Activator-assisted electroless deposition of copper nanostructured films

Abstract

This paper showed simple and effective synthesis of copper nanoparticles within controlled diameter using direct electroless deposition on glass substrates, following the sensitization and activation steps. Electroless-deposited metals, such as Cu, Co, Ni, and Ag, and their alloys had many advantages in micro- and nanotechnologies. The structural, morphological, and optical properties of copper deposits were characterized using X-ray diffraction (XRD), atomic force microscopy (AFM), and UV-Vis spectroscopy. The structural data was further analyzed using the Rietveld refinement program. Structural studies reveal that the deposited copper prefers a (111) orientation. AFM studies suggest the deposited materials form compact, uniform, and nanocrystalline phases with a high tendency to self-organize. The data show that the particle size can be controlled by controlling the activator concentration. The absorption spectra of the as-deposited copper nanoparticles reveal that the plasmonic peak broadens and exhibits a blue shift with decreasing particle size.

Keywords

nanostructured materials / thin films / copper / electroless plating / deposition

References

[1] Lin J C, Lee C. Grain boundary diffusion of copper in tantalum nitride thin films. J. Electrochem. Soc., 1999, 146(9): 3466.

[2] Vaškelis A. Coatings Technology Handbook, 2001, New York, Marcel Dekker, 213

[3] Abe S, Ohkubo M, Fujinami T, Honma H. The electroless copper plating of small via holes. Trans. Inst. Met. Finish., 1998, 76, 12

[4] O’Kelly J P, Mongey KF, Gobil Y, Torres J, Kelly PV, Crean GM. Room temperature electroless plating copper seed layer process for damascene interlevel metal structures. Microelectron. Eng., 2000, 50, 473.

[5] Tang S C, Meng XK. Controllable synthesis of metal particles by a direct current electrochemical approach. Sci. China, Ser. E, 2009, 52(9): 2709.

[6] Hafezi B, Majidi MR. A sensitive and fast electrochemical sensor based on copper nanostructures for nitrate determination in foodstuffs and mineral waters. Anal. Methods, 2013, 5, 3552.

[7] Hollahan J R, Rosler RS. Thin Film Processes, 1978, New York, Academic Press, 335.

[8] Dubin V M, Shacham-Diamand Y, Zhao B, Vasudev PK, Ting CH. Selective and blanket electroless copper deposition for ultralarge scale integration. J. Electrochem. Soc., 1997, 144(3): 898.

[9] Valenzuela K, Raghavan S, Deymier PA, Hoying J. Formation of copper nanowires by electroless deposition using microtubules as templates. J. Nanosci. Nanotechnol., 2008, 8, 1.

[10] Yan C L, Xue DF. A Modified electroless deposition route to dendritic Cu metal nanostructures. Cryst. Growth Des., 2008, 8(6): 1849.

[11] Yu L, Guo L, Preisser R, Akolkar R. Autocatalysis during electroless copper deposition using glyoxylic acid as reducing agent. J. Electrochem. Soc., 2013, 160(12): D3004.

[12] Bhusari D, Hayden H, Tanikella R, Allen SAB, Kohl PA. Plasma treatment and surface analysis of polyimide films for electroless copper buildup process. J. Electrochem. Soc., 2005, 152(10): F162.

[13] Lee C L, Huang YC, Kuo LC. Catalytic effect of Pd nanoparticles on electroless copper deposition. J. Solid State Electrochem., 2007, 11(5): 639.

[14] Byeon J H, Yoon KY, Jung YK, Hwang J. Thermophoretic deposition of palladium aerosol nanoparticles for electroless micropatterning of copper. Electrochem. Commun., 2008, 10, 1272.

[15] Schlesinger M, Paunovic M. Modern Electroplating, 2010 5th ed. Hoboken, New Jersey, John Wiley & Sons, Inc.

[16] Fritz N, Koo HC, Wilson Z, Uzunlar E, Wen ZS, Yeow XY, Allen SAB, Kohl PA. Electroless deposition of copper on organic and inorganic substrates using a Sn/Ag catalyst. J. Electrochem. Soc., 2012, 159(6): D386.

[17] Sard R. The nucleation, growth, and structure of electroless copper deposits. J. Electrochem. Soc., 1970, 117(7): 864.

[18] Bindra P, White JR. Electroless Plating: Fundamentals and Applications, 1990, New York, William Andrew Publishing, 289

[19] Hsu H H, Teng CW, Lin SJ, Yeh JW. Sn/Pd catalyzation and electroless Cu deposition on TaN diffusion barrier layers. J. Electrochem. Soc., 2002, 149(3): C143.

[20] Hsu H H, Hsieh CC, Chen MH, Lin SJ, Yeh JW. Displacement activation of tantalum diffusion barrier layer for electroless copper deposition. J. Electrochem. Soc., 2001, 148(9): C590.

[21] Chang S Y, Hsu CJ, Fang RH, Lin SJ. Electrochemical deposition of nanoscaled palladium catalysts for 65 nm copper metallization. J. Electrochem. Soc., 2003, 150(9): C603.

[22] Palanna O G. Engineering Chemistry, 2009, New Delhi, Tata McGraw Hill Publications, 191

[23] Cullity B D, Stock SR. Elements of X-ray Diffraction, 1978, Menlo Park, California, Addison-Wesley Publishing Company, 102

[24] Barret C S, Massalski TB. Structure of Metals, 1980, Oxford, Pergamon Press, 204

[25] Kreibig U, Vollmer M. Optical Properties of Metal Clusters, 1995, Berlin, Springer, 184.

[26] Yeshchenko O A, Dmitruk IM, Dmytruk AM, Alexeenko AA. Influence of annealing conditions on size and optical properties of copper nanoparticles embedded in silica matrix. Mater. Sci. Eng., B, 2007, 137, 247.

[27] Pileni M P. Optical properties of nanosized particles dispersed in colloidal solutions or arranged in 2D or 3D superlattices. New J. Chem., 1998, 22, 693.

[28] Jana N R, Wang ZL, Sau T K, Pal T. Seed-mediated growth method to prepare cubic copper nanoparticles. Curr. Sci., 2000, 79(9): 1367

[29] Wang D S, Kerker M. Enhanced Raman scattering by molecules adsorbed at the surface of colloidal spheroids. Phys. Rev. B, 1981, 24(4): 1777.

[30] Blosi M, Albonetti S, Dondi M, Martelli C, Baldi G. Microwave-assisted polyol synthesis of Cu nanoparticles. J. Nanopart. Res., 2011, 13, 127.

[31] Garcia M A. Surface plasmons in metallic nanoparticles: fundamentals and applications. J. Phys. D, 2011, 44(28): 1.

[32] Link S, El-Sayed MA. Shape and size dependence of radiative, non-radiative and photothermal properties of gold nanocrystals. Int. Rev. Phys. Chem., 2000, 19(3): 409.