جوانهزنی و رشد الکتروشیمیایی مس روی پایه مولیبدن: اثر pH، پتانسیل و روش تمیز کردن سطح
محورهای موضوعی : فصلنامه علمی - پژوهشی مواد نوینغلامرضا حیدری 1 , سید محمد موسوی خوئی 2 , مهدی قاسمی فرد 3 , مهران جوانبخت 4
1 - دانشگاه صنعتی اسفراین، اسفراین، ایران
2 - دانشکده معدن و متالورژی، دانشگاه صنعتی امیرکبیر، تهران، ایران
3 - دانشگاه صنعتی اسفراین، اسفراین، ایران
4 - دانشکده مستقل شیمی، دانشگاه صنعتی امیرکبیر، تهران، ایران
کلید واژه: مولیبدن, مس, رسوبدهی الکتروشیمیایی, جوانهزنی و رشد,
چکیده مقاله :
در این تحقیق با استفاده از تکنیکهای ولتامتری سیکلی[1] و کرونوآمپرومتری[2] مراحل اولیه رسوبدهی الکتروشیمیایی مس روی فلز پایه مولیبدن در محلول اندکی اسیدی مطالعه شده است. رسوبدهی الکتروشیمیایی مس بر روی فلز پایه مولیبدن از دیدگاه ترمودینامیکی، سینتیکی، مکانیزم جوانهزنی و رشد مورد ارزیابی قرار گرفت. با استفاده از ولتامتری سیکلی تعیین شد که رسوبدهی الکتروشیمیایی مس روی فلز پایه مولیبدن یک فرایند برگشتناپذیر و تحت کنترل نفوذ میباشد. تحت کنترل نفوذ بودن رسوبدهی الکتروشیمیایی مس بر روی فلز پایه مولیبدن توسط رابطهی Randles-Sevcik تایید گردید. ضریب نفوذ مس در 3 pH= و 4 با استفاده از رابطهی Randles-Sevcik و رابطهی Cottrel محاسبه شدند که در تطابق خوبی با هم بودند. با استفاده از مدل Sharifker-Hills منحنیهای جریان گذرا[3]مس تحلیل شدند. مکانیزم جوانهزنی مس به عنوان تابعی از pH و پتانسیل مورد بررسی قرار گرفتند. در3 pH= و 4 مکانیزم جوانهزنی و رشد مس روی نمونه سمباده شده به‌صورت ترکیبی از آنی[4] و پیشرونده[5] سه بعدی بود درحالی‌که با افزایش pH و پتانسیل مکانیزم جوانهزنی به سمت مکانیزم آنی سه بعدی متمایل شد. غوطه‌ور کردن فلز پایه در محلول حاوی آمونیاک و سپس اسید کلریدریک بعد از سمباده زدن تاثیری بر روی مکانیزم جوانهزنی و رشد نداشت. اچ کردن فلز پایه در محلول حاوی اسید سولفوریک، اسید نیتریک و اسید کلریدریک بعد از سمباده زدن مکانیزم جوانهزنی را از حالت آنی سه بعدی به پیشرونده سه بعدی تغییر داد.
[1] -Cyclic voltammetry
[2] -Chronoamperometry
[3] -current transient
[4]- instantaneous
[5]- progressive
In this study, the early stages of copper electrodeposition on molybdenum substrate from slightly acidic electrolyte were studied by cyclic voltammetry (CV) and chronoamperometry. The electrochemical deposition of copper on molybdenum substrate was investigated from the view point of thermodynamic, kinetic, and nucleation and growth mechanism. According to the CV analysis, the electrodeposition of copper on molybdenum substrate was determined to be irreversible process with diffusion controlled and it was confirmed by Randles-Sevcik equation. Diffusion coefficient of copper species at pH=3 and 4 was determined by Randles-Sevcik and Cottrel equations and their results were in agreement with each other. Using Scharifker-Hills model, the current transients of copper were analyzed. The copper nucleation mechanisms were evaluated as a function of solution pH and deposition potential. It was found that at pH=3 and 4, the nucleation mechanism of copper on grounded substrate was mixed, while with increasing the pH and potential, the nucleation mechanism shifts toward 3D instantaneous. Soaking of substrate in NH3 and then HCl solution after grounding did not change the nucleation mechanism. Etching the substrate in solution containing H2SO4, HNO3 and HCl after grounding changed the nucleation mechanism from 3D instantaneous to 3D progressive.
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