Thin Solid Films 471 (2005) 186 193 www.elsevier.

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The effect of saccharin addition on the mechanical properties and fracture behavior of electroless NiCuP deposit on Al
Jen-Che Hsu*, Kwang-Lung Lin
Department of Materials Science and Engineering, National Cheng Kung University, Tainan, Taiwan 701, R. O. C. Received 21 August 2003; received in revised form 14 April 2004; accepted 17 August 2004 Available online 27 October 2004

Abstract In a previous study, the effects of additive saccharin on internal stress, diffusion, and crystallization behaviors of electroless NiCuP deposits on Al were examined. In this study, tensile test results and microhardness measurements were used to investigate the effect of additive saccharin on the mechanical properties and fracture behavior of electroless NiCuP deposits on Al. An increase in the saccharin content of the plating solution from 0 to 12 g/L results in nodule growth and void elimination in the deposits. The denser nodules in the deposit also cause a decrease in the tensile stress and reveal the effect of DTCE on compressive stress generation. Consequently, the mechanical properties of NiCuP/Al deposits in terms of microhardness, yield strength, modulus of elasticity, and ultimate tensile strength were improved. The fracture behavior of the deposit changes from transnodular to internodular when the saccharin addition is above 4 g/L. D 2004 Elsevier B.V. All rights reserved.
Keywords: Tensile test; Microhardness; Amorphous; Electroless NiCuP

1. Introduction The addition of Cu to the electroless NiP alloy improves properties, such as electrical conductivity [1], thermal stability [2], corrosion resistance [3], and solderability [4], and enhances performance as a diffusion barrier [5] and as an undercoat for hard discs [6]. The uniformity of the elemental distribution in NiCuP deposits has been investigated [7] and improved by adjusting the addition of the complexing agent in the deposition solution [8]. The phosphorus content of the solution influences the type of residual stresses (i.e., tensile or compressive) in electroless nickel (EN) deposits [9]. Furthermore, the intrinsic tensile stress in the deposits that causes peeling, cracking, and the acceleration of stress corrosion is affected by the substrate, plating solution, additives, and plating temperature [10]. The internal stress can be transformed from tensile to

* Corresponding author. Tel.: +886 6275757562929; fax: +886 62759602. E-mail address: allenfox@cubic.mat.ncku.edu.tw (J.-C. Hsu). 0040-6090/$ - see front matter D 2004 Elsevier B.V. All rights reserved. doi:10.1016/j.tsf.2004.08.025

compressive by introducing saccharin (C7H5NO3S), which restrains the coalescence of the NiCuP nodules [11] and affects the elemental diffusion and crystallization of electroless NiCuP deposits on Al [12]. The additive saccharin acts as a grain refiner and leveler during electrodeposition of nickel [13] because of the effect on electrode kinetics and the structure of the electrical double layer at the plating surface [14]. Numerous mechanisms have been suggested to explain the behavior of the additive and have been discussed in the comprehensive reviews [15,16]. For practical applications, the mechanical properties of EN and electroplated nickel (e-Ni) coatings are evaluated by fatigue, hardness, and tensile tests. The thickness, grain size, structure, type of compounds formed, and internal stresses of a deposit all affect its mechanical properties [17,18]. The Vickers hardness (Hv) measurement has been applied to amorphous thin-film coatings [19]. Tensile testing reveals the relation between stress and strain and strength of the bond between coating and substrate [20]. This present work investigated the mechanical properties with respect to a saccharin addition, and thus, the different types of stress in NiCuP deposits on Al.

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2. Experimental details Aluminum substrates of 99.5% purity, 63130.1 mm, were punched into tensile test specimens, as shown in Fig. 1. The specimens were annealed at 350 8C for 1 h in order to relieve any residual stress. Then the Al substrate was consecutively degreased in 5 wt.% sodium hydroxide (NaOH), deoxidized in 10 vol.% nitric acid (HNO3), rinsed with deionized water, and zincated in a zincating solution composed of 120 g/L sodium hydroxide, 20 g/L zinc oxide (ZnO), 1 g/L sodium nitrate (NaNO3), and 50 g/L sodium . gluconate (CatC4H4KNaO64H2O). Then, the prepared substrates underwent deposition in an electroless NiCuP solution at 90 8C with stirring for 30 min. The plating . solution consisted of 15 g/L nickel sulphate (NiSO46H2O), . 0.2 g/L copper sulphate (CuSO45H2O), 15 g/L sodium . hypophosphite (NaH2PO2H2O), 30 g/L sodium citrate . (Na3C6H5O72H2O), 40 g/L ammonium chloride (NH4Cl), and 012 g/L saccharin (C7H5NO3S). The initial pH value of the bath was adjusted with ammonia to be 8.0. These specific plating conditions have been utilized to investigate the internal stress per unit thickness and deposit thickness with respect to saccharin concentration [12]. It exhibited the uniformity in bulk and surface of the NiCuP deposits after deposition [8]. Tensile tests were conducted at a strain rate of 0.9 mm/ min according to the ASTM-A370 standard at room temperature. The Vickers hardness measurement was carried out at a load of 25 gf. In general, the measurement of the microhardness of a thin film is affected by the substrate. Thus, all measurements were conducted on five samples and films with a thickness of about 5 Am confirmed by scanning electron microscope (SEM) cross-sectional observations. The morphologies of the resulting films were examined in top and side views by using a JEOL JXA-840 scanning electron microscope (SEM).

Fig. 2. The internal stress [12] and microhardness of the as-deposited Ni CuP deposit with respect to saccharin concentration.

deposit reaches zero stress after the addition of 8 g/L of saccharin. Further addition of saccharin (10 and 12 g/L) results in compressive stress. Fig. 2 also shows the relationship between the average hardness value (Hv) and saccharin concentration. The average hardness value of the Al substrates was around 25 Hv, while that of the coated specimen was 58.4 Hv for a deposit obtained without the use of saccharin. The average hardness value remains at this level when less than 8 g/L of saccharin is added to the solution, but suddenly increases to 118.4 Hv at a concentration of 8 g/L. The average hardness remains at a value of approximately 100 Hv with further addition of saccharin (10 and 12 g/L). 3.2. Stressstrain behavior Fig. 3 shows the actual stressstrain curves of NiCuP deposits on Al substrates with respect to the saccharin concentration in the plating solution. The effects of adding saccharin to the plating solution on the properties of the resulting NiCuP deposits are described in the following subsections. 3.2.1. Yield stress and ultimate tensile stress Fig. 4 shows the effect of saccharin concentration on yield stress (YS) and ultimate tensile stress (UTS) of the specimens. The average yield stress value increased from 40.4 MPa of Al to 51.0 MPa when the Al substrate is plated without saccharin in the solution. The lowest average yield stress value is 46.0 MPa at a saccharin addition of 2 g/L. However, from that point on, the average yield stress value gradually increases to 80.7 MPa at a saccharin addition of 12 g/L. Meanwhile, the average UTS value also increases from 76.7 to 86.1 MPa when the Al substrate is plated without a saccharin addition. It remains in the range of 81.286.1 MPa at a saccharin concentration of 8 g/L or less.

3. Results 3.1. Vickers hardness (Hv) The internal stress per unit thickness in the NiCuP deposits with respect to saccharin concentration was exhibited as seen in Fig. 2 [12]. The tensile stress decreases sharply after adding 2 g/L of saccharin to the solution. The

Fig. 1. The schematic diagram of tensile specimen.

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J.-C. Hsu, K.-L. Lin / Thin Solid Films 471 (2005) 186193 Table 1 The modulus of elasticity (E) of Al substrate and NiCuP deposits on Al substrates, obtained with respect to saccharin concentration Tensile specimen Al substrate, E Al Deposit with 0 g/L saccharin addition, E S0 Deposit with 2 g/L saccharin addition, E S2 Deposit with 4 g/L saccharin addition, E S4 Deposit with 6 g/L saccharin addition, E S6 Deposit with 8 g/L saccharin addition, E S8 Deposit with 10 g/L saccharin addition, E S10 Deposit with 12 g/L saccharin addition, E S12 Modulus of elasticity, E (GPa) 4.21 1.82 1.64 2.17 3.32 3.93 6.21 7.34

Fig. 3. The stressstrain diagrams of tensile specimens with respect to saccharin concentration.

saccharin concentration (E S0E S12) was calculated as listed in Table 1. The average modulus of elasticity of the Al substrate is 4.21 GPa. The average modulus of elasticity of the NiCuP/Al specimens increases from 1.82 to 3.93 GPa for saccharin concentrations between 0 and 8 g/L. The modulus of elasticity increases dramatically to 6.21 GPa at 10 g/L saccharin, and to 7.34 GPa at 12 g/L saccharin. 3.2.3. Elongation Fig. 5 shows the elongation of an uncoated Al sample and the NiCuP/Al specimens with respect to saccharin concentration. The elongation decreases from 25.1% for the pure Al substrate to 18.0% for the NiCuP/Al specimen coated without saccharin in the solution. The elongation further decreases to 4.4% as the saccharin content is increased to 10 g/L. The elongation approaches a minimum values of 3.35.1% at a saccharin concentration of 10 g/L or more. 3.3. Morphology before tensile test Fig. 6 shows the surface morphologies of as-deposited NiCuP specimens with respect to saccharin concentration

The addition of saccharin at 10 and 12 g/L resulted in the higher average UTS values of 94.5 and 88.2 MPa, respectively. 3.2.2. Modulus of elasticity, E The modulus of elasticity (i.e., Youngs modulus) is defined as the ratio of stress to strain in the elastic region before any plastic deformation occurs. The property affects spring-back and shape distortion at low strain [21]. The modulus of elasticity was calculated according to Hookes law (Eq. (1)). E stress strain 1

The average modulus of elasticity of an Al substrate (E Al) and NiCuP/Al specimen obtained with respect to

Fig. 4. The yield stress (YS) and ultimate tensile stress (UTS) values of the tensile specimens with respect to saccharin concentration.

Fig. 5. The elongation (El) values of the as-deposited NiCuP deposits with respect to saccharin concentration and internal stress [12].

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Fig. 6. The surface morphologies of the as-deposited NiCuP specimens with respect to saccharin concentration and internal stress [12].

in the plating solution. The images show larger nodule size and a smearing of the boundary along with decreasing nodule roughness when the saccharin concentration is at 6 g/ L or higher. These phenomena can be ascribed to bnodule coalescenceQ [11].

3.4. Fracture behavior after tensile test 3.4.1. Propagation of fracture Fig. 7 shows the fracture of NiCuP deposits with respect to saccharin concentration after tensile testing.

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Fig. 7. The surface morphologies of NiCuP deposits with respect to saccharin concentration after tensile test, (a and b) 0 g, (c and d) 2 g, (e and f) 4 g, (g and h) 8 g.

After the tensile test, the appearance of the cleavage suggests that the fracture of deposits propagates linearly when the saccharin concentration is 2 g/L or lower. The cracks in deposits without saccharin addition propagate transnodularly and result in block rupture (Fig. 7a and b). The shape of the cracks becomes band-like at a saccharin

concentration of 2 g/L (Fig. 7c). At a concentration of 4 g/ L, the crack becomes zigzag and propagates internodularly (Fig. 7e and f). At 8 g/L and above of saccharin concentration, the number of cracks is drastically diminished (Fig. 7g) and the fractures all occur internodularly (Fig. 7h).

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3.4.2. Fracture surface The fracture surfaces of NiCuP deposits with respect to the saccharin concentration are presented in Fig. 8. Fig. 8a and b reveals the existence of voids in the deposit plated at a saccharin concentration of 0 and 2 g/L, respectively. The voids disappear at higher saccharin concentrations. Fig.

8c to g shows that the fracture mechanism gradually changes from transnodular to internodular as saccharin addition increases. The SEM images of fracture surfaces seen in Fig. 9 show that no peeling occurs for the specimens regardless of tensile (0 g/L saccharin) or compressive (10 g/ L saccharin) stress, or a lack thereof (8 g/L saccharin). This

Fig. 8. The fracture surfaces of NiCuP deposits with respect to saccharin concentration after tensile test, (a) 0 g, (b) 2 g, (c) 4 g, (d) 6 g, (e) 8 g, (f) 10 g, (g) 12 g.

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crystallinity, deposit thickness, composition, and adhesion when discussing the mechanical properties and fracture mechanism. 4.1. Internal stress generation Previous research [8] demonstrated that stress varies with the nodular size of the deposit after aging. Aging results in nodule coalescence and an increase in the magnitude of the stress, while not changing the type of stress. Compressive stress generation in deposits was ascribed to the differences in the thermal coefficient of expansion (DTCE) between the NiCuP deposit and the Al substrate [8]. Thus, an increase in compressive stress in the deposits at saccharin concentrations of 10 and 12 g/L was ascribed to nodule coalescence as shown in Fig. 6f and g. The tensile stresses in the NiCuP deposits obtained with 0 and 2 g/L saccharin concentrations may be ascribed to the existence of voids as shown in the fracture surface in Fig. 9a and b. The addition of saccharin promotes the coalescence of the islands and the disappearance of voids within the NiCuP nodules. The denser nodules in the deposit cause a decrease in tensile stress and reveal the effect of DTCE on compressive stress generation. 4.2. Mechanical properties The mechanical behavior of the investigated NiCuP/Al specimen is related to the existence of voids in the nodules and the growth and coalescence of nodules. Voids are observed for the deposits obtained at 0 and 2 g/L saccharin concentrations, while they are absent at greater concentration (Fig. 8). Fig. 8 indicates that the nodule dimensions suddenly increase when the saccharin concentration increases from 6 to 8 g/L. Denser nodules in the presence of further saccharin addition exhibit higher resistance to deformation, indicated by the microhardness measurement found in Fig. 2, and higher stiffness (modulus of elasticity in Table 1). The microhardness (Fig. 2) of the deposits show a parallel jump in magnitude in this region. The modulus of elasticity (Table 1) generally increases as the saccharin concentration increases. A sharp increase in the modulus of elasticity and UTS (Fig. 4) also occurs above a saccharin concentration of 8 g/L. The yield stress (Fig. 4) of the specimen increases with an increase in saccharin concentration. It is concluded from these results that the addition of saccharin generally aids the elimination of voids and the growth of nodules, and increases deformation resistance and stiffness. It is also responsible for the improvement in yield stress and UTS of the electroless NiCuP deposit on Al. 4.3. Fracture mechanism The relatively low microhardness and low modulus of elasticity for the deposited specimen indicate that the

Fig. 9. The fracture surfaces of NiCuP deposits obtained with (a) 0 g/L, (b) 8 g/L, and (c) 10 g/L saccharin concentration after tensile test in lower magnification.

indicates good adhesion between the deposit and substrate. In other words, the cracks propagate across the deposit but not along the interface between the deposit and the substrate.

4. Discussion The electron diffraction pattern of as-plated NiCuP showed the amorphous structure of the deposit [8]. Furthermore, the deposit thickness remains roughly constant at about 5 Am after 30 min in the solution, regardless of the saccharin concentration [12]. EDS analysis shows the deposit to be Ni6.20Cu11.75P, but, with a slight increase in Ni and a decrease in P upon saccharin addition. Good adhesion between the deposit and substrate was shown in Fig. 9. These observations eliminate the concerns about

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deposit obtained at low saccharin concentrations easily deforms. Consequently, the cleavages in the deposit were seen to occur perpendicularly as well as in parallel to the direction of the applied tensile force, as seen in Fig. 7a and c. The cleavages were seen to propagate linearly. Both top views (Fig. 7b and d) and fracture surface images (Fig. 8a and b) indicate that the fracture takes place transnodularly for deposits obtained at 0 and 2 g/L saccharin concentrations. The crack propagation becomes zigzag at 4 g/L. The crack density is greatest at 6 g/L. The top view (Fig. 8) and fracture surface (Fig. 9) of deposits obtained at 412 g/L saccharin concentrations show a change of fracture behavior from transnodular to internodular as the saccharin concentration increases. This transition in fracture mechanism is believed to be due to the gradual strengthening of the deposit as the saccharin concentration increases. The increase in the strength of the nodule, as indicated by void elimination and increase in microhardness, tends to retard the propagation of fractures. As a result, the fractures detour and propagate along the nodular boundary. The rapid change in the direction of fracture propagation during tensile testing gives rise to strong oscillations in the stressstrain curve (Fig. 3) of deposits formed at saccharin concentrations of 812 g/L.

Acknowledgements The authors acknowledge the National Science Council of the Republic of China for the financial support of this study under NSC89-2216-E-006-088.

References
[1] O. Takano, K. Aoki, J. Met. Finish. Soc. Jpn. 34 (1983) 316. [2] N. Krasteva, V. Fotty, S. Armyanov, J. Electrochem. Soc. 141 (1994) 2864. [3] Y.W. Wang, C.G. Xiao, Z.G. Deng, Plat. Surf. Finish 79 (1992) 57. [4] C.Y. Lee, K.L. Lin, Jpn. J. Appl. Phys. 33 (1994) 4708. [5] C.J. Chen, K.L. Lin, J. Electrochem. Soc. 146 (1999) 137. [6] H. Ashassi-Sorkhabi, H. Dolati, N. Parvini-Ahmadi, J. Manzoori, Appl. Surf. Sci. 185 (2002) 155. [7] S. Armyanov, O. Steenhaut, N. Krasteva, J.-L. Delplancke, R. Winand, J. Vereecken, J. Electrochem. Soc. 143 (1996) 3692. [8] J.C. Hsu, K.L. Lin, J. Electrochem. Soc. 150 (2003) C653. [9] K. Parker, H. Shah, Plating 58 (1971) 230. [10] J.W. Dini, Electrodeposition, Noyes Publications, Park Ridge, NJ, 1993, p. 284. [11] C.J. Chen, K.L. Lin, Thin Solid Films 370 (2000) 106. [12] J.C. Hsu, K.L. Lin, J. Mater. Res. 18 (2003) 2221. [13] J.A. Henricks, Met. Finish. 79 (1981) 45. [14] D.M. Hembree, Plat. Surf. Finish 73 (1986) 54. [15] T.C. Franklin, Surf. Coat. Technol. 30 (1987) 415. [16] L. Oniciu, L. Muresan, Plat. Surf. Finish 21 (1991) 565. [17] J.A. Berrios, M.H. Staia, E.C. Hernandez, H. Hintermann, E.S. Puchi, Surf. Coat. Technol. 108/109 (1998) 466. [18] F. Czerwinski, Electrochim. Acta 44 (1998) 667. [19] R. Wiedemann, V. Weihnacht, H. Oettel, Surf. Coat. Technol. 116/119 (1999) 302. [20] ASTM Designation C633Standard Method of Test for Adhesive or Cohesive Strength of Flame-Sprayed Coatings, Annual Book of ASTM Standards, 19th, vol. 17, ASTM, Philadelphia, PA, 1969, p. 636. [21] G.W. Powell, S.E. Mahmoud, K. Mills (Eds.), Metals Handbook, 9th, vol. 8, Metals Park, Ohio, 1986, p. 555.

5. Conclusions The increase in saccharin concentration, from 0 to 12 g/ L, in the electroless deposition bath results in the growth of deposit nodules. It also eliminates voids from the deposit and causes a decrease in the tensile stress and the generation of compressive stress. The microhardness of the deposit, yield strength, modulus of elasticity, and ultimate tensile strength of the deposited NiCuP/Al specimen were thus improved. The fracture of the deposit takes place transnodularly at 0 and 2 g/L saccharin concentrations and becomes internodular when the saccharin concentration is above 4 g/L.