# Electrodeposition of Alloys and Compounds in the Era of Microelectronics and Energy Conversion Technology

## Abstract

**:**

## 1. Introduction

## 2. Electrodeposition at the Macroscopic Scale

#### 2.1. Thermodynamics and Redox Potential

^{z}

^{+}and consequently the redox potential E

_{eq}of the reaction A

^{z}

^{+}+ ze → A

_{crystal}, which is given by the Nernst equation:

_{Az+}, is the activity of the ion A

^{z}

^{+}[19].

_{appl}is more negative than E

_{eq}(A); the driving force for film formation is the deviation from equilibrium, and is called overpotential:

_{appl}– E

_{eq}(A)

_{eq}(A).

^{z}

^{+}on a foreign substrate S, and an equilibrium for this system cannot be defined rigorously unless the system is left to spontaneously achieve its own equilibrium. In some instances, this equilibrium could be reached quickly—with highly reactive metal substrates for example; in other cases though, for example metal electrodeposition on Silicon, the approach to equilibrium can be sluggish. In this case an onset or nucleation overpotential can be defined, at which deposition starts to occur [20]; this value can be determined for example by using an electrochemical quartz crystal microbalance. The corresponding potential can be significantly more negative (~200 mV) than the redox potential of A, depending on the atomistic details of the nucleation process, which will be considered in Section 3.

_{Az+}, a

_{Bw+}in solution, and a

_{Aalloy}, a

_{Balloy}at the electrode, only three are independent. For a generic alloy composition and a generic metal ion concentration ratio the equilibrium conditions may not be all satisfied, and the alloy composition/ion concentration would change in response via selective dissolution or deposition in order to establish equilibrium. Due to the activities of A and B in the alloy being different from unity, the Nernst equations for the two equilibria A

^{z}

^{+}+ ze → A

_{alloy}and B

^{w}

^{+}+ we → B

_{alloy}are modified as follows:

_{mix}being the free energy of mixing of the alloy, x

_{A}and x

_{B}= 1 − x

_{A}the molar fraction of the components in the alloy, z and w the oxidation states of A and B, respectively. Similar expressions for an n-component alloy are discussed and reported in Reference [21].

_{mix}is negative and a

_{Aalloy}, a

_{Balloy}are <1. This results in a positive shift of the redox potential of both A and B. This shift in potential can be significant and may lead to a detectable effect; this process is called underpotential codeposition (UPCD) and can be used to grow alloys with improved compositional control, as will be discussed in Section 4.

#### 2.2. Kinetics and Growth Rate

_{0}[exp(−αfη) − exp((1 − α)fη)]

_{0}the exchange current density, α is the transfer coefficient, f = F/RT, and η the overpotential. Note that Equation (6) implies that a reduction current is positive when the overpotential is negative. This expression can be corrected for mass transfer effects to take into account that eventually, at high overpotentials the reduction rate will be limited by the rate of arrival of ions at the electrode [22]. Under restricting conditions, various approximations of the Butler-Volmer relation can be used at small overpotentials (linear approximation) or high overpotentials (ǀηǀ > 120 mV), the latter being referred to as the Tafel approximation:

_{0}[exp(−αfη)]

^{+}. Any other metal ion is reduced through a distinct multi-step mechanism, involving a series of electrochemical (charge transfer), as well as other chemical steps. In this case, the reduction rate at steady state is determined by hypothesizing a definite mechanism and writing the rate equations for each step, assuming all these steps to be at equilibrium. Often, one step (the Rate-Determining Step, RDS) is much slower than the others, and this step alone determines the overall kinetics. Only if an electron transfer is the RDS would the j-η relationship depend exponentially on potential, resulting in a quick approach to the limiting mass transfer conditions. A detailed analysis of multi-electron transfer kinetics for various mechanisms is provided in Reference [23].

_{A}j

_{A}/z + M

_{B}j

_{B}/w)

_{A}, M

_{B}being the atomic weight of A and B, j

_{A}, j

_{B}, the partial currents for the reduction of the two components, z and w the respective oxidation states. These equations should be corrected in the case that additional spurious reactions (such as hydrogen evolution) occur. Once the partial currents are known, it is also possible to calculate alloy composition:

_{A}= n

_{A}/(n

_{A}+ n

_{B}) = (j

_{A}/z)/(j

_{A}/z + j

_{B}/w)

_{i}represents the number of moles of element i.

## 3. Electrodeposition at the Atomic Scale

#### 3.1. Ion Transport

^{7}–10

^{9}V/m, sufficient to strip the water sheath bound to the metal ion. The double layer thickness L is of the order of the nm and depends on the ionic strength of the electrolyte through the relationship:

_{i}

^{0}and z

_{i}are the number density and the charge of ions i, respectively, and the sum is taken over all ionic species present in the electrolyte. In the denominator, ε

_{0}and ε

_{r}are the vacuum and the relative permittivity, respectively, k

_{B}is the Boltzmann constant, and T the absolute temperature.

#### 3.2. Mechanism of Electron Transfer

^{+}reduction at an electrode has shown that the ion in the double layer region exhibits an energy minimum 2.9 Å away from the electrode, sufficiently close to allow the ion to electronically interact with the electrode; the interaction between the 5 s orbital of Ag

^{+}and the sp band of the Ag electrode is therefore sufficiently strong to enable the fast deposition rate that is experimentally observed [30]. This theory, unfortunately, does not describe clearly the dynamic transition from ion to atom that Gileadi sought to understand. In our opinion, the process should be analyzed in terms of the large electric field at the interface using a quantum description for the progressive delocalization of the electron being exchanged. Such a theory has not been considered yet.

#### 3.3. Kinetics of Film Growth

^{4}F, where a is the lattice constant of the crystal structure being grown (m), D is the adatom diffusion coefficient (m

^{2}/s) and F the deposition flux (n

_{atoms}/m

^{2}s). Conventionally, this parameter is referred to in the literature as D/F, assuming a = 1; typical values of D/F then vary between 10

^{4}and 10

^{8}; thermodynamic growth conditions are observed for D/F → ∞, when the ion flux is low and adatoms have sufficient time to settle at minimum energy locations; in contrast, purely kinetically controlled growth obeys the condition D/F → 0, leading to adatoms frozen in metastable configurations [31]. Commercial electrodeposition process are usually very fast and kinetic growth conditions are most common; deposition close to the thermodynamic limit in contrast can be achieved by using very low metal ion concentrations, thus resulting in small current densities that correspond to the diffusion limiting current. The latter conditions are used for fundamental studies, in particular STM growth experiments; see, for example, Reference [32].

#### 3.4. Growth and Film Morphology

_{R}, a surface in vacuum undergoes a roughening transition; typical values of T

_{R}are 320–720 K for Cu(11n) surfaces, 450–750 K for Ni surfaces [33]. Above T

_{R}the energy to form a step is significantly lowered, resulting in an increase in defect density; note that such surface is not necessarily rough in the usual sense, since height differences may still be small. In electrolytes, the roughening transition may occur close to ambient temperatures, but this transition is strongly affected by the anions present in solution; chloride ions for example restore singular facets in Cu surfaces [34]. On rough surfaces, the density of kinks is reported to be about one every 3rd, 5th atom [35].

_{d}a

^{2}/4)exp(−E

_{d}/k

_{B}T)

_{d}being an atomic vibration frequency (attempt rate), a the jump distance (roughly the lattice constant), E

_{d}the activation energy for diffusion. If the average diffusion length is sufficiently large adsorbed atoms will encounter other atoms, forming small clusters. Below a critical size these clusters are not stable, due to their additional surface energy. The free energy of formation for a cluster containing N atoms:

_{c}and the minimum number of atoms N

_{c}needed for the cluster to be stable. In particular, for a 3-D nucleus:

_{c}= (8/27)·B·(v

_{m}

^{2}σ

^{3})/(zeǀηǀ)

^{3}

^{3}/V

^{2}, S being the total surface and V the volume of the nucleus) and v

_{m}is the atomic volume; and for a 2-D nucleus:

_{c}= bsε

^{2}/(zeη)

^{2}

^{2}/4S relates the surface area S of the nucleus to its perimeter L, s is the area occupied by an atom on the surface, and ε the line energy [35]. Close to equilibrium the actual shape of the nucleus is determined by minimization of the surface energy; possible nuclei shapes include 3-D (Volmer-Weber type growth) or 2D (Frank-van der Merwe type growth) [37]. With increasing overpotential, the critical nucleus tends to become smaller and more 2-D. The decrease of N

_{c}with increasing overvoltage implies that the nucleus may at a certain point contain few atoms, thereby invalidating the definition of thermodynamic functions, such as chemical potential and surface energy. An atomistic approach to nucleation has been developed [35], which generally resulted in small deviations from the estimates obtained using the continuum approach. It should be noted that the nucleation process dominates only at smooth surfaces; above T

_{R}the density of kinks is sufficiently high to directly accommodate incoming adatoms, eliminating any energy barrier for nucleation.

_{c}/k

_{B}T)

_{N}M, the number of growing nuclei is given by:

_{0}·[1−exp(−k

_{N}t)]

_{0}being the number of nuclei at saturation.

_{N}t >> 1): M(t) = M

_{0}

_{N}t << 1): M(t) = k

_{N}M

_{0}t

^{-}or Cl

^{-}. The growth is now limited at fewer nucleation sites. A judicious combination of inhibitors and accelerators is at the basis of the superfilling technology that has been so successful in providing high quality Cu interconnects within semiconductor chips [48].

## 4. Overview and Taxonomy of Alloy Deposition Processes

_{tot}= j

_{A}+ j

_{B}or, in the case that hydrogen reduction (HER) may occur in parallel in the potential range of interest, the equation above becomes:

_{tot}= j

_{A}+ j

_{B}+ j

_{HER}

_{0}and the Tafel slope b; knowledge of these quantities enables sketching of the j-V curves for the single metals and by summation for alloy deposition, allowing calculation of the alloy composition as a function of potential via Equation (10). Consider, for example, Figure 2: Under the approximation of current superposition, knowing the partial currents it is possible to determine the total current (a) (in this case j

_{HER}is neglected) and, therefore, the composition as a function of potential (b).

**Figure 2.**(

**a**) Construction of the j

_{TOT}vs. applied voltage characteristics under the assumption of current superposition; (

**b**) The corresponding calculation of alloy composition vs. applied voltage.

#### 4.1. Interactions in the Bulk Electrolyte

**Figure 3.**Calculated concentration of free Co

^{2+}and free Ni

^{2+}before and after the addition of the Ni ions. Dots: concentration of free Co

^{2+}ions in a solution of 0.1 M CoSO

_{4}, 0.2 M NaC

_{6}H

_{5}O

_{7}; triangles: concentration of free Co

^{2+}ions and diamonds: concentration of free Ni

^{2+}ions in a solution of 0.1 M CoSO

_{4}, 0.1M NiSO

_{4}, 0.2 M NaC

_{6}H

_{5}O

_{7}.

#### 4.2. Interactions in the Solid

_{mix}; formation of solid solutions in particular results in a redox potential shift in the positive direction; the phenomenon is referred to as underpotential co-deposition (UPCD). The relationship between the free energy of mixing [51]:

_{mix}= ΔH

_{mix}−TΔS

_{mix}= (W

_{GA}x

_{A}+ W

_{GB}x

_{B})x

_{A}x

_{B}+ RT(x

_{A}lnx

_{A}+ x

_{B}lnx

_{B})

_{alloy}derived from Equation (21) is able to reproduce the whole range of composition vs. potential [52]. Earlier works focused on the UPCD of Pt alloys for magnetic and catalytic applications, demonstrating again that alloy composition could be closely controlled [53,54,55]. UPCD of Pt with the transition metals Fe, Co, Ni however resulted in codeposition only under diffusion limiting conditions for Pt, resulting in hydrogen evolution, pH increase at the interface, and oxygen incorporation in the films [54]. This problem was overcome by utilizing a Pt complex to shift the onset of Pt deposition more negative, leading to closer onset potentials for Fe and Pt and mostly avoiding oxygen incorporation [56,57]; the improved purity also resulted in an earlier onset of the phase transformation of FCC Fe-Pt to the high anisotropy tetragonal structure of interest in magnetic recording [58].

#### 4.3. Interactions at the Interface

^{+}in sulfate solutions and MeCl

^{+}in chloride solutions. Calculation of the potential dependence of adsorption of Me(I) and Fe(I) shows that the Fe(I) adsorbs at much more positive potentials than Ni(I), and in the case of competitive adsorption, the rate of adsorption of Ni(I) is strongly inhibited, resulting in a low Ni fraction in the alloy [63]. Anomalous codeposition occurs only under activation control for both metals, and this phenomenon disappears at high overpotentials, under diffusion limiting conditions. More recently, it has been observed that not only codeposition of Fe inhibits Ni reduction, but also Ni codeposition enhances the Fe reduction rate, meaning that the absolute reduction rate of Fe is increased with respect to that of Fe alone in the presence of Ni

^{2+}in solution. This latter effect has not been fully understood yet but mathematical models have been proposed, where a mixed complex is assumed to form at the surface, providing an additional route for Fe reduction [64,65].

_{4})(Cit)H

^{2−}[69], linking its stoichiometry to the limiting composition (~50:50) that has been achieved. More recently, the observed increase in Re faradaic efficiency (FE) when codeposited with Ni has been interpreted along the same lines, despite the fact that elemental Re can be deposited, even if only at low FE. Specifically, the Re deposition rate is found to be accelerated by an electroless process involving metallic Ni on the substrate, the oxidation of which enables the reduction of ReO− 4 to ReO− 3or Re

^{0}. The hypothesis of an induced deposition process via a mixed complex was ruled out due to the fact that compositions with Re > 50 at% could be achieved [70].

#### 4.4. Peculiarities of Alloy Deposition

## 5. Surface-Limited Electrochemical Processes for Materials Synthesis

^{z}

^{+}and the substrate S being stronger than the pairwise atomic interactions for M-M and S-S. UPD is unique to electrochemical processes; it is in fact possible only due to the low energy of the precursor ions (of the order of kT ~ 0.025 eV), which is of the order of the typical interaction in bulk alloys, typically between 0.01 eV and 0.1 eV. The first comprehensive work on UPD phenomena was carried out by Kolb whom, upon studying a large set of M-S pairs, derived a phenomenological correlation between the underpotential shift ΔE

_{UPD}and the work function Φ of M and S [73]:

_{UPD}= 0.5 V/eV·(Φ

_{S}−Φ

_{M})

^{z}

^{+}to M-S [74].

^{z}

^{+}; the details of this process are determined by various features, including the difference in electronegativity of the two elements, the attractive forces M-S, and the repulsive interaction between UPD atoms. In addition, strain developing during the growth process may contribute to the overall energetics of the system.

^{4+}reduction may require oxidation of two Cu atoms to Cu

^{2+}, leading to the overall reduction of 0.5 ML of Pt. In presence of Cl

^{−}however, Cu is oxidized to ${\text{CuCl}}_{2}^{-}$, i.e., to Cu

^{+}, therefore, the coverage by Pt would be only 0.25 mL. In reality, other modes of Pt reduction related to the presence of defects lead to an increased coverage [78].

**Figure 4.**Schematics of the Surface Limited Redox Reaction process. (

**a**) immersion of Pd substrate in Cu

^{2+}solution; (

**b**) UPD of Cu monolayer on Pd; (

**c**) rinsing and immersion in a Pt

^{4+}solution; (

**d**) the Pt ions are exchanged with Cu atoms to form a Pt submonolayer.

^{2-}from sulfide solution to sulfur monolayers. Transition metals (TMs), such as Mn, Fe, Co, Ni, tend not to UPD on noble metals, such as Au or Ag, but, as a consequence of the strong bonding interactions in TM sulfides, they can UPD on sulfur monolayers. After formation of the TM-S bilayer, the S layer is removed by reducing it back to S

^{2-}, leaving the TM monolayer behind. This method has been named Selective Electrodesorption Based Atomic Layer Deposition (SEBALD) [79]. An additional variant of this process is the use of oxygen monolayers instead of S monolayers; it has been claimed for example that an oxidized Au surface can be used to form a UPD Zn layer; repeating this process a ZnO film made up of Zn/O bilayers can be formed [80].

_{2}S; oxidative deposition of S is observed around −0.8 V

_{SCE}. Figure 5b shows the cyclic voltammetry for Cd reduction from a pH 9.2 ammonia buffer with 0.5 mM CdSO

_{4}at a Ag(111) singe crystal, bare (broken trace) and modified with a S monolayer (continuous trace). The ECALE cycle consists in the oxidation of S from Na

_{2}S at −0.75 V

_{SCE}, followed by rinsing of the cell, and injection of the Cd solution into the cell while keeping the same potential constant for about 30 s.

**Figure 5.**ECALE cycle for CdS deposition. (

**a**) cyclic voltammetry for an ammonia buffered solution containing Na

_{2}S at a Ag(111) single crystal. (

**b**) cyclic voltammetry for an ammonia buffered solution containing CdSO

_{4}at a Ag(111) single crystal (broken trace) and a S-covered Ag(111) (continuous trace). From Reference [83], reproduced with permission of the Electrochemical Society.

**Figure 6.**(

**a**,

**b**) HAADF-STEM images of Pt@Pd nanoparticles: (

**a**) 1 ML Pt, (

**b**) 4 ML Pt. (

**c**,

**d**) Intensity profiles from scan lines across images (

**a**) and (

**b**), respectively. (

**e**,

**f**) reconstruction of the atomic structure of (

**a**) and (

**b**) and structure models. Reprinted with permission from Reference [84]. Copyright 2009 American Chemical Society.

## 6. Final Remarks

## Acknowledgement

## Conflicts of Interest

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**MDPI and ACS Style**

Zangari, G.
Electrodeposition of Alloys and Compounds in the Era of Microelectronics and Energy Conversion Technology. *Coatings* **2015**, *5*, 195-218.
https://doi.org/10.3390/coatings5020195

**AMA Style**

Zangari G.
Electrodeposition of Alloys and Compounds in the Era of Microelectronics and Energy Conversion Technology. *Coatings*. 2015; 5(2):195-218.
https://doi.org/10.3390/coatings5020195

**Chicago/Turabian Style**

Zangari, Giovanni.
2015. "Electrodeposition of Alloys and Compounds in the Era of Microelectronics and Energy Conversion Technology" *Coatings* 5, no. 2: 195-218.
https://doi.org/10.3390/coatings5020195