臺灣博碩士論文加值系統

本研究針對n-type (100)矽晶片，研究直接在其表面析鍍無電鍍鎳磷層，並探討基材前處理方式，以及鍍液組成對鍍層磷含量、鍍層結晶性質、系統門檻鍍溫、析鍍速率的影響，最後並測試鍍層附著力。對於矽晶片前處理，乙醇的效果比傳統粗化、敏化活化程序好，鍍層不會中途掀離。當鍍液的初始負荷為5cm2/dm3，鍍液組成為40g/L NiSO4、40g/L NaH2PO2、60g/L Na3C6H5O7、1.5ppm Pb(CH3COO)2‧2H2O、1.5ppmC12H25O4SNa、糖精8 g/L。鍍溫80℃、NH4OH添加量20ml/L，可製備析鍍速率為15.1μm/hr且磷含量在7 wt%以上的無電鍍鎳磷鍍層，X光繞射圖顯示其趨向非晶質，而鍍液中還原劑的濃度對鍍層磷含量影響不顯著。
當鍍液裡不含NaF，添加鎢酸鈉可將門檻鍍溫由78℃降至72℃；再添加6g/L NaF，可降至65℃，若NaF添加量達到12g/L，門檻鍍溫會降至60℃，但鍍液變得不穩定。雖然鍍層確實不含W，但鎢酸鈉對門檻鍍溫的影響與K. Chen以鋼鐵為基材的研究結果不甚相符。
如果鍍液不含糖精，鍍層容易龜裂，由表面破裂型態可知鍍層受到拉伸應力。在鍍液裡添加8g/L糖精，可避免鍍層龜裂，以薄膜附著力測試系統測試，可知Si/Ni-P試片結合強度為9.8~14.7Mpa。
觀察鍍層表面與截面的SEM型態，確實可發現大小顆粒夾雜出現，與Takano等人提出的第三種不含還原劑的反應機構相符，並可針對漏鍍、鍍層龜裂等現象提出可能的解釋。但如果鍍液不含還原劑，析鍍反應就不會發生，與Takano等人的實驗結果不同，因此無法確認Takano等人提出的反應機構。

This research is to investigate the direct electroless Ni-P plating on the n-type (100) silicon wafer. We also study the pretreatment process for the silicon substrate, and the relationship between the composition of the plating solution and the threshold plating temperature, the plating rate, and the phosphorous content and the crystallinity of the as-plated layer.
For the pretreatment of the silicon wafer, the simple ethanol process is more convenient and better than the traditional roughening, sensitizing, and activation processes. When the original load of the plating solution is 5cm2/dm3, if we add 40g/L NiSO4, 40g/LNaH2PO2, 60g/L Na3C6H5O7, 8g/L saccharin, 1.5ppm Pb(CH3COO)2, 1.5ppm C12H25O4SNa, and 20ml/L NH4OH, we can produce electroless Ni-P
layer at 80℃with phosphorous content above 7 wt%. The plating rate is about 15.1μm/hr. The results of X-ray diffraction show the amorphous tendency. Furthermore, the influence of the reducing agent concentration on the phosphorous content of the plated layer is not obvious.
If the plating solution is not composed of NaF, we can decrease the threshold plating temperature from 78℃to 72℃ by adding Na2WO4.If we further add 6g/L NaF, the threshold plating temperature drops to 65℃.If the concentration of NaF increases to 12g/L, the threshold plating temperature continuously drops to 60℃, but the plating solution becomes unstable. Although there is indeed no W in the plated layer, the other result about reducing threshold plating temperature does not agree well with K. Chen’s study, in which the substrate is low-carbon steel.
Without adding saccharin in the plating solution, the plated layer chaps easily. From the surface SEM micrograph, we can conclude that the plated layer is under tensile stress. If we add 8g/L saccharin in the plating solution, the plated layer will no longer chap . From the results of the adhesion test, the adhesion strength of Si/Ni-P is 9.8~14.7 MPa.
By observing the surface and cross-section SEM morphology of the plated layer, we indeed find that there are both large and small particles deposited on the substrate.This observation is in accordance with Takano’s third reaction mechanism without the reducing agent. But in our experiment there is no plating reaction occurred without the reducing agent, so we cannot confirm the reaction mechanism supposed by Takano.

中文摘要------------------------------------------------------Ⅰ
英文摘要------------------------------------------------------Ⅱ
目錄----------------------------------------------------------Ⅳ
圖目錄--------------------------------------------------------Ⅶ
表目錄--------------------------------------------------------Ⅸ
第壹章 緒論 ---------------------------------------------- 1
1-1研究背景-------------------------------------------------- 1
1-1-1研究動機---------------------------------------------- 1
1-1-2矽晶片無電鍍鎳的應用---------------------------------- 1
1-2無電鍍鎳技術-----------------------------------------------2
1-2-1無電鍍鎳的發展歷史-------------------------------------2
1-2-2無電鍍鎳與擴散障礙層-----------------------------------3
1-2-3無電鍍鎳磷層的磷含量-----------------------------------5
1-2-4無電鍍鎳的優點與應用-----------------------------------7
1-2-5無電鍍鎳的反應機構-------------------------------------9
1-3無電鍍鎳鍍液-----------------------------------------------11
1-3-1鍍液簡介-----------------------------------------------11
1-3-2鎳鹽與還原劑-------------------------------------------14
1-3-3鉗合劑與穩定劑-----------------------------------------15
1-3-4促進劑與緩衝劑-----------------------------------------16
1-3-5光澤劑與界面活性劑-------------------------------------17
1-3-6應力消滅劑---------------------------------------------17
1-4無電鍍鎳鍍液配方-------------------------------------------20
1-4-1無電鍍Ni-P系統的配方-----------------------------------20
1-4-2低鍍溫無電鍍Ni-P系統-----------------------------------21
1-4-3無電鍍Ni-B與Ni-P-B系統的配方---------------------------22
1-4-4無電鍍多元合金-----------------------------------------23
1-5矽晶片無電鍍鎳---------------------------------------------24
1-6基材前處理-------------------------------------------------28
1-7析鍍速率---------------------------------------------------33
1-8鍍層附著性-------------------------------------------------35
第貳章 實驗方法與步驟-----------------------------------------37
2-1 化學藥品--------------------------------------------------37
2-2 實驗構想及設計--------------------------------------------37
2-3無電鍍鎳磷合金之析鍍---------------------------------------39
2-3-1 矽晶片前處理------------------------------------------39
2-3-2 矽晶片上析鍍無電鍍鎳磷層------------------------------40
2-3-3 鍍層表面型態、化學組成與晶體結構之分析----------------41
2-3-4 鍍層析鍍速率分析--------------------------------------41
2-3-5 鍍層結合強度分析--------------------------------------42
第參章 結果與討論---------------------------------------------43
3-1 矽晶片前處理----------------------------------------------43
3-1-1 經傳統粗化與敏化活化劑處理的矽晶片--------------------44
3-1-2 經3-1-1節程序處理後的鍍層-----------------------------45
3-1-3乙醇前處理---------------------------------------------45
3-2非晶質無電鍍鎳磷合金之製作與結晶行為-----------------------46
3-2-1 鍍液組成對無電鍍鎳磷合金磷含量的影響------------------46
3-2-2 鍍液組成對析鍍速率的影響------------------------------48
3-2-3 鎢酸鈉對門檻鍍溫的影響--------------------------------49
3-2-4 磷含量對無電鍍鎳磷合金晶體結構的影響------------------51
3-3無電鍍鎳磷層之內應力及對結合強度的影響---------------------53
3-3-1糖精對無電鍍鎳磷層內應力的影響-------------------------55
3-3-2 內應力對無電鍍鎳磷層結合強度之影響--------------------56
3-4 關於無電鍍鎳反應機構的討論--------------------------------56
第肆章 結論---------------------------------------------------60
第伍章 未來研究方向之建議-------------------------------------62
參考文獻------------------------------------------------------63
自述----------------------------------------------------------72

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