Electrochemical Atomic Layer Deposition (E-ALD) of Palladium Nanofilms by Surface Limited Redox Replacement (SLRR), with EDTA Complexation

Sheridan, Leah B.; Czerwiniski, Justin; Jayaraju, N.; Gebregziabiher, Daniel K.; Stickney, John L.; Robinson, David B.; Soriaga, Manuel P.

doi:10.1007/s12678-012-0080-7

Cited by 35 publications

(68 citation statements)

References 50 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…To asses this hypothesis, EDTA and excess chloride [58] were used to complex Pd 2+ ions, with the general being aim to slow down the Cu À Pd exchange rate. Both complexing agents led to a decrease in the rate of replacement, producing more homogeneous films [57,58]. Although the use of EDTA improved the homogeneity, it also decreased the deposit thickness by a factor of 3 compared to the thickness obtained via the use of chloride.…”

Section: Pd and Ru Depositionmentioning

confidence: 98%

“…More specifically, it has been reported that films tend to grow unevenly and in turn feature varied roughness depending upon the proximity to the electrolyte inlet and outlet [56,57]. This issue that apparently is strongly related to a concentration gradient across the flow cell in the onset of the replacement step of the SLRR cycle has been addressed by introducing complexing agents to the growth solution for slowing down the deposition process and thus minimizing the trends to uneven growth [57,58]. While positive effect has been obtained in general, the latter intervention carries risks for lowering the efficiency and contaminating the deposit.…”

Section: The Flow-cell Approachmentioning

confidence: 99%

“…The deposition of Pd on Pt (111) and on Au (111) by the SLRR of a pre-deposited UPD layer of Cu was studied in detail by Soriaga et al [82] and Stickney et al [57], respectively. The results obtained are of significant interest given the applicability of thin Pd coatings in a variety of scenarios associated with fuel-cell catalysis [83,84].…”

Section: Pd and Ru Depositionmentioning

confidence: 99%

“…Pd thin films were formed by the SLRR of Cu UPD layers on polycrystalline Au substrates in an electrochemical flow deposition system [57]. The initial step was Cu UPD, followed by its exchange for Pd ions at open circuit, and finishing with a blank rinse to complete the cycle.…”

Section: Pd and Ru Depositionmentioning

confidence: 99%

“…Deposits were formed with up to 75 cycles and displayed proportional deposit thicknesses. It was demonstrated by electron probe microanalysis (EPMA) that excess Pd deposition at the flow cell ingress occurs when the SLRR deposition of Pd takes place in a solution containing PdCl 2 salt only [57]. Such results suggested according to the authors that the SLRR mechanism did not involve direct transfer between a Cu UPD atom and a Pd 2+ ion directly occupying the Cu UPD atom position.…”

Section: Pd and Ru Depositionmentioning

confidence: 99%

See 4 more Smart Citations

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

Dimitrov

2016

Electrochimica Acta

View full text Add to dashboard Cite

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...

show abstract

Section: Pd and Ru Depositionmentioning

confidence: 98%

Section: The Flow-cell Approachmentioning

confidence: 99%

Section: Pd and Ru Depositionmentioning

confidence: 99%

Section: Pd and Ru Depositionmentioning

confidence: 99%

Section: Pd and Ru Depositionmentioning

confidence: 99%

See 3 more Smart Citations

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

Dimitrov

2016

Electrochimica Acta

View full text Add to dashboard Cite

show abstract

Electrochemical Deposition of PdBiSn Catalyst for Glycerol Oxidation in Alkaline Medium

et al. 2020

View full text Add to dashboard Cite

PdBiSn thin film on Au substrate was prepared by means of the electrochemical atomic layer deposition (E-ALD) technique. The morphology and elemental distribution of the catalysts was determined using scanning electron microscope equipped with energy dispersive spectroscopy (EDS) detector. The catalysts contained all the deposited elements distributed evenly on the surface. Electro-oxidation of glycerol was tested in alkaline media using cyclic voltammetry (CV) and chronoamperometry (CA). The activity of the catalysts towards the oxidation of glycerol improved with the addition of Sn and Bi with the binary PdBi catalyst being the most improved.

show abstract

Electroformation of Pd‐modified Thin Film Electrocatalysts Using E‐ALD Technique

et al. 2021

View full text Add to dashboard Cite

Electrochemical atomic layer deposition was used to form bimetallic (BiPd, CuPd) and trimetallic (CuBiPd) thin films via surface‐confined reactions. Pd thin films were characterized by cyclic voltammetry, scanning electron microscopy (SEM) and the alloy formation with preferred Au/Pd(111) orientation was confirmed by XRD. AFM revealed uniform grain distribution, with 3D islands growing on CuBiPd. EDX verified the presence of all deposited elements. Compared to other prepared catalysts, CuBiPd catalyst showed higher activity and stability towards the ethanol oxidation reaction (EOR), as confirmed by the peak current and onset potential trends, respectively: CuBiPd (1.35 mA, −0.450 V)>CuPd (0.6016 mA, −0.442 V)>BiPd (0.275 mA, −0.384 V)>Pd (0.186 mA, −0.350 V). The EOR current on CuBiPd improved by 2.5 folds relative to Pd. The results show that CuBiPd electrocatalyst is a promising material for EOR with enhanced catalytic properties for direct ethanol fuel cell

show abstract

Electrochemical Atomic Layer Deposition (E-ALD) of Palladium Nanofilms by Surface Limited Redox Replacement (SLRR), with EDTA Complexation

Cited by 35 publications

References 50 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

Electrochemical Deposition of PdBiSn Catalyst for Glycerol Oxidation in Alkaline Medium

Electroformation of Pd‐modified Thin Film Electrocatalysts Using E‐ALD Technique

Contact Info

Product

Resources

About