Alloys, deposition

SJng Je Rod-Fed Electron Beam Source. The disadvantages of multiple sources for alloy deposition can be avoided by using a single wire-fed or rod-fed source (Fig. 3) (3). A molten pool of limited depth is above the soHd rod. If the equiUbrium vapor pressures of the components of an alloy A B are in the ratio of 10 1 and the composition of the molten pool is A qB, under steady-state conditions, the composition of the vapor is the same as that of the soHd being fed into the molten pool. The procedure can be started with a pellet of appropriate composition A qB on top of a rod A B to form the molten pool initially, or with a rod of alloy A B to evaporate the molten pool until it reaches composition A qB. The temperature and volume of... 

Only about 10 elements, ie, Cr, Ni, Zn, Sn, In, Ag, Cd, Au, Pb, and Rh, are commercially deposited from aqueous solutions, though alloy deposition such as Cu—Zn (brass), Cu—Sn (bronze), Pb—Sn (solder), Au—Co, Sn—Ni, and Ni—Fe (permalloy) raise this number somewhat. In addition, 10—15 other elements are electrodeposited ia small-scale specialty appHcations. Typically, electrodeposited materials are crystalline, but amorphous metal alloys may also be deposited. One such amorphous alloy is Ni—Cr—P. In some cases, chemical compounds can be electrodeposited at the cathode. For example, black chrome and black molybdenum electrodeposits, both metal oxide particles ia a metallic matrix, are used for decorative purposes and as selective solar thermal absorbers (19). 

The fact that the composition of the speculum deposit must be closely controlled to obtain the best results has been a serious drawback to development. The coating finds uses on decorative hollow-ware, oil lamps and tableware. The bronze deposits with 10 or 20% tin are used lacquered in decorative metal-ware for domestic and personal ornament and, in thick layers to protect hydraulic pit props against corrosion and abrasion. They have also been used with success as undercoatings for nickel-chromium or tin-nickel alloy deposits. 

Copper-tin Although a wide range of copper-zinc alloy deposits can be plated, most experience has been gained with two compositions, i.e. the red copper-rich tin-bronze which contains 90-93% copper and 10-7% tin and the white speculum which contains 50-60% copper and 50-40% tin. 

Let us add here that the fabrication of polycrystalline semiconductive films with enhanced photoresponse and increased resistance to electrochemical corrosion has been attempted by introducing semiconductor particles of colloidal dimensions to bulk deposited films, following the well-developed practice of producing composite metal and alloy deposits with improved thermal, mechanical, or anti-corrosion properties. Eor instance, it has been reported that colloidal cadmium sulfide [105] or mercuric sulfide [106] inclusions significanfly improve photoactivity and corrosion resistance of electrodeposited cadmium selenide. 

STM, SXRD, and X-ray reflectivity are excellent techniques for in situ studies of metal and alloy deposition. XRD is also useful for determining the crystal orientation of deposits. 

The alternate-multilayer formation in the alloy deposit can also be explained on the basis of the above mechanism. First, we have to note that thej value in the low-current... 

Note that essentially the same behavior as for the Ni-P alloy deposition was observed in electrodeposition of other iron-group alloys, such as Co-W and Ni-W alloys. Namely, the deposition current in the presence of Na2W04 (the W-source of the Co-W and Ni-W alloys) started to flow at a more positive potential than in the absence of Na2W04, indicating that the electrodeposition of the Co-W and Ni-W alloys occurs by essentially the same mechanism as that of the Ni-P alloy, suggesting the presence of a general mechanism for the induced co-deposition of these alloys. 

As mentioned above, the Ni-P (Co-W, Ni-W) alloy deposition current in the presence of the P-source (W-source) starts to flow at a more positive potential than in... 

W. Luft and Y. S. Tsuo, Hydrogenated Amorphous Silicon Alloy Deposition Processes. Marcel Dekker, New York, 1993. 

The decomposition of formic acid over evaporated Pd-Au alloy films has been studied by Clarke and Rafter (69) the same reaction on Pd-Au alloy wires was studied by Eley and Luetic (128). The alloy films were prepared in a conventional high vacuum system by simultaneous evaporation of the component metals from tungsten hairpins. The alloy films were characterized by X-ray diffraction and electron microscopy. The X-ray diffractometer peaks were analyzed by a method first used by Moss and Thomas (SO). It was found that alloys deposited at a substrate temperature of 450°C followed by annealing for one hour at the same temperature were substantially homogeneous. Electron microscopy revealed that all compositions were subject to preferred orientation (Section III). 

The composition of the codeposition bath is defined not only by the concentration and type of electrolyte used for depositing the matrix metal, but also by the particle loading in suspension, the pH, the temperature, and the additives used. A variety of electrolytes have been used for the electrocodeposition process including simple metal sulfate or acidic metal sulfate baths to form a metal matrix of copper, iron, nickel, cobalt, or chromium, or their alloys. Deposition of a nickel matrix has also been conducted using a Watts bath which consists of nickel sulfate, nickel chloride and boric acid, and electrolyte baths based on nickel fluoborate or nickel sulfamate. Although many of the bath chemistries used provide high current efficiency, the effect of hydrogen evolution on electrocodeposition is not discussed in the literature. 

For practical as well as fundamental reasons, there has been considerable interest in the deposition of alloys containing metals such as W, Mo, and Sn. In their pure forms, these metals do not catalyze the oxidation of the usual electroless reducing agents. Therefore, their mechanism of codeposition is intriguing, and developing an understanding of it should help to better understand the mechanism of electroless deposition as whole. Obvious questions in ternary and quaternary alloy deposition include the effect of the third or fourth element containing ions in solution on the rate of electroless deposition, as well as on the P and B contents in the case of alloys such as Ni-P and Ni-B. 

Similar complex data has been reported by Haowen et al. [109] for Ni-Sn-P films, again using citrate as a complexant, and by Aoki and Takano [110] for the influence of citrate concentration on the composition W in Ni-W-P alloys. In a study of the deposition of films containing up to 30 at% Sn, Osaka and coworkers [111] observed simpler behavior, evidently due to the more selective complexation of Ni2+ by citrate as a function of citrate concentration, they reported a rapid decrease in alloy deposition rate, an increase in Sn content in the deposit, and a slow decline in P content of the deposits. 

Electroless Ni-Ge-P was studied as a model system for ternary alloy deposition [112], A chloride-free solution with GeC>2 as a source of Ge, hypophosphite as reducing agent, aspartic acid as a selective complexant for Ni2+ ions, which was operated at 80 °C in the pH range of 5-5.8, was developed for depositing Ni-Ge-P films with a tunable Ge content from 0 to 25+ at%. The use of a complexant such as citric acid, which complexed Ge(IY) ions as well as Ni2+ ions, resulted in a much lower Ge content in the electroless deposit, and a more complicated solution to study for the reasons discussed above. The aspartate-containing electroless solution, with its non-complexing pH buffer (succinic acid), approximated a modular system, and, with the exception of the aspartic acid - Ni2+ complexation reaction, exhibited a minimum level of interactions in solution. 

The metal ion in electroless solutions may be significantly complexed as discussed earlier. Not all of the metal ion species in solution will be active for electroless deposition, possibly only the uncomplexed, or aquo-ions hexaquo in the case of Ni2+, and perhaps the ML or M2L2 type complexes. Hence, the concentration of active metal ions may be much less than the overall concentration of metal ions. This raises the possibility that diffusion of metal ions active for the reduction reaction could be a significant factor in the electroless reaction in cases where the patterned elements undergoing deposition are smaller than the linear, or planar, diffusion layer thickness of these ions. In such instances, due to nonlinear diffusion, there is more efficient mass transport of metal ion to the smaller features than to large area (relative to the diffusion layer thickness) features. Thus, neglecting for the moment the opposite effects of additives and dissolved 02, the deposit thickness will tend to be greater on the smaller features, and deposit composition may be nonuniform in the case of alloy deposition. 

Adsorbed additives also tend to undergo reduction during the electroless process, and become incorporated as impurities into deposits, most likely via a mechanism similar to that involved in ternary alloy deposition. In a manner similar to that discussed below in greater detail for dissolved 02, electroless deposition rates will be lower for features smaller than the stabilizer diffusion layer thickness. The edges of larger features, which experience higher stabilizer levels due to enhanced nonplanar... 

The electrodeposition of alloys at potentials positive of the reversible potential of the less noble species has been observed in several binary alloy systems. This shift in the deposition potential of the less noble species has been attributed to the decrease in free energy accompanying the formation of solid solutions and/or intermetallic compounds [61, 62], Co-deposition of this type is often called underpotential alloy deposition to distinguish it from the classical phenomenon of underpotential deposition (UPD) of monolayers onto metal surfaces [63],... 

Several binary alloys of technological importance are known to form by way of an underpotential co-deposition mechanism. The abnormal composition-potential relationship observed in Cu-Zn alloys deposited from cyanide-based electrolytes, one of the most widely used commercial alloy plating processes, is attributed to the underpotential co-deposition of Zn [64]. The UPD of Zn is also known to occur on Co and Fe and has been included in treatments focusing on the anomalous co-deposition of Co-Zn [65] and Ni-Zn alloys [66-68]. Alloys of Cu-Cd have been shown to incorporate Cd at underpotentials when deposited from ethylene diamine solution [69-71]. 

Underpotential alloy deposition is particularly well suited for systems where only small amounts of the less noble species are required. The addition of trace quantities... 

An empirical treatment developed by Kolb et al. [81, 82] relating UPD behavior to the difference in work function between the substrate and depositing species has been used to explain anomalous co-deposition behavior observed in Ni-Fe and Ni-Zn alloys [83]. Although the relationship appears to hold for pure underpotential deposition limited to a monolayer, it does not satisfactorily predict bulk alloy behavior. For example, based on work function data alone, one would expect Zn-Al and Sb-Al alloys to be formed by underpotential alloy deposition. Recent reports in the literature, however, indicate that alloying in these systems does not occur [46, 84]. 

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