本文關鍵詞： 填孔鍍銅 超填孔 抑制劑 填孔率 RRDE　出處：《哈爾濱工業(yè)大學》2013年博士論文　論文類型：學位論文

【摘要】：盲孔金屬化是實現(xiàn)印制電路板(Printed Circuit Board, PCB)層與層之間電器互聯(lián)的有效手段，更是高密度互聯(lián)(High Density Interconnection, HDI)板發(fā)展的關鍵技術之一。為保證電路連接的可靠性，盲孔需要被電鍍銅層完全填充，在此工藝過程中電鍍時間、面銅厚度以及盲孔的填孔率是衡量酸銅鍍液性能的重要指標。目前，國內(nèi)市場上的電鍍銅填盲孔鍍液幾乎被國外品牌所壟斷，這對我國PCB產(chǎn)業(yè)的發(fā)展極為不利。因此，開發(fā)一種具有自主知識產(chǎn)權的高效盲孔鍍銅液具有十分重要的現(xiàn)實意義。 一般而言，在不含添加劑的酸銅鍍液中電鍍銅填盲孔時，由于孔底部的電流密度相對較小，沉銅速度相對緩慢，因此無法實現(xiàn)對盲孔的填充。只有當鍍液中含有氯離子、加速劑、抑制劑和整平劑時，通過添加劑之間的相互作用，改變盲孔底部與面板表面電流密度的分布差異，才能最終實現(xiàn)對盲孔的完美填充，也稱作超填孔(Superfilling)。 本研究以EPE系列(由環(huán)氧乙烷EO與環(huán)氧丙烷PO組成的三嵌段聚合物)抑制劑的篩選為切入點，通過研究抑制劑的抑制強度與盲孔填孔率的關系，最終篩選出綜合性最佳的抑制劑EPE2900，其EO含量為40%，分子量為2900。對比實驗結果表明，作為電鍍銅填盲孔的抑制劑，EPE2900比常規(guī)抑制劑PEG6000更優(yōu)秀。因此，本文選擇EPE2900為抑制劑，以填盲孔的效果為衡量標準對電鍍銅填盲孔的工藝配方進行了優(yōu)化，優(yōu)化結果：220g/L CuSO4·5H2O、54g/L H2SO4、60mg/L Cl-、6mg/L SPS、200mg/L EPE2900和4mg/L JGB。采用此優(yōu)化配方，控制電流密度2A/dm2，電鍍時間60min，鍍液溫度25℃，填孔(孔徑125μm，孔深100μm)實驗結束后，面銅厚度約為16μm，填孔率高達95%。 在優(yōu)化的電鍍銅填盲孔配方中，使用旋轉(zhuǎn)圓盤電極，采用循環(huán)伏安法和計時電位法，系統(tǒng)地研究了各種添加劑的獨立作用以及相互作用。研究結果表明，EPE2900與Cl-之間存在明顯的正協(xié)同作用，換句話說，Cl-的存在可以大幅度提高EPE2900對銅離子沉積的抑制作用。此外，對于每一個固定濃度的EPE2900，都存在一個最佳的Cl-濃度使其對銅沉積的抑制作用達到最大值。抑制劑EPE2900在陰極表面的吸附是一個快速過程，而SPS在陰極表面的吸附則是緩慢進行的，二者在電極表面發(fā)生競爭吸附，強對流有利于EPE2900的吸附。在鍍液中引入整平劑JGB，可以協(xié)同提高EPE2900的抑制作用。循環(huán)伏安實驗結果表明，與其它添加劑相比，EPE2900與Cl-之間的協(xié)同作用最為顯著，其對銅離子沉積的穩(wěn)定電位具有決定性的影響。 利用Material Studio(MS)模擬軟件和Gaussian計算軟件分別對EPE2900分子在水溶液中的空間構型以及分子中氧原子的電負性進行了模擬計算。在分析不同條件下的填孔實驗結果的基礎上，結合EPE2900與其他添加劑之間的相互作用，提出了EPE2900在陰極表面吸附的簡單模型。然后利用線性掃描、計時電位和電化學阻抗等電化學測試方法對提出的模型進行了證明。 為進一步明確EPE2900在電極表面的吸附機制，本文采用循環(huán)伏安溶出法(CVS)，，對銅溶解峰的積分面積值Q受EPE2900和Cl-濃度的影響進行了系統(tǒng)研究。結果表明，當鍍液中含有固定濃度的EPE2900時，隨著Cl-濃度在一定范圍內(nèi)增加，Q值逐漸減小，這說明Cl-濃度的增加可以提高EPE2900的抑制作用。重要的是，我們發(fā)現(xiàn)當Cl-濃度在0~10mg/L之間增大時，Q值下降得很快；然而當Cl-濃度大于10mg/L時，隨著Cl-濃度的增加，Q值的下降速度明顯變緩。據(jù)此實驗現(xiàn)象，采用分段線性擬合的方法，計算出曲線拐點的橫坐標，此橫坐標對應的Cl-濃度，即是EPE2900在陰極表面達到臨界吸附時所需的最低Cl-濃度。用相同的研究方法計算出當鍍液中含有固定濃度的Cl-時，曲線拐點的橫坐標，即達到臨界吸附時所需的EPE2900的最低濃度。多組平行實驗的結果都證明，EPE2900在電極表面達到臨界吸附時，鍍液中EPE2900和Cl-的最低濃度分別為11.46mg/L和4.85mg/L。根據(jù)Q值隨EPE2900和Cl-濃度增加而下降的變化趨勢，提出了EPE2900在臨界吸附狀態(tài)時的吸附模型，同時詳細地描述了隨著EPE2900和Cl-濃度的增加吸附模型的改變情況。特別的，本文引入旋轉(zhuǎn)環(huán)盤電極(RRDE)測試技術證明了EPE2900可以和Cu+相互作用，佐證了EPE2900吸附模型的合理性。
[Abstract]:The blind hole metallization is a printed circuit board (Printed Circuit, Board, PCB) effective means between layer and layer electrical interconnection, is of high density interconnection (High Density Interconnection, HDI) is one of the key technologies in development. In order to ensure the reliability of circuit connection, blind hole copper plating layer needs to be completely filled, the plating time in this process in the process of filling rate and thickness on the surface of the blind hole is an important index to measure the acid copper plating solution performance. At present, the domestic market of the copper plating bath filled hole is almost monopolized by foreign brands, the development of China's PCB industry is extremely unfavorable. So it has very important practical significance to develop a blind, with independent intellectual property rights of the copper plating solution.
In general, in acid copper containing no additives in the plating solution for electroplating copper with blind hole, because the current density at the bottom of the hole is relatively small, the copper deposition speed is relatively slow, it can not be filled to the blind hole. Only when the plating solution containing chloride ions, accelerating agent, inhibitor and leveling agent, through the interaction of additive the difference of distribution of current density at the bottom of the blind hole with the surface of the panel, to achieve the perfect blind hole filling and ultimately to, also known as super pore filling (Superfilling).
This research is based on the EPE series (composed of ethylene oxide and propylene oxide EO PO three block copolymer) inhibitor screening as the starting point, the relationship between strength and research of inhibitors by inhibiting the blind hole filling rate, finally screened the best synthesis inhibitor EPE2900, the content of EO is 40%, the molecular weight of 2900. experiments the results show that the inhibitor for copper electroplating filling blind, EPE2900 PEG6000 is more excellent than conventional inhibitors. Therefore, this paper chooses EPE2900 as the inhibitor, formulation standard for copper electroplating of the blind hole to fill the hole filling effect is optimized, the optimization results: 220g/L CuSO4, 5H2O 54g/L, H2SO4,60mg/L Cl-, 6mg/L SPS, 200mg/L EPE2900 4mg/L and JGB. using the optimized formulation, control the current density of 2A/dm2, plating time 60min, bath temperature of 25 DEG C, filling holes (diameter 125 m, hole depth 100 m) after the end of the experiment, the surface copper thickness is about 16 m, fill in The hole rate is up to 95%.
Fill in the blind hole copper plating formula optimization, using the rotating disk electrode by cyclic voltammetry and chronopotentiometry, systematically studied the independent effects of various additives and interaction. The results show that there are obvious synergistic effect between EPE2900 and Cl-, in other words, the presence of Cl- can greatly improve the inhibition effect of EPE2900 on copper deposition. In addition, for each fixed concentration of EPE2900, there is an optimal Cl- concentration to its inhibitory effect on the deposition of copper reaches the maximum value. Inhibitor EPE2900 on the cathode surface adsorption is a fast process, and the adsorption of SPS on the cathode surface is slow the two has a competition adsorption on the electrode surface, strong convection favors the adsorption of EPE2900. The introduction of JGB leveling agent in the bath, can enhance the inhibitory effect of EPE2900. The experimental results show that cyclic voltammetry, Compared with other additives, the synergistic effect between EPE2900 and Cl- is the most significant, and it has a decisive influence on the stable potential of copper ion deposition.
The use of Material Studio (MS) simulation software and Gaussian software respectively on the spatial structure of EPE2900 molecule in aqueous solution and molecular oxygen in the electronegativity of atoms was simulated under different conditions. In the analysis of hole filling on the basis of experimental results, combined with the interaction between EPE2900 and he put forward EPE2900 additive. In a simple model of the cathode surface adsorption. Then linear scanning, chronoamperometry and electrochemical impedance and other electrochemical method to demonstrate the proposed model.
In order to further clarify the mechanism of EPE2900 adsorption on the electrode surface, the dissolution method by cyclic voltammetry (CVS), the integral area of copper dissolution peak value of Q is affected by EPE2900 and Cl- concentration were studied. The results show that, when the fixed concentration in the bath containing EPE2900, with the increase of Cl- concentration in a certain within the range of Q value decreased gradually, indicating that the increase of Cl- concentration can enhance the inhibitory effect of EPE2900. Importantly, we found that when the concentration of Cl- in 0~10mg/L increased, Q decreased quickly; however, when the concentration of Cl- is higher than 10mg/L, with the increase of Cl- concentration, Q value of the rate of decline significantly slow. According to the experimental phenomena, by using the method of piecewise linear fitting, calculate the horizontal coordinate curve inflection point, the horizontal axis corresponds to the concentration of Cl-, which is the lowest concentration of Cl- EPE2900 required to reach the critical adsorption on the surface of the cathode. The use of the same. Method to calculate when the fixed concentration in the bath containing Cl-, the abscissa curve inflection point, namely the minimum concentration required to reach the critical adsorption of EPE2900. Multi group parallel experimental results show that the EPE2900 reaches the critical adsorption on the electrode surface, the lowest concentration of EPE2900 and Cl- in the plating solution were changing trend 11.46mg/L and 4.85mg/L. decreased according to the value of Q with EPE2900 and Cl- concentration increased, adsorption model was proposed in EPE2900 critical adsorption state, and a detailed description of the EPE2900 and Cl- concentration increased with the change of adsorption model. Especially, this paper introduces a rotating ring disk electrode (RRDE) test proved that the EPE2900 can the interaction between Cu+ and EPE2900, proved the rationality of adsorption model.

【學位授予單位】：哈爾濱工業(yè)大學
【學位級別】：博士
【學位授予年份】：2013
【分類號】：TQ153.1

【參考文獻】

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本文編號：1448544