جوانه‌زنی و رشد الکتروشیمیایی مس روی پایه مولیبدن: اثر pH، پتانسیل و روش تمیز کردن سطح

فصلنامه علمی - پژوهشی مواد نوین

مقاله 9، دوره 7، شماره 28، مرداد و شهریور 1396، صفحه 81-94   

نوع مقاله: مقاله پژوهشی

نویسندگان

غلامرضا حیدری^{* 1}؛ سید محمد موسوی خوئی²؛ مهدی قاسمی فرد¹؛ مهران جوانبخت³

¹دانشگاه صنعتی اسفراین، اسفراین، ایران

²دانشکده معدن و متالورژی، دانشگاه صنعتی امیرکبیر، تهران، ایران

³دانشکده مستقل شیمی، دانشگاه صنعتی امیرکبیر، تهران، ایران

تاریخ دریافت: 25 تیر 1394،  تاریخ بازنگری: 05 آبان 1394،  تاریخ پذیرش: 25 آبان 1396 

چکیده

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

کلیدواژه‌ها

رسوب‌دهی الکتروشیمیایی؛ مس؛ جوانه‌زنی و رشد؛ مولیبدن

عنوان مقاله [English]

Electrochemical Nucleation and Growth of Copper on Molybdenum Substrate: Effect of pH, Potential and Cleaning procedure

نویسندگان [English]

G Heidari¹؛ S. M Mousavi Khoie²؛ M Ghasemifard¹؛ M Javanbakht³

چکیده [English]

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.

کلیدواژه‌ها [English]

Electrodeposition, Copper, Nucleation and Growth, Molybdenum

مراجع

1-K.-H. Liao, C.-Y. Su, Y.-T. Ding, H.-S. Koo, "Microstructural characterization of CIGS formation using different selenization processes", Applied Surface Science, Vol. 270, pp. 139-144, 2013.

2-G.-X. Liang, P. Fan, C.-M. Chen, Z.-H. Zheng, D.-P. Zhang, "A promising sputtering for in situ fabrication of CIGS thin films without post-selenization",

Journal of Alloys and Compounds, Vol. 610, pp. 337-340, 2014.

3-S.-J. Sung, M.S. Park, D.-H. Kim, J.-K. Kang, "Effect of Soft-annealing on the

 

 

Properties of CIGSe Thin Films Prepared from Solution Precursors", Bull. Korean Chem. Soc, Vol. 34, pp. 1473, 2013.

4-E. Ahmed, M. Amar, W. Ahmed, R.D. Pilkington, A.E. Hill, M.J. Jackson, "Laser annealing of flash-evaporated CuInSe2 thin films", J. of Materi Eng and Perform, Vol. 15, pp. 213-217, 2006.

5-K.R. Murali, A. Shanmugavel, K. Srinivasan, "Photoelectrochemical characteristics of pulse electrodeposited CuInS2 films", Ionics, Vol. 17, pp. 157-162, 2011.        

6-M. Ikhlasul Amal, K. Kim, "Structural and optical properties of sulfurized Cu2ZnSnS4 thin films from Cu–Zn–Sn alloy precursors", J Mater Sci: Mater Electron, Vol. 24, pp. 559-566, 2013.

7-J. Zhang, L. Shao, "Cu2ZnSnS4 thin films prepared by sulfurizing different multilayer metal precursors", Sci. China Ser. E-Technol. Sci., Vol. 52, pp. 269-272, 2009. 

8-M. Danilson, M. Altosaar, M. Kauk, A. Katerski, J. Krustok, J. Raudoja, "XPS study of CZTSSe monograin powders", Thin Solid Films, Vol. 519, pp. 7407-7411, 2011.    

9-H. Katagiri, K. Jimbo, W.S. Maw, K. Oishi, M. Yamazaki, H. Araki, A. Takeuchi, "Development of CZTS-based thin film solar cells", Thin Solid Films, Vol. 517, pp. 2455-2460, 2009.           

10-N. Aihara, H. Araki, A. Takeuchi, K. Jimbo, H. Katagiri, "Fabrication of Cu2SnS3 thin films by sulfurization of evaporated Cu-Sn precursors for solar cells", physica status solidi (c), Vol. 10, pp. 1086-1092, 2013. 

11-C. Kotaro, K. Junpei, E. Shinya, A. Hideaki, N. Ryota, J. Kazuo, K. Hironori, "Preparation of Cu 2 SnS 3 Thin Films by Sulfurization of Cu/Sn Stacked Precursors", Japanese Journal of Applied Physics, Vol. 51, pp. 10NC35, 2012.

12-M.R. Khelladi, L. Mentar, A. Azizi, L. Makhloufi, G. Schmerber, A. Dinia, "The potential dependence of Co–Cu alloy thin films electrodeposited on n-Si(100) substrate", J Mater Sci: Mater Electron, Vol. 23, pp. 2245-2250, 2012.

13-G. Heidari, H. Tavakoli, S.M. Mousavi Khoie, "Nano SiC-Nickel Composite Coatings from a Sulfamat Bath Using Direct Current and Pulsed Direct Current", J. of Materi Eng and Perform, Vol. 19, pp. 1183-1188, 2010.           

14-Y. Kwon, H.-G. Hong, "Electrodeposition of Graphene–Zn/Al Layered Double Hydroxide (LDH) Composite for Selective Determination of Hydroquinone", Bull. Korean Chem. Soc, Vol. 34, pp. 1755, 2013.      

15-ر.س. گیلاکجانی, ف. محبوبی, م. کاظمی, "        بررسی رفتار تریبولوژیکی پوشش کامپوزیتیNi-P-SiC ایجاد شده روی آلیاژ آلومینیم Al6061 به روش آبکاری شیمیایی", فصلنامه علمی - پژوهشی مواد نوین، جلد 5، ص 1-9، 1394. 
 

16-S.M. Pawar, B.S. Pawar, A.V. Moholkar, D.S. Choi, J.H. Yun, J.H. Moon, S.S. Kolekar, J.H. Kim, "Single step electrosynthesis of Cu2ZnSnS4 (CZTS) thin films for solar cell application", Electrochimica Acta, Vol. 55, pp. 4057-4061, 2010. 

17-B.S. Pawar, S.M. Pawar, S.W. Shin, D.S. Choi, C.J. Park, S.S. Kolekar, J.H. Kim, "Effect of complexing agent on the properties of electrochemically deposited Cu2ZnSnS4 (CZTS) thin films", Applied Surface Science, Vol. 257, pp. 1786-1791, 2010.

18-M. Jeon, Y. Tanaka, T. Shimizu, S. Shingubara, "Formation and characterization of single-step electrodeposited Cu2ZnSnS4 thin films: Effect of complexing agent volume", Energy Procedia, Vol. 10, pp. 255-260, 2011.

19-M. Jeon, T. Shimizu, S. Shingubara, "Cu2ZnSnS4 thin films and nanowires prepared by different single-step electrodeposition method in quaternary electrolyte", Materials Letters, Vol. 65, pp. 2364-2367, 2011.           

20-R. Schurr, A. Hölzing, S. Jost, R. Hock, T. Voβ, J. Schulze, A. Kirbs, A. Ennaoui, M. Lux-Steiner, A. Weber, I. Kötschau, H.W. Schock, "The crystallisation of Cu2ZnSnS4 thin film solar cell absorbers from co-electroplated Cu–Zn–Sn precursors", Thin Solid Films, Vol. 517, pp. 2465-2468, 2009. 

21-J. Li, T. Ma, M. Wei, W. Liu, G. Jiang, C. Zhu, "The Cu2ZnSnSe4 thin films solar cells synthesized by electrodeposition route", Applied Surface Science, Vol. 258, pp. 6261-6265, 2012.

22-E.M. Mkawi, K. Ibrahim, M.K.M. Ali, K.M.A. Saron, M.A. Farrukh, N. Allam, "Influence of substrate temperature on the properties of electrodeposited kesterite Cu2ZnSnS4 (CZTS) thin films for photovoltaic applications", J Mater Sci: Mater Electron, Vol. pp. 1-7, 2014.     

23-E.M. Mkawi, K. Ibrahim, M.K.M. Ali, M.A. Farrukh, A.S. Mohamed, "Dependence of the properties of copper zinc tin sulfide thin films prepared by electrochemical deposition on sulfurization temperature", J Mater Sci: Mater Electron, Vol. 25, pp. 857-863, 2014.

24-P.K. Sarswat, M. Snure, M.L. Free, A. Tiwari, "CZTS thin films on transparent conducting electrodes by electrochemical technique", Thin Solid Films, Vol. 520, pp. 1694-1697, 2012.

25-D.M. Berg, R. Djemour, L. Gütay, G. Zoppi, S. Siebentritt, P.J. Dale, "Thin film solar cells based on the ternary compound Cu2SnS3", Thin Solid Films, Vol. 520, pp. 6291-6294, 2012.       

26-J.J. Scragg, D.M. Berg, P.J. Dale, "A 3.2% efficient Kesterite device from electrodeposited stacked elemental layers", Journal of Electroanalytical Chemistry, Vol. 646, pp. 52-59, 2010.       

27-J.J. Scragg, P.J. Dale, L.M. Peter, "Towards sustainable materials for solar energy conversion: Preparation and photoelectrochemical characterization of Cu2ZnSnS4", Electrochemistry Communications, Vol. 10, pp. 639-642, 2008.

28-J.J. Scragg, P.J. Dale, L.M. Peter, "Synthesis and characterization of Cu2ZnSnS4 absorber layers by an electrodeposition-annealing route", Thin Solid Films, Vol. 517, pp. 2481-2484, 2009.

29-G. Ma, T. Minegishi, D. Yokoyama, J. Kubota, K. Domen, "Photoelectrochemical hydrogen production on Cu2ZnSnS4/Mo-mesh thin-film electrodes prepared by electroplating", Chemical Physics Letters, Vol. 501, pp. 619-622, 2011.      

30-J. Kelber, S. Rudenja, C. Bjelkevig, "Electrodeposition of copper on Ru(0 0 0 1) in sulfuric acid solution: Growth kinetics and nucleation behavior", Electrochimica Acta, Vol. 51, pp. 3086-3090, 2006.         

31-D. Grujicic, B. Pesic, "Electrodeposition of copper: the nucleation mechanisms", Electrochimica Acta, Vol. 47, pp. 2901-2912, 2002.       

32-A.I. Danilov, E.B. Molodkina, Y.M. Polukarov, "Initial Stages of Copper Electrocrystallization on a Glassy-Carbon Ring–Disk Electrode from Sulfate Electrolytes of Various Acidity: A Cyclic Voltammetry Study", Russian Journal of Electrochemistry, Vol. 38, pp. 732-742, 2002.

33-D. Mercier, E. Delbos, H. El Belghiti, J. Vigneron, M. Bouttemy, A. Etcheberry, "Study of Copper Electrodeposition Mechanism on Molybdenum Substrate", Journal of The Electrochemical Society, Vol. 160, pp. D3103-D3109, 2013.       

34-A.V. Rudnev, E.B. Molodkina, A.I. Danilov, Y.M. Polukarov, J.M. Feliu, "Kinetics of underpotential deposition and nucleation of copper on the Pt(111) face in the presence of acetonitrile", Russian Journal of Electrochemistry, Vol. 42, pp. 381-392, 2006.         

35-A. Radisic, P.M. Vereecken, P.C. Searson, F.M. Ross, "The morphology and nucleation kinetics of copper islands during electrodeposition", Surface Science, Vol. 600, pp. 1817-1826, 2006.

36-S.B. Kim, K.T. Kim, C.J. Park, H.S. Kwon, "Electrochemical nucleation and growth of copper on chromium-plated electrodes", Journal of Applied Electrochemistry, Vol. 32, pp. 1247-1255, 2002.

37-R. Krumm, B. Guel, C. Schmitz, G. Staikov, "Nucleation and growth in electrodeposition of metals on n-Si(111)", Electrochimica Acta, Vol. 45, pp. 3255-3262, 2000. 

38-P. Ren, N. Dai, H. Deng, J. Zhang, "Growth Kinetics and Microstructures of Cu Nanofilms on Mo Substrate by Electrodeposition", Journal of The Electrochemical Society, Vol. 162, pp. D9-D14, 2015.

39-S.M.M.K. G.Heidari, M. Ebrahimizadeh Abrishami, M. Javanbakht, "Electrodeposition of Cu-Sn Alloys : Theoretical and Experimental Approaches", Journal of Materials Science: Materials in Electronics, Article in press, Vol. pp.          

40-F.I. Lizama Tzec, G. Oskam, "Electrodeposition of Copper in Trenches From a Citrate Plating Bath", ECS Transactions, Vol. 25, pp. 195-201, 2010.

41-M. Rezaei, M. Ghorbani, A. Dolati, "Electrochemical investigation of electrodeposited Fe–Pd alloy thin films", Electrochimica Acta, Vol. 56, pp. 483-490, 2010.          

42-L. Soleimany, A. Dolati, M. Ghorbani, "A study on the kinetics of gold nanowire electrodeposition in polycarbonate templates", Journal of Electroanalytical Chemistry, Vol. 645, pp. 28-34, 2010.  

43-L.R.F. Allen J. Bard, Electrochemical Methods: Fundamentals and Applications, 2nd ed., Wiley, New York, 2001.

44-M. Majidi, K. Asadpour-Zeynali, B. Hafezi, "Reaction and nucleation mechanisms of copper electrodeposition on disposable pencil graphite electrode", Electrochimica Acta, Vol. 54, pp. 1119-1126, 2009.

45-L.D. Zhou, Yatang ; Zhang, Huan ; Jia, Yurong ; Zhang, Jie ; Li, Changxiong ;, "Nucleation and Growth of Bismuth Electrodeposition from Alkaline Electrolyte", Bulletin of the Korean Chemical Society, Vol. 33, pp. 1541-1546, 2012. 

46-B. Scharifker, G. Hills, "Theoretical and experimental studies of multiple nucleation", Electrochimica Acta, Vol. 28, pp. 879-889, 1983.     

47-C. Han, Q. Liu, D.G. Ivey, "Nucleation of Sn and Sn–Cu alloys on Pt during electrodeposition from Sn–citrate and Sn–Cu–citrate solutions", Electrochimica Acta, Vol. 54, pp. 3419-3427, 2009.

48-D. Grujicic, B. Pesic, "Reaction and nucleation mechanisms of copper electrodeposition from ammoniacal solutions on vitreous carbon", Electrochimica Acta, Vol. 50, pp. 4426-4443, 2005.