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

• Published in: Electrochimica acta 2016-08, Vol.209, p.599-622
• Main Author: Dimitrov, Nikolay
• Format: Article
• Language: English
• Subjects: Alloys; catalysts; Categories; Deposition; E-ALD; Epitaxial growth; galvanic displacement; growth; Mathematical models; Modelling; Multilayers; Reaction kinetics; SLRR
• ISSN: 0013-4686; 1873-3859
• DOI: 10.1016/j.electacta.2016.05.115

•Recent advances in the development of approaches for flat epitaxial growth are presented.•The SLRR approach is introduced as a viable avenue for epitaxial deposition of metals and alloys.•A description of all experimental approaches of handling the SLRR deposition cycle is provided.•A description of all results of SLRR based deposition in a variety of systems is presented.•Results of the existing modelling work on the SLRR reaction are also presented and discussed. In 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