Electrodeposition metals and alloys

W. H. Safranek, The Properties of Electrodeposited Metals and Alloys, 2nd ed., American Electroplaters and Surface Finishers Society, Orlando, Fla.,... 

The key factors that control the rate of electrodeposition and the structure, physical properties, uniformity, and composition of electrodeposited metals and alloys are (1) thermodynamics (where the electric potential is based on the standard electromotive series) (2) electrode kinetics (which may vary with the structure of the electrodeposit) and (3) mass transport (which is important at high current densities, where the delivery of reactant to the cathode surface affects the local deposition rate and the structure of the deposit). 

The properties of electroplated gold, as often is the case for electrodeposited metals and alloys, are scattered in a number of technical and scientific publications, the only comprehensive review being the chapter devoted to it in the book of Safranek [7]. 

Gold and Gold Alloys, in Pmperties of Electrodeposited Metals and Alloys, William H. Safranek, Elsevier, 1974 American Electroplaters Surface Finishers S 2nd Edition, 1986, pp. 141—194. 

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. 

Electroless deposition as we know it today has had many applications, e.g., in corrosion prevention [5-8], and electronics [9]. Although it yields a limited number of metals and alloys compared to electrodeposition, materials with unique properties, such as Ni-P (corrosion resistance) and Co-P (magnetic properties), are readily obtained by electroless deposition. It is in principle easier to obtain coatings of uniform thickness and composition using the electroless process, since one does not have the current density uniformity problem of electrodeposition. However, as we shall see, the practitioner of electroless deposition needs to be aware of the actions of solution additives and dissolved O2 gas on deposition kinetics, which affect deposit thickness and composition uniformity. Nevertheless, electroless deposition is experiencing increased interest in microelectronics, in part due to the need to replace expensive vacuum metallization methods with less expensive and selective deposition methods. The need to find creative deposition methods in the emerging field of nanofabrication is generating much interest in electroless deposition, at the present time more so as a useful process however, than as a subject of serious research. 

A comparison was made between Ni and Co diffusion barriers produced by electroless, electro-, and evaporation deposition (64). This comparison shows that only electrolessly deposited metals and alloys, at a thickness of 1000 im, have barrier properties for Cu diffusion. For Co(P) 1000-pm-thick barriers, annealed for 14h, the amount of Cu interdiffused into Co(P) is less than 1 at %. Thicker barriers of Ni(P), Ni(B), and Co(B) are required for the same degree of Cu interdiffusion. The same metals, if electrodeposited, both do and do not have inferior barrier properties. This... 

Most solutions used in electrodeposition of metals and alloys contain one or more inorganic or organic additives that have specific functions in the deposition process. These additives affect deposition and crystal-building processes as adsorbates at the surface of the cathode. Thus, in this chapter we first describe adsorption and the factors that determine adsorbate-surface interaction. There are two sets of factors that determine adsorption substrate and adsorbate factors. Substrate factors include electron density, d-band location, and the shape of substrate electronic orbitals. Adsorbate factors include electronegativity and the shape of adsorbate orbitals. 

It is not relevant within the context of this chapter to detail the technical aspects of the electrodeposition of all possible metals and alloys. Such information is available in a number of specialist texts1 2 or handbooks.19 However, it is pertinent to illustrate more specifically than in the above sections the role of coordination compounds in particular cases. 

The electrodeposition of metals from ionic liquids is a novel method for the production of nanocrystalline metals and alloys, because the grain size can be adjusted by varying the electrochemical parameters such as over-potential, current density, pulse parameters, bath composition and temperature and the liquids themselves. Recently, for the first time, nanocrystalline electrodeposition of Al, Fe and Al-Mn alloy has been demonstrated. 

Over the past two decades, ionic liquids (ILs) have attracted considerable interest as media for a wide range of applications. For electrochemical applications they exhibit several advantages over the conventional molecular solvents and high temperature molten salts they show good electrical conductivity, wide electrochemical windows of up to 6 V, low vapor pressure, non-flammability in most cases, and thermal windows of 300-400 °C (see Chapter 4). Moreover, ionic liquids are, in most cases, aprotic so that the complications associated with hydrogen evolution that occur in aqueous baths are eliminated. Thus ILs are suitable for the electrodeposition of metals and alloys, especially those that are difficult to prepare in an aqueous bath. Several reviews on the electrodeposition of metals and alloys in ILs have already been published [1-4], A selection of published examples of the electrodeposition of alloys from ionic liquids is listed in Table 5.1 [5-40]. Ionic liquids can be classified into water/air sensitive and water/air stable ones (see Chapter 3). Historically, the water-sensitive chloroaluminate first generation ILs are the most intensively studied. However, in future the focus will rather be on air- and water-stable ionic liquids due to their variety and the less strict conditions under which... 

The pulsed electrodeposition technique (PED) is a versatile method for the preparation of nanostructured metals and alloys [47]. In the last two decades PED has received much attention worldwide because it allows the preparation of large bulk samples with high purity, low porosity and enhanced thermal stability. 

The electrodeposition of metals and alloys has been investigated extensively in the chloroaluminate ionic liquids. Many kinds of metal salts, mostly chlorides, can be dissolved in ionic liquids with their Lewis acidity or basicity controlled by changing the composition of AICI3. In the case of acidic ionic liquids that contain AICI3 at more than 50 mol%, a dimeric chloroaluminate anion, AI2CI7, acts as a Lewis... 

The electrodeposition of several metals and alloys has been investigated in tetrafluoroborate ionic liquids. In contrast to the chloroaluminate ionic liquids, the tetrafluoroborate ionic liquids are considerably more stable against moisture and are expected to be applicable to practical use. Moreover the co-deposition of... 

Some ionic liquids composed of organic halides and metal halides have been studied for the electrodeposition of the metals and alloys. Most of these ionic liquids are hygroscopic and unstable against water, the same as the chloroaluminate ionic liquids. Moreover some of these ionic liquids are viscous to the extent that they need elevating temperature and/or addition of co-solvents. The electrodeposition of Ga [108], Ga-As [109], In-Sb [110], Sn [111], and Nb-Sn [112-114] has been reported in these ionic liquids. 

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