勻成長型（Anti_c〇nf〇rmal) 或半均勻成長型（Subconformal)以及爆發填孔型 (Super-filling)等二種填充結果。當孔頂上方與孔底的沉積 速率致時，最後填充的結果會是均勻成長的情況，孔的 中心會產生一條細縫（seam)，一般來說，均勻成長型及半 均勾成長型的填充結果對印刷電路板的信賴度都會有不 良的影響。因此，為了改善電鍍銅的填充結果，便發展出 在電鍵液中添加特定的添加劑來調控盲孔孔底及孔頂上 方處銅的沉積速率，以在電鍍過程中一方面抑制銅在孔頂 5 1292295 上方上的/儿積，一方面加速銅在孔内的沉積，而達到最佳 的爆發填孔效果。 在實際生產線上，有時會發生電鍵槽液中每個添加劑 的/辰度都正吊’但最後的填孔能力卻異常的現象。目前一 般凰抆填孔的方法皆為監控單一添加劑濃度的變化，當其 中某個添加劑濃度不夠時，填孔的效果就可能受到影 響；但實際上填孔的行為不僅僅是單—添加劑所產生的行 為，而是靠彼此間的交互作用所產生的，因此，應該監控 造成此填充結果的交互作用彳能符合實際的情況。 因此，需要一種可以監控整個電鍍槽系統内交互作用 的方法在進行填孔之前即可提供關於此電鍍槽系統填孔 能力的預測’以達到提升電鍍品f進而控制成本、提高生 產力的積極目的。 【發明内容】 口此本發明的目的就是在提供一種監控銅電鐘液填 孔能力的方法，可用以解決傳統監測方法僅能監控電鍍配 方中單一添加劑的濃度改變，而忽略添加劑間的交互作用 對電鍵配方之影響的缺點。 因此本發明的目的就是在提供一種監控銅電鍍液填 孔月b力的方法，可在電鍍前預測電鍍配方的填孔能力，用 以解決長時間使用的電鍍配方中添加劑濃度正常而填孔 功能卻異常的問題。 根據本發明之上述目的，提出一種監控銅電鍍液填孔 6 1292295 月匕力的方& ’係利用—^電流量測方法（galVanostat asurement)，以一銅旋轉電極於第一轉數下測得電鍍配 方^第一相對電位值，並利用此銅旋轉電極於第二轉數下 測传電鑛配方之第二相對電位值，此第—轉數與第二轉數 之，度間具有—高低差；再將第-及第二相對電位值相減 以侍到一電位差值’電位差值代表孔頂上方與孔底間沉積 速率之異差，目此電減值敍時其填孔能力越佳。 由上述可知，本發明具有下列優點·· 1·可藉由偵測整個電鍍系統之電位差值改變，來監控 電錢過知中電鐘配方内所有添加劑間的交互作用，達到提 t、更準確的填孔能力預測，適時調整適當的電鍍液配方， 以確保電鍍品質的目標。 2·利用簡單的操作及分析方法，可在電鑛前預先評估 電鍍液的填孔能力，不僅適料卫廠生產線，可達到降低 成本，提高生產力的㈣，亦適詩學術研究，更能達到 促進相關領域科研進步的積極目的。 為了使本發明之構成特徵、操作方法、目的及優點更 加容易了解’故於下文中配合圖示及文字敘述，說明本發 明之實施例。 【實施方式】 實施例之一種可 示意圖。定電流 請參照弟1圖’係繪示本發明之較佳 監控銅電鍵液填孔能力的定電流量測系統 一恆電位/電流儀120、一 量測系統100包含一電腦110、 1292295 工作電極l3〇、一參考電極140、一辅助電極150及一玻 璃容器160。 其中，電腦110係用來接收並處理量測時所得到的數 據；恆電位/電流儀120係用來控制電化學實驗過程中輸 出的電壓及電流大小；工作電極130為直徑約3毫米的一 白金旋轉電極（platinum rotating disk electrode; Pt-RDE); 參考電極 140為一飽和汞-硫酸亞汞電極（saturated mercury-mercurous sulfate electrode; SMSE);輔助電極 150 為一小銅棒，被放在一含有空白組電解液的小玻璃管中， 其中此空白組電解液含有濃度為0.88 M (lM=249.7g/L)的 硫酸銅（CuS04_5H20)及 0.54 M (lM=98.08g/L)的硫酸 (H2S04)，且此小玻璃管的末端以一多孔聚合材料密封，以 預防在分析過程中添加劑與輔助電極直接接觸，產生不好 的副產物。此外，在進行每一次電化學分析之前，會在一 個僅含有空白電解液的預沉積槽中，使白金旋轉電極預沉 積一層薄薄的銅層，厚度約為500奈米。 請參照第2圖，係繪示本發明較佳實施例之定電流量 測方法之步驟流程圖，在一電流密度為18ASF(ASFe19.4 毫安培/平方公分）下使用銅旋轉電極（Cu-RDE)來完成；此 外，每個待測之電鍍液配方都以定電流量測方法量測2 次，一次在轉數約為50〜200轉數（revolutions per minute; rpm)下，另一次則在轉數約為700〜3000 rpm下量測。首 先，如步驟210所示，在定電流量測開始的時候，於玻璃 容器160中提供一電解液，其僅含有空白電解液及百萬分 81292295 IX. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a method for monitoring the ability of a copper-electric liquid-filled liquid to fill a hole, and particularly relates to an electro- ore bath liquid which can be used for monitoring long-term use. The change in the filling capacity' and the constant current measurement method for predicting the filling ability of the plating solution. [Prior Art] Most of today's printed circuit boards use electroplated copper to make metal wires and fill holes for the upper and lower layers. In this case, various additives must be added to the copper lysate to accelerate the bottom deposition rate of the blind holes. The filling phenomenon of the bottom up (b〇ttom up), so the analysis and control of the concentration of the additive in the plating solution is an important subject in current research. In the process of blind hole electroplating copper deposition, different filling results will occur depending on the plating operation, and the common filling results can be divided into C〇nformal type and non-uniform growth type (Anti_c〇). Nf〇rmal) or semi-uniform growth (Subconformal) and explosive filling type (Super-filling) and other two filling results. When the deposition rate above the top of the hole and the bottom of the hole is caused, the result of the final filling will be uniform growth, and a seam will be formed at the center of the hole. Generally, the uniform growth type and the semi-uniform growth type are formed. Filling results can have a negative impact on the reliability of printed circuit boards. Therefore, in order to improve the filling result of the electroplated copper, it is developed to add a specific additive to the key liquid to regulate the deposition rate of copper at the bottom of the blind hole and above the top of the hole to suppress copper on the top of the hole during the electroplating process. 1292295 The upper side of the child, on the one hand, accelerates the deposition of copper in the hole to achieve the best burst hole filling effect. In the actual production line, sometimes the occurrence of each additive in the key bath is positively hoisted, but the final filling ability is abnormal. At present, the method of filling holes in the general phoenix is to monitor the change of the concentration of a single additive. When the concentration of one of the additives is not enough, the effect of filling the hole may be affected; but in fact, the behavior of filling the hole is not only the single-additive The behavior is generated by the interaction between each other. Therefore, the interactions that cause the result of this filling should be monitored to meet the actual situation. Therefore, there is a need for a method that can monitor the interaction within the entire plating bath system to provide a prediction of the filling capacity of the plating tank system prior to filling the hole to achieve the positive goal of improving the plating product f, thereby controlling cost and increasing productivity. SUMMARY OF THE INVENTION The object of the present invention is to provide a method for monitoring the filling ability of a copper electric bell liquid, which can be used to solve the traditional monitoring method and can only monitor the concentration change of a single additive in the electroplating formulation, while ignoring the interaction between the additives. Disadvantages of the impact on the key recipe. Therefore, the object of the present invention is to provide a method for monitoring the monthly b-force of a copper plating solution, which can predict the filling ability of the plating formulation before electroplating, and can be used to solve the problem of normal concentration of the additive in the electroplating formulation for a long time. But the problem is abnormal. According to the above object of the present invention, a method for monitoring the monthly filling force of a copper plating solution filling hole 6 1292295 is proposed, which is measured by a galvanic electrode at a first number of revolutions. The electroplating formula ^ first relative potential value is obtained, and the second relative potential value of the electric ore formula is measured by the copper rotating electrode at the second rotation number, and the first-rotation number and the second rotation number have a degree between High and low difference; then subtract the first and second relative potential values to meet a potential difference' potential difference represents the difference between the top of the hole top and the bottom of the hole deposition rate, the more the filling capacity of the electric depreciation good. It can be seen from the above that the present invention has the following advantages: 1. The utility model can monitor the interaction between all the additives in the electric clock formula by detecting the change of the potential difference of the entire electroplating system, so as to achieve t, more accurate The ability to fill the hole is predicted, and the proper plating solution formulation is adjusted in time to ensure the goal of plating quality. 2. Using simple operation and analysis methods, the filling ability of the plating solution can be pre-evaluated before the electric mine. It is not only suitable for the production line of the factory, but also can reduce the cost and improve the productivity. (4) It is also suitable for academic research of poetry. Promote the positive purpose of scientific research in related fields. In order to make the features, operation, objects, and advantages of the present invention easier to understand, the embodiments of the present invention are described below in conjunction with the drawings. [Embodiment] A schematic diagram of an embodiment can be given. The constant current, please refer to the figure 1 of the figure, which shows the constant current measuring system of the preferred monitoring copper electric key filling ability of the present invention. A constant potential/current meter 120, a measuring system 100 comprises a computer 110, 1292295 working electrode L3, a reference electrode 140, an auxiliary electrode 150, and a glass container 160. The computer 110 is used to receive and process the data obtained during the measurement; the constant potential/current meter 120 is used to control the voltage and current output during the electrochemical experiment; the working electrode 130 is a diameter of about 3 mm. Platinum rotating disk electrode (Pt-RDE); reference electrode 140 is a saturated mercury-mercurous sulfate electrode (SSEM); auxiliary electrode 150 is a small copper rod, placed in a In the small glass tube containing the blank group electrolyte, the blank group electrolyte contains copper sulfate (CuS04_5H20) and 0.54 M (lM=98.08 g/L) sulfuric acid at a concentration of 0.88 M (lM=249.7 g/L). H2S04), and the end of the small glass tube is sealed with a porous polymeric material to prevent direct contact of the additive with the auxiliary electrode during the analysis, resulting in undesirable by-products. In addition, prior to each electrochemical analysis, the platinum rotating electrode is pre-precipitated with a thin layer of copper having a thickness of about 500 nm in a pre-deposition bath containing only a blank electrolyte. 2 is a flow chart showing the steps of a constant current measuring method according to a preferred embodiment of the present invention, using a copper rotating electrode (Cu- at a current density of 18 ASF (ASFe 19.4 mA/cm 2 ). RDE) is completed; in addition, each plating solution to be tested is measured twice by constant current measurement method, once at a revolution of about 50 to 200 revolutions (revolutions per minute; rpm), and once again Measured at a number of revolutions of approximately 700 to 3000 rpm. First, as shown in step 210, at the beginning of the constant current measurement, an electrolyte is provided in the glass vessel 160, which contains only the blank electrolyte and millions of points.
1292295 之六十（60 ppm)的氯離子，用以進行定電流量測，定電流 量測法係以固定電流來監控電壓的改變，電壓愈高表示反 應愈難進行，藉此觀察反應進行之難易度。 接著，如步驟220所示，當定電流量測進行至500秒 時，將 200 ppm 的抑制劑聚乙二醇（Polyethylene glycol; PEG)注入到此玻璃容器160中。隨後如步驟230所示，在 1000秒的時候注入0.3 ppm加速劑雙（3-磺酸丙基）二硫化 物（Bis(3-Sufopropy) Disulfide; SPS)，接著再如步驟 240 所 示，於2000秒的時候注入濃度為1 ppm之不同的平整劑， 利用上述方式，可觀察平整劑濃度對於填孔能力的影響。 此電化學實驗中的所有溶液皆以去離子水配製；添加劑例 如 SPS、JGB (Janus Green B)、DB (Diazine Black)、ABPV (Alcian Blue)及BTA (Benzotriazole)的製備則分別自濃縮 原液稀釋成適當的濃度；電鍍液的溫度皆控制於20至30°C 之間。此外，填孔的效率可經由在金像顯微鏡（optical microscope; OM)下所拍攝之微米孔洞的截面來觀察。 由於填孔能力必須由孔洞的截面圖來判定，因此須將 電鍍完之盲孔板利用沖床機沖下含有孔洞的鍍膜，然後加 以灌膠、研磨、拋光、蝕刻後以金像顯微鏡觀察量測其填 孔結果並拍照紀錄。請參照第3圖，係繪示一填孔的示意 圖，包含一基材310、一内銅層320、一介電層330、一孔 洞340及一銅沉積層350。其中，銅沉積層3 50具有一高 度360，係沉積於一介電層330之上的銅沉積層3 50加上 介電層330高度的總和；孔洞中的銅沉積層亦具有一高度 9 1292295 370。填孔能力之定義為：（高度370+高度360)xl〇〇%。 實例一 明參照第4圖，係利用空白電解液及6〇ppm的氯離子 為土礎於疋電流量測進行至500秒時，將200 ppm的抑 ㈣（PEG)注人，隨後在麵秒的時候注入G.3 ppm加速 :(SPS)以進行定電流量測，在不同的電極轉數下分別量測 二相對電位，可觀察不含平整劑時對於填孔能力的影響。 藉由在兩種轉數下的量測結果可得到-電位差值(△㈠， 係由在l〇〇rpm下測得的電位減去在lOOOrpm下所測得的 電位之電位差，以作為填孔能力的指標。如果電位差值為 正值，表不此配方具有填孔的能力，&之如果電位差值為 負值，就表示不能進行填孔的行為。 結果顯不，第4圖所示之電鍍配方可產生一個正的電 差值亦即在间電極轉數下（i _ rpm)測得的相對電位 較^高（虛線b)，而低轉數下（1〇〇 rpm)測得的相對電位較低 (實線a) ’其兩者之間具有—正的電位差值，因此可知此配 方具有填孔的能力。 此外，利用金像顯微鏡配合觀察此配方之實際電鍍填 孔情形，請參照第5圖，為使用第4圖所示之配方進行填 孔的孔洞的截面圖。作為電鍍樣品的盲孔板的尺寸為4·5 X 6公分，微米孔洞的直徑約為13〇微米，深度約為85微米， 其㈣首先利用無電電鍍銅以進行金屬化’接著在填孔電 鍍之前，以銅電鍍沉積增加銅種晶層的厚度到2〜3微米， 12922951292295 Sixty (60 ppm) of chloride ions are used for constant current measurement. The constant current measurement method uses a fixed current to monitor the change of voltage. The higher the voltage, the more difficult the reaction is, thereby observing the reaction. Degree of difficulty. Next, as shown in step 220, 200 ppm of inhibitor polyethylene glycol (PEG) was injected into the glass vessel 160 when the constant current measurement was carried out for 500 seconds. Subsequently, as shown in step 230, 0.3 ppm of accelerator bis(3-sulfopropyl)disulfide (SPS) is injected at 1000 seconds, followed by step 240, as shown in step 240. In 2000 seconds, a different leveling agent with a concentration of 1 ppm was injected. Using the above method, the influence of the concentration of the leveling agent on the filling ability can be observed. All solutions in this electrochemical experiment were prepared in deionized water; additives such as SPS, JGB (Janus Green B), DB (Diazine Black), ABPV (Alcian Blue) and BTA (Benzotriazole) were separately diluted from the concentrated stock solution. The appropriate concentration; the temperature of the plating solution is controlled between 20 and 30 ° C. In addition, the efficiency of the hole filling can be observed through a cross section of a microscopic hole taken under an optical microscope (OM). Since the hole-filling ability must be determined by the cross-sectional view of the hole, the plated blind hole plate must be punched down with a punching machine, and then filled, glued, polished, etched and measured by a gold microscope. The result of filling the hole and taking a photo record. Referring to FIG. 3, a schematic diagram of a hole-filling hole is shown, including a substrate 310, an inner copper layer 320, a dielectric layer 330, a hole 340, and a copper deposition layer 350. The copper deposition layer 350 has a height 360, which is the sum of the heights of the copper deposition layer 350 and the dielectric layer 330 deposited on a dielectric layer 330; the copper deposition layer in the hole also has a height of 9 1292295 370. The filling ability is defined as: (height 370 + height 360) x l 〇〇 %. Example 1 refers to Figure 4, using a blank electrolyte and 6 〇 ppm of chloride ions as the basis for the 疋 current measurement to 500 seconds, 200 ppm of the (tetra) (PEG) injection, followed by the surface seconds At the time of injection G.3 ppm acceleration: (SPS) for constant current measurement, the two relative potentials are measured under different electrode revolutions, and the effect on the filling ability without the leveling agent can be observed. The -potential difference (Δ(1) is obtained by the measurement results under two kinds of revolutions, and the potential difference measured at l〇〇 rpm minus the potential measured at 1000 rpm is used as a hole filling. Capability index. If the potential difference is positive, the formula does not have the ability to fill holes. If the potential difference is negative, it means that the hole filling behavior cannot be performed. The result is not shown in Figure 4. The plating recipe produces a positive electrical difference, that is, the relative potential measured at the number of revolutions of the interelectrode (i _ rpm) is higher (dashed line b), and measured at a lower number of revolutions (1 rpm). The relative potential is low (solid line a) 'there is a positive potential difference between the two, so it is known that this formula has the ability to fill holes. In addition, using the gold microscope to observe the actual plating hole filling of this formula, please Referring to Fig. 5, a cross-sectional view of a hole for filling holes using the formulation shown in Fig. 4. The size of the blind via plate as a plating sample is 4·5 X 6 cm, and the diameter of the micro hole is about 13 μm. The depth is about 85 microns, and (4) first use electroless copper plating for gold The genus' is then deposited by copper electroplating to increase the thickness of the copper seed layer to 2 to 3 microns, 1292295
接著將盲孔板在一電流密度18 ASF下電鍍70分鐘。正極 為兩個含磷的銅片，直接放在一 700毫升工作體積的電鍍 槽中。在電鍍的過程中利用一連續流過的氣泡以每小時2.5 公升的流速持續授動電鐘槽液，以確保良好的對流。結果 如第5圖所示，此配方具有良好的填孔能力，由於並未加 入平整劑，因此其孔頂上方具有一半圓形的凸起。由此孔 洞的截面圖所顯示的良好填孔效果與第4圖所示之定電流 實驗的結果相互吻合，可驗證本發明之較佳實施例之定電 流量測方法的可信度。 由於第4圖的配方是沒有平整劑存在時的現象，然而 實際上工業界所使用的配方中都含有平整劑，因此下文中 其他實施例皆加入平整劑進行量測。 實例二The blind vias were then plated for 70 minutes at a current density of 18 ASF. The positive electrode is two copper-containing copper sheets placed directly in a 700 ml working volume plating bath. During the electroplating process, a continuous flow of air bubbles is used to continuously energize the electric clock bath at a flow rate of 2.5 liters per hour to ensure good convection. Results As shown in Fig. 5, this formulation has a good hole-filling ability, and since no flattening agent is added, it has a semi-circular projection above the top of the hole. Thus, the good hole-filling effect shown by the cross-sectional view of the hole coincides with the result of the constant current experiment shown in Fig. 4, and the reliability of the constant current flow measuring method of the preferred embodiment of the present invention can be verified. Since the formulation of Fig. 4 is a phenomenon in the absence of a leveling agent, in practice, the formulation used in the industry contains a leveling agent, and therefore, other examples are added to the leveling agent for measurement. Example two
請參照第6圖，當配方中的SPS濃度由0.3 ppm提高 到1 ppm時，所顯示出的填孔能力預測。當注入1 ppm的 SPS到含200 ppm抑制劑（PEG)以及60 ppm氯離子的基礎 電鍍液後，呈現出高電極轉數下（1〇〇〇 rpm)測得之相對電 位較低（虛線b)，而低轉數下（1000 rpm)測得之相對電位較 高（實線a)，其兩者之間具有一負的電位差值，因此可知此 配方應不具填孔的能力。此結果可歸因於過高的SPS濃度 使銅在盲孔板上過度加速沉積，此去極化行為的原因是1 ppm的SPS注入電鍵槽液之後，原本200 ppm的抑制劑 (PEG)以及60 ppm氯離子與濃度為0.3 ppm的加速劑SPS 11 1292295 之交互作用被破壞了。因此，在第7圖之孔洞截面圖上亦 可看到銅在盲孔板上均勻的沉積，顯示其為不良的填孔配 方，先前第6圖的定電流量測結果亦與此行為相吻合，亦 印證了定電流量測之預測。 繼續參照第6圖，值得注意的是，在2000秒時注入1 ppm的平整劑（DB)於此一含有200 ppm抑制劑（PEG)、60 ppm的氯離子及1 ppm SPS的配方，其添加劑的對流有關 性吸附（convection-dependent adsorption; CDA)行為又回復 了，也就是如第6圖所示，旋轉電極於轉數1000 rpm時的 相對電位（虛線b)回復到一個較高於轉數100 rpm時的相對 電位（實線a)。因此，在含有濃度1 ppm SPS之情況下，其 孔底上移的行為也在加入濃度1 ppm的DB時回復了。在 第8圖之孔洞截面圖上亦可看到此配方具有填孔的能力。 此外，由於DB為JGB的衍生物，已知JGB可與PEG產 生交互作用，而成為一複合式抑制劑，而此複合式抑制劑 具有很強的CDA行為，因此加入濃度1 ppm的DB時並未 出現如第5圖的半圓形凸起。 實例三 請參照第9圖，係將DB改成注入1 ppm之JGB，結果 顯示旋轉電極於轉數1〇〇〇 rpm時的相對電位（虛線b)較高 於轉數100 rpm時的相對電位（實線a)，與第6圖相較，其 電位差值較大，故預測此配方應具有良好的填孔能力。接 著，請參照第10圖的孔洞截面圖，以此配方進行電鍍之 12 1292295 孔网果絲現出很好的填孔結果，與第9圖的定電流量測 結果相符合。 /繼續參照第10圖，此沉積銅的孔頂上方並未出現半圓 /的凸 < 而疋呈現一平坦的表面，與第5圖相較，應可 歸因於JGB可提高抑制劑（pEG)的效果。此結果亦顯:， 在電鍍中，如果沒有平整劑與抑制劑的交互作用所產生之 較強的抑制效果時，在電鍍後孔頂上方就有可能產生半圓 形的凸起現象。 實例四 請參照第11圖，改以ABPV作為平整劑，於2〇〇〇秒 時注入電鍍液中。並參照第12圖的孔洞截面圖，結果顯 示加入1 ppm的ABPV可有效的改善銅沉積的均勻成長， 而成為爆發填孔型的成長，並有些許的半圓形狀出現在孔 頂上方。第11圖亦呈現了一致的極化曲線，定電流量測顯 示高電極轉數與低電極轉數下測得的相對電位之間具有 一個明顯的正電位差值，因此這是一個有效的電鍍液配 方，可應用作微米孔洞的填充。 最後以一個已知無效的填孔配方，來測試此填孔能力 的量測方法之可信度。於2000秒時注入1 pprn的BTA， 其疋電流夏測的結果係繪示於第13圖，在高電極轉數與 低電極轉數下測得的相對電位之間僅有些微的電位差，且 13 1292295 其電位差值為負值，故與預期的結果相符合。而實際電鍍 填孔的結果則顯示於第14圖，使用含1 ppm的SPS及1 ppm的BTA之基礎電解液配方之後，確實只有均勻成長型 的沉積發生’經嘗試過不同的BTA濃度，結果仍然都只呈 現出均勻成長沉積結果（未顯示於圖上）。 實例六Please refer to Figure 6 for the predicted filling capacity when the SPS concentration in the formulation is increased from 0.3 ppm to 1 ppm. When a 1 ppm SPS is injected into a base plating solution containing 200 ppm inhibitor (PEG) and 60 ppm chloride, the relative potential measured at high electrode revolutions (1 rpm) is low (dashed line b) ), and the relative potential measured at a low number of revolutions (1000 rpm) is higher (solid line a), which has a negative potential difference between the two, so it is known that the formulation should not have the ability to fill holes. This result can be attributed to the excessively high SPS concentration causing excessive accelerated deposition of copper on the blind via plate. This depolarization behavior is due to the original 200 ppm inhibitor (PEG) after the injection of 1 ppm of SPS into the bath solution. The interaction of 60 ppm chloride with the 0.3 ppm accelerator, SPS 11 1292295, was destroyed. Therefore, the uniform deposition of copper on the blind via plate can also be seen on the cross-sectional view of the hole in Fig. 7, which shows that it is a poor hole-filling formula. The previous current measurement results in Fig. 6 are also consistent with this behavior. It also confirms the prediction of constant current measurement. With continued reference to Figure 6, it is worth noting that 1 ppm of leveling agent (DB) was injected at 2000 seconds for this formulation containing 200 ppm inhibitor (PEG), 60 ppm chloride, and 1 ppm SPS. The convection-dependent adsorption (CDA) behavior is restored, that is, as shown in Fig. 6, the relative potential of the rotating electrode at the number of revolutions of 1000 rpm (dashed line b) returns to a higher number of revolutions. Relative potential at 100 rpm (solid line a). Therefore, in the case of a concentration of 1 ppm SPS, the behavior of the bottom shift is also restored when a DB of 1 ppm is added. This formulation also has the ability to fill holes in the hole cross-section of Figure 8. In addition, since DB is a derivative of JGB, it is known that JGB can interact with PEG to become a complex inhibitor, and this complex inhibitor has a strong CDA behavior, so when adding a concentration of 1 ppm DB The semicircular projections as shown in Fig. 5 did not appear. For the third example, please refer to Figure 9. The DB is changed to the JGB of 1 ppm. The result shows that the relative potential of the rotating electrode at 1 rpm (dashed line b) is higher than the relative potential at 100 rpm. (solid line a), compared with Figure 6, the potential difference is large, so it is predicted that this formula should have a good hole filling ability. Next, please refer to the hole cross-section of Figure 10, and the 12 1292295 mesh wire is electroplated with this formula to produce a good hole filling result, which is consistent with the constant current measurement result in Figure 9. /Continuously referring to Fig. 10, the semicircle/convex does not appear above the top of the deposited copper; and the crucible presents a flat surface, which is attributable to the JGB enhancement inhibitor (pEG) compared to Fig. 5. )Effect. This result also shows that, in the electroplating, if there is no strong inhibitory effect by the interaction of the leveling agent and the inhibitor, a semi-circular bulging phenomenon may occur above the top of the hole after electroplating. Example 4 Referring to Figure 11, the ABPV was used as a leveling agent and injected into the plating solution at 2 sec. Referring to the hole cross-section of Fig. 12, the results show that the addition of 1 ppm of ABPV can effectively improve the uniform growth of copper deposits, and it becomes the growth of the explosive hole-filling type, and a slight semicircular shape appears above the top of the hole. Figure 11 also shows a consistent polarization curve. The constant current measurement shows a significant positive potential difference between the high electrode rotation number and the relative potential measured at the low electrode rotation number, so this is an effective plating solution. Formulated for filling of micropores. Finally, the credibility of the measurement method for this hole-filling ability is tested with a known invalid fill-in formulation. Injecting 1 pprn of BTA at 2000 seconds, the results of the 疋 current summer measurement are shown in Fig. 13, and there is only a slight potential difference between the relative potential measured at the high electrode number and the low electrode number, and 13 1292295 The potential difference is negative and therefore consistent with the expected results. The actual results of electroplating and filling are shown in Figure 14. After using the base electrolyte formulation with 1 ppm SPS and 1 ppm BTA, only the uniform growth of the deposition occurred. 'After experimenting with different BTA concentrations, the results have been tried. Still only showing uniform growth deposition results (not shown). Example six
明參照第1 5圖’繪示了電位差值與填孔能力的相關 性，其中橫軸為對應各配方的電位差值，縱軸為對應各配 方的填孔能力。如第15圖所示，僅含有lppmSPS、2〇〇ppm PEG及60 ppm之氯離子的電鍍配方（實心方塊）及含有1 ppm SPS、200 ppm peg 及 60 ppm 之氯離子加丨 ppm BTA 的電鍍配方（實心圓）之電位差值均在5毫伏特（mV)以下， 其中僅含有lPPmSPS、200 PpmpEG及60ppm之氯離子 的電鍍配方於不同轉數下所測得之電位差值為負數，相對 的，填孔能力也很低（20%以下），而其餘配方之電位差值 車又间其表現出之填孔能力也遠高於前面兩組配方。顯然 地，當電位差值超過某一個數值時，其填孔能力即很好， 而當電位差值报小或甚至是負值時，就會發生均勻成長沉 積。負的電位差值意味著此-電鍍槽液系統不會出現cda =為，因為依照CDA的定義，鋼電極在高轉數下應該會 有較低的沉積速率，也就是較高的還原電位。因此，本發 :較佳實施例之定電流量測方法所測得之電位差值確^ 肩配方之填孔能力之間有顯著的關連，可達到正確預 1292295 測填孔能力的功能。 貫例-至實例四顯示，由物理化學的交互 :CDA行為可以利用定電流量測方法來定量分析：;二 電鑛過程中的添加劑濃度監控結果係綠示於帛16圖。:The relationship between the potential difference and the hole-filling ability is shown with reference to Fig. 5, wherein the horizontal axis is the potential difference corresponding to each formula, and the vertical axis is the filling ability of each of the recipes. As shown in Figure 15, an electroplated formulation containing only 1 ppm SPS, 2 〇〇ppm PEG, and 60 ppm chloride (solid squares) and plating with 1 ppm SPS, 200 ppm peg, and 60 ppm chloride ion plus ppm BTA The potential difference of the formulation (filled circle) is below 5 millivolts (mV), and the electroplating formula containing only lPPmSPS, 200 PpmpEG and 60 ppm of chloride ions has a negative difference in the potential difference measured at different revolutions, in contrast, The hole filling ability is also very low (below 20%), and the potential difference of the other formulas shows that the hole filling ability is also much higher than the previous two groups of formulas. Obviously, when the potential difference exceeds a certain value, the hole filling ability is good, and when the potential difference is small or even negative, uniform growth and deposition occurs. A negative potential difference means that the electroplating bath system does not exhibit cda = Yes, because according to the definition of CDA, the steel electrode should have a lower deposition rate at a higher number of revolutions, that is, a higher reduction potential. Therefore, in the present invention, the potential difference measured by the constant current measurement method of the preferred embodiment has a significant correlation between the hole filling ability of the shoulder formula, and the function of correctly correcting the filling ability of the 1292295 can be achieved. The example-to-fourth example shows the interaction between physicochemicals: CDA behavior can be quantified using a constant current measurement method: • The additive concentration monitoring result in the electro-mineral process is shown in Figure 16. :
中’⑷、（b)曲線為不含舰下測得之相對電位變化，其 電位差值為負值；⑷、⑷曲線為濃度〇. 5 ppm時測得 =才目對電位變化，其電位差值為正值；⑷、⑺曲線為卿 浪度為1 PPm時測得之相對電位變化，其電位差值為正 值’（g)、（h)曲線為JGB濃度為3 ppm時測得之相對電位 變化’其電位差值亦為正值’由帛16圖可觀察到各電鑛 配方的電位差值（介於兩個不同極化曲線間的電位差異）會 隨著JGB濃度的增加而出現一最大值；即在jgb濃度為^ ppm時，隨後降低的電位差值代表因為JGB濃度過高所導 致的孔頂與孔底間的沉積速率之差異縮小，由上述結果亦 可證明本發明較佳實施例之定電流量測方法無論在有無 平整劑存在的情況下皆可適用，能提供準確的填孔能力預 測。 實例八 請參照第17圖，係統計不同JGB濃度下的填孔能力與 電位差值的趨勢，其電位差值及填孔能力的數據係由前述 之貫驗結果所提供。如第17圖所示，不同JGB濃度所產 15 1292295 生之填孔能力的趨勢與不同JGB濃度所產生之電位差值 非常吻合，表示本發明較佳實施例之定電流量測方法可實 際運用於監控一電鍍槽液的填孔能力。 實例九 最後明參照第18圖，為利用一商品化的電鍍配方來驗 證本發明較佳實施例之定電流量測方法對於監控電鍍槽 φ ’夜之填孔旎力的可偉度。在電鍍過程中，隨著電鍍槽液由 新鮮慢慢老化，再持續添加新藥液、生產、分析之過程分 別取樣來進行本發明較佳實施例之定電流量測，並計算其 電位差值的結果。如第18圖所示，其呈現一線性的行為。 因此，可利用定電流量測方法去建立此電鍍配方的資料 庫，將新鮮剛配好的槽液之電位差值做為基準，如果待測 的槽液測出之電位差值比基準值小，則其填孔能力會較 差’如果接近基準值就表示其填孔能力可達到預期。 • 由上述本發明之較佳實施例可知，應用本發明具有之 優點為： ~ . 本發明較佳實施例之定電流量測方法藉由偵測整個電 . 鍍系統之電位差值改變，來監控電鍍過程中電鍍配方内所 有添加劑間的交互作用’其可信度高，更能準確預測電鑛 配方之填孔能力，可快速分析電鍍配方的良劣及適用性。 除此之外，依照其可提供之良好的線性關係，可實際運用 於監控一電鍍槽液的填孔能力改變。 雖然本發明已以較佳實施例揭露如上，然其並非用以 16 1292295 限定本發明，任何熟習此技藝者，在不脫離本發明之精神 和範圍内，當可作各種之更動與潤飾，因此本發明之較佳 實施例之保護範圍當視後附之申請專利範圍所界定者為 準。 【圖式簡單說明】The curves of '(4) and (b) are not including the relative potential changes measured under the ship, and the potential difference is negative; (4), (4) the curve is the concentration 〇. 5 ppm when measured = only the potential change, the potential difference It is a positive value; (4), (7) is the relative potential change measured when the wave length is 1 PPm, and the potential difference is positive value '(g), (h) curve is the relative potential measured when the JGB concentration is 3 ppm. The change 'the potential difference is also positive'. From the 帛16 diagram, it can be observed that the potential difference of each electric ore formula (potential difference between two different polarization curves) will appear as a maximum with the increase of JGB concentration. That is, when the jgb concentration is ^ppm, the subsequently decreased potential difference represents a decrease in the deposition rate between the top of the hole and the bottom of the hole due to the excessive JGB concentration, and the above results can also prove the preferred embodiment of the present invention. The constant current measurement method can be applied in the presence or absence of a leveling agent, and can provide accurate prediction of the hole filling ability. Example 8 Referring to Figure 17, the system calculates the difference between the hole-filling capacity and the potential difference at different JGB concentrations. The data of the potential difference and the hole-filling capacity are provided by the above-mentioned results. As shown in Fig. 17, the trend of the hole filling ability of 15 1292295 produced by different JGB concentrations is very consistent with the potential difference generated by different JGB concentrations, indicating that the constant current measuring method of the preferred embodiment of the present invention can be practically applied. Monitor the filling ability of a plating bath. EXAMPLE 9 Finally, with reference to Fig. 18, a commercially available plating formulation was used to verify the measurability of the constant current measurement method of the preferred embodiment of the present invention for monitoring the filling force of the plating bath φ ́ night. In the electroplating process, as the electroplating bath liquid slowly ages, the process of continuously adding new liquid medicine, production, and analysis is separately sampled to perform the constant current measurement of the preferred embodiment of the present invention, and the potential difference is calculated. result. As shown in Figure 18, it exhibits a linear behavior. Therefore, the constant current measurement method can be used to establish a database of the plating recipe, and the potential difference of the freshly prepared bath is used as a reference. If the potential difference measured by the bath to be tested is smaller than the reference value, then Its hole filling ability will be poor'. If it is close to the reference value, it means that its hole filling ability can be expected. It will be apparent from the above-described preferred embodiments of the present invention that the application of the present invention has the following advantages: ~ The constant current measuring method of the preferred embodiment of the present invention monitors by detecting the change in the potential difference of the entire electroplating system. The interaction between all the additives in the electroplating process during the electroplating process is highly reliable, and it can accurately predict the filling ability of the electro-mineral formula, and can quickly analyze the goodness and applicability of the electroplating formula. In addition, according to the good linear relationship that can be provided, it can be practically used to monitor the change of the filling ability of a plating bath. While the present invention has been described in its preferred embodiments, the present invention is not limited to the scope of the present invention, and it is possible to make various modifications and retouchings without departing from the spirit and scope of the invention. The scope of protection of the preferred embodiments of the invention is defined by the scope of the appended claims. [Simple description of the map]
為讓本發明之上述和其他目的、特徵、優點與實施例 月b更明顯易懂，所附圖式之詳細說明如下： 、第1圖係繪示本發明較佳實施例之一種可監控銅電鍍 液之填孔能力的定電流量測系統之示意圖。 又 旦：2圖係繪不依照本發明一較佳實施例的一種定電流 里測方法之步驟流程圖。 第3圖係繪示一填孔的示意圖。 =圖係繪示不含平整劑時之定電流量測結果。 用第4圖所示之配方進行填孔的孔洞截面 第6圖係緣示加 第7圖係利用第 圖。 第8圖係利用第 圖。 入平整劑時之定電流量測結果。 6圖所不之配方進行填孔的孔洞截面 圖所不之配方進行填孔的孔洞截面 面圖 17 1292295 第 第 二係繪示加入平整劑時之定電流量測結果。 θ係利用第11圖所示之配方進行填孔的孔洞截 面圖。 ^圖係綠不加入平整劑時之定電流量測結果。 第圖係利用第13圖所示之配方進行填孔的孔洞截 面圖 第 第 15圖係繪示電位差值與填孔能力之相關性比較圖。 16圖係繪示添加劑濃度與電位差值之相對關係比 較圖。 第17圖係繪示添加劑濃度、電位差值與填孔能力之 相對關係比較圖。 第18圖係緣示一 力的相關性比較圖。 商業電鍍配方之電位 【主要元件符號說明】 100 :定電流量測系統 110 :電腦 120 :恆電位/電流儀 130 :工作電極 140 :參考電極 15 0 :辅助電極 160 :玻璃容器 210 :步驟 220 :步驟 230 :步驟 240 :步驟 310 :基材 320 :内銅層 330 :介電層 340 ·孔洞 3 5 0 :銅沉積層 360 •馬度 370 ··高度 18In order to make the above and other objects, features, advantages and embodiments of the present invention more obvious, the detailed description of the drawings is as follows: FIG. 1 is a diagram showing a monitorable copper according to a preferred embodiment of the present invention. Schematic diagram of a constant current measurement system for the filling ability of a plating solution. Further, Fig. 2 is a flow chart showing the steps of a constant current measurement method which is not in accordance with a preferred embodiment of the present invention. Figure 3 is a schematic view showing a hole filling. = The graph shows the steady current measurement results without the leveling agent. The hole section of the hole filled with the formulation shown in Fig. 4 is shown in Fig. 7. The figure is shown in Fig. 7. Figure 8 uses the figure. The current measurement result when the leveling agent is added. Figure 6 shows the hole cross-section of the hole in the formulation. Figure 17 1292295 The second series shows the measurement results of the constant current when adding the leveling agent. The θ system is a cross-sectional view of the hole filled with the formulation shown in Fig. 11. ^ The system is the measurement result of the constant current when the greening agent is not added. The figure is a cross-sectional view of the hole filled with the formulation shown in Fig. 13. Fig. 15 is a graph showing the correlation between the potential difference and the filling ability. Figure 16 shows a comparison of the relative relationship between additive concentration and potential difference. Figure 17 is a graph showing the relative relationship between additive concentration, potential difference, and hole-filling ability. Figure 18 is a comparison of the correlations of the forces. Commercial plating recipe potential [Main component symbol description] 100: Constant current measurement system 110: Computer 120: Constant potential/current meter 130: Working electrode 140: Reference electrode 15 0: Auxiliary electrode 160: Glass container 210: Step 220: Step 230: Step 240: Step 310: Substrate 320: Inner copper layer 330: Dielectric layer 340 · Hole 3 5 0: Copper deposition layer 360 • Horse 370 · Height 18