Electrodeposition of Pt<sub>100−x</sub>Pb<sub>x</sub> Metastable Alloys and Intermetallics

Hwang, Sun-Mi; Bonevich, John E.; Kim, Jae Jeong; Moffat, Thomas P.

doi:10.1149/1.3572049

Cited by 22 publications

(32 citation statements)

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“…This is referred to as underpotential alloy co-deposition (UPCD) [16] and has been studied in detail and implemented for the growth of alloys with controlled thickness, structure, and composition. One direction of UPCD studies followed the deposition of Pt alloys aimed at applications in the electronic industry (Pt-Co, Pt-Fe) [17][18][19][20] and catalysis (Pt-Cu, Pt-Pb) [21][22][23]. From a fundamental standpoint UPCD has been of interest with its ability to produce metastable configurations in electrodeposited Au-Ni alloys [24] and to ensure a great deal of compositional control by even inverting the thermodynamics of the co-depositing metals (Au-Cu alloys) [25,26].…”

Section: Introductionmentioning

confidence: 99%

Recent Advances in the Growth of Metals, Alloys, and Multilayers by Surface Limited Redox Replacement (SLRR) Based Approaches

Dimitrov

2016

Electrochimica Acta

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A B S T R A C TIn the realm of ever increasing importance of nanotechnology, the deposition of ultrathin metal/alloy layers with perfect structure and unique functionality becomes an objective of paramount importance. In the last decade many research groups have been working on the development and application of a new method for epitaxial thin film growth that employs a surface limited redox replacement (SLRR) as a building block reaction. The multiple repetition of this reaction enables the controlled deposition of a monolayer of metal or alloy per cycle. Work in the field has been done on the development of SLRR deposition protocols along with understanding and modelling of the SLRR reaction kinetics, on comparative studies of SLRR based routines, and on other deposition approaches. Most recently, the development of SLRR was extended to the application of all-electroless approaches for carrying out the SLRR (ESLRR). In this paper an overview of all SLRR, ESLRR and related approaches is presented. The description of the background and reaction formalism introduces the method with emphasis on its general applicability and limitations. The discussion then continues with the description of experimental approaches for carrying out a deposition process by SLRR. In this section specific consideration is given to the deposition by shuttling of the working electrode, the flow-cell configuration, the one-cell configuration, and the all-electroless approaches for realizing the repetitive application of a single-cycle SLRR reaction. Next, the ability of these approaches to produce epitaxial, flat and uniform deposits will be discussed through results of electrochemical, in-situ scanning tunneling microscopy, X-ray Photoelectron Spectroscopy and other characterization experiments showing advantages and limitations of SLRR growth in a variety of systems classified into three categories. In the first of these categories Cu, Ag, and Au are used as model systems to introduce the deposition by SLRR. In the second category Pd and Ru deposition by SLRR has been discussed. In the third category all studies concerning a variety of scenarios for Pt deposition by SLRR are presented and in the last part of that section deposition of alloys and multilayers is critically discussed. The paper then continues with a section presenting and discussing modelling approaches of studying the kinetics of a single-cycle SLRR reaction and concludes with the presentation of the extension of modelling to a system where multi-cycle SLRR deposition processes have been investigated. The analysis in this part focuses on the kinetic parameters of the replacement reaction like rate constant, order of the reaction, type of adsorption behavior of the sacrificial metal etc. Finally, this section concludes with a discussion of the mechanistic aspects of the SLRR reaction and more specifically on the factors impacting the deposition process and in turn the resulting structure, morphology, uniformity and continuity of the accordingly grown thin films. The paper a...

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Section: Introductionmentioning

confidence: 99%

Recent Advances in the Growth of Metals, Alloys, and Multilayers by Surface Limited Redox Replacement (SLRR) Based Approaches

Dimitrov

2016

Electrochimica Acta

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“…In particular, Figure 4 b reveals Pb segregation at grain boundaries throughout the Pt electrode, consistent with the very limited solubility of Pb in Pt away from the Pt 3 Pb line compound. [ 32,33 ] Overall, the STEM-EDS and XRD measurements in stage II suggest that Pt 3 Pb is a transient phase which is not involved in the nucleation of perovskite PZT, though the next stage in the process (stage III, Figure 5 ) will corroborate this more directly.…”

Section: Resultsmentioning

confidence: 91%

Combined Experimental and Computational Methods Reveal the Evolution of Buried Interfaces during Synthesis of Ferroelectric Thin Films

Jones

LeBeau

Nikkel

et al. 2015

Adv Materials Inter

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(1 of 10) 1500181 wileyonlinelibrary.com IntroductionFerroelectric thin fi lms have broad application in society ranging from nonvolatile memories to microrobotics and integrated capacitors. As the sizes of devices and the thicknesses of fi lms decrease, the specifi c surface and interfacial areas increase signifi cantly. At these progressively smaller length scales, interfacial phenomena such as interdiffusion and interface reactions are promoted and can have benefi cial or deleterious consequences on the resultant fi lm and device properties and functionality. [1][2][3][4] Thus, an understanding of interfacial phenomena between dissimilar materials is of paramount importance in materials and devices of small length scale.Solution-based chemical routes have become effective for the synthesis of ferroelectric lead zirconate titanate (PZT) thin fi lms on diverse substrates. [5][6][7][8] In these routes, a solution is spin cast on a substrate and then subsequently heated to induce crystallization of the ferroelectric fi lm. For Pb-based ferroelectric fi lms Understanding interfaces between dissimilar materials is crucial to the development of modern technologies, for example, semiconductor-dielectric and thermoelectric-semiconductor interfaces in emerging electronic devices. However, the structural characterization of buried interfaces is challenging because many measurement techniques are surface sensitive by design. When interested in interface evolution during synthesis, the experimental challenges multiply and often necessitate in situ techniques. For solution-derived lead zirconate titanate (PZT) ferroelectric thin fi lms, the evolution of buried interfaces during synthesis (including dielectricmetal and metal-metal) is thought to dramatically infl uence the resultant dielectric and ferroelectric properties. In the present work, multiple experimental and computational methods are combined to characterize interface evolution during synthesis of ferroelectric PZT fi lms on platinized Si wafers-including in situ X-ray diffraction during thermal treatment, aberration-corrected scanning transmission electron microscopy of samples quenched from various synthesis states, and calculations using density functional theory. Substantial interactions at buried interfaces in the PZT/Pt/Ti/SiO x /Si heterostructure are observed and discussed relative to their role(s) in the synthesis process. The results prove that perovskite PZT nucleates directly from the platinum (111)-oriented bottom electrode and reveal the roles of Pb and O diffusion and intermetallic Pt 3 Pb and Pt 3 Ti phases.

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“…A similar behavior is observed in UPCD alloy films; incorporation of B in the alloy is proportional to the surface coverage, and a solid solution having the crystal structure of A is preferentially formed since this requires no nucleation of a new phase. The example of Pt-Pb discussed in Section 3.4.2 exemplifies this behavior: the lattice constant of FCC Pt-Pb alloys is observed to gradually increase up to 40 at% Pb, suggesting solid solution formation; the bulk solubility of Pb in Pt however is negligible [101]. In addition, random solid solutions are often observed even in alloy systems that form ordered structures (such as in equiatomic Fe-Pt [112,113] or Co-Pt [114]) or intermetallic compounds (again, in Pt-Pb [101]).…”

Section: Crystallographic Structure and Microstructurementioning

confidence: 85%

“…The example of Pt-Pb discussed in Section 3.4.2 exemplifies this behavior: the lattice constant of FCC Pt-Pb alloys is observed to gradually increase up to 40 at% Pb, suggesting solid solution formation; the bulk solubility of Pb in Pt however is negligible [101]. In addition, random solid solutions are often observed even in alloy systems that form ordered structures (such as in equiatomic Fe-Pt [112,113] or Co-Pt [114]) or intermetallic compounds (again, in Pt-Pb [101]). The metastable solid solution in these instances grows preferentially since the number of atomic configurations resulting in the competing ordered structure is much lower, leading to a statistical preference for the former.…”

Section: Crystallographic Structure and Microstructurementioning

confidence: 85%

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Electrochemical Surface Processes and Opportunities for Material Synthesis

Brankovic¹,

Zangari²

2015

Advances in Electrochemical Sciences and Engineering

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Technological advances in the operation and performance of microelectronic, optical, magnetic, and, more recently, energy conversion devices depend in large part on an ever-increasing accuracy of material synthesis and film fabrication methods. In particular, the ongoing miniaturization of devices requires strict control of the crystal structure and microstructure in film as well as patterned structures, often down to the atomic scale.Electrodeposition has an important role to play in this pursuit toward miniaturization and enhanced performance [1]. Underpotential deposition (UPD) [2, 3] and surface-limited redox replacement (SLRR) [4] exploit the low energy of the metal ion precursors in solution (of the order of the thermal energy, 0.025-0.03 eV) to control the formation or replacement of single atomic layers via self-limiting processes. In UPD, a monoatomic layer of metal M is deposited on a conductive substrate S at a potential more positive than the redox potential of M [2]. This shift in redox potential is made possible by the fact that the M-S bond is stronger than the M-M bond; since the effective pair interaction V eff = V MM + V SS − 2V MS is typically in the order of 0.01-0.1 eV, only low energy precursors are sensitive to these energy differences, thus limiting the deposit to one (or sometimes two) atomic layers. SLRR involves UPD monolayer formation, followed by displacement of this layer with a full or partial monolayer of a more noble element, through a cementation process [4]. An analogous process, selective electrodesorption-based atomic layer deposition (SEBALD) consists in the formation at UPD of a sacrificial sulfur monolayer to induce UPD of late transition metals such as Fe, Co, and Ni in the form of monolayers or nanosized islands [5].Underpotential codeposition (UPCD) is a generalization of the UPD process, whereby alloy electrodeposition occurs at potentials more positive than the redox potential of the less noble element [6]. UPCD is made possible by the effective atomic pair interactions in the solid state, or equivalently by the alloying bond enthalpy. In contrast with UPD, UPCD is used to form alloy films of arbitrary

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Electrodeposition of Pt_100−xPb_x Metastable Alloys and Intermetallics

Cited by 22 publications

References 56 publications

Recent Advances in the Growth of Metals, Alloys, and Multilayers by Surface Limited Redox Replacement (SLRR) Based Approaches

Recent Advances in the Growth of Metals, Alloys, and Multilayers by Surface Limited Redox Replacement (SLRR) Based Approaches

Combined Experimental and Computational Methods Reveal the Evolution of Buried Interfaces during Synthesis of Ferroelectric Thin Films

Electrochemical Surface Processes and Opportunities for Material Synthesis

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Electrodeposition of Pt100−xPbx Metastable Alloys and Intermetallics

Cited by 22 publications

References 56 publications

Recent Advances in the Growth of Metals, Alloys, and Multilayers by Surface Limited Redox Replacement (SLRR) Based Approaches

Recent Advances in the Growth of Metals, Alloys, and Multilayers by Surface Limited Redox Replacement (SLRR) Based Approaches

Combined Experimental and Computational Methods Reveal the Evolution of Buried Interfaces during Synthesis of Ferroelectric Thin Films

Electrochemical Surface Processes and Opportunities for Material Synthesis

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Electrodeposition of Pt_100−xPb_x Metastable Alloys and Intermetallics