Development and Application of a New Method for Epitaxial Growth of Metals, Alloys and Multilayers by Surface Limited Redox Replacement

Nikolay Dimitrov, SUNY at Binghamton, DMR 0742016

A quantitative study of the impact of key Cu plating parameters on the voiding propensity of solder joints with Cu plated in a commercially available plating solution (CAPS) is performed on a small Cu rotating disk electrode. It is shown that void-prone samples are deposited predominantly at higher overpotentials. Also, a Hull cell with a large cathode is used to scale up the voiding study. It is shown that plating conditions could be chosen in a way to generate both, void-prone and void-proof Cu on the same cathode panel, thus controlling the voiding propensity at larger scale.This work proposes “green” alternatives for fabrication of viable and cost-efficient fuel cell catalysts coated by a thin Pt film. The research is aimed at establishing a protocol for the growth of continuous Pt thin films on foreign substrate surfaces. Unlike in previously reported studies, in this work SLRR is carried out via displacement of H UPD layer eliminating completely contaminations coming from Cu or Pb, used presently for platinization. The work explores SLRR of H UPD prone and no H UPD exhibiting substrates warranting direct or seeded growth, respectively.

CAPS for Acidic Cu2+

PlatingCAPS Plating in a Hull Cell

Seeded SLRRSeeded SLRR

Direct SLRRDirect SLRR

Only slight surfaceroughening after SLRRin comparison with OPD growth

Considerableincrease ofthe surfacearea and roughness after growth on Pd nano-particles

0

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0 0.05 0.1 0.15 0.2 0.25 0.3

Te

mp

era

ture

/oC

Cu

rren

t De

ns

ity/m

A c

m-2

Overpotential/V ×(-1)

VOIDING

solder balls

10 cm

4 cm

away from the anode close to the anode

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-0.8 -0.6 -0.4 -0.2 0 0.2 0.4

Pd/Pt

Pd

E, V (SSE)

Cu

rre

nt

(A

)

-80

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-0.8 -0.6 -0.4 -0.2 0 0.2 0.4

Pt/Au10R H10R OPD

Cu

rre

nt

(A

)

E, V (SSE)Me + H UPD - YES

Me + H UPD - NO

H atomPt atom

Pt growth by H UPD

Dissemination: A large portion of the activities on development of protocols based on SLRR of Pb UPD for Pt deposition and fundamentals of electrochemical deposition by UPD mediated techniques, both supported by this grant, was presented as invited talks by Nikolay Dimitrov in May 2011 at the 219th Meeting of ECS, Montreal, Canada. Fred Wafula and Dan McCurry presented posters at MARM-ACS meeting in College Park, MD in May 2011. Two related papers were also published in the last nine months in Langmuir and Journal of Applied Electrochemistry.

Dr. Natasa VasiljevicDepartment of Physics,University of Bristol, UK

Professional Development

Fred Wafula received the Chemistry Department Award for Outstanding Achievements in Teaching.

During the summer of 2011 Alexandra Foxx was involved in a summer REU work with our research group.

Development and Application of a New Method for Epitaxial Growth of Metals, Alloys and Multilayers by Surface Limited Redox Replacement

Nikolay Dimitrov, SUNY at Binghamton, DMR 0742016

Alexandra Foxx, a junior student in Chemical Engineering at Johns Hopkins University joined in May 2011 the PI’s group for a ten-week summer REU activity sponsored by NSF. She participated in a research associated with improving of our practices in making STM tips and she worked closely on strategies for SLRR deposition of Pt on foreign substrates .

Dr. Peter Borgesen

Ongoing Collaborations

Studies of the SLRR of Pt by H UPD have been carried out in collaboration with Dr. Natasa Vasiljevic from University of Bristol, UK.

Work on the catalytic activity of PtxCu(1-x) (hkl) alloy nanoparticles has been performed in collaboration with Dr. Fang’s group at SUNY Binghamton.

Glass interposers metalized with combined electroless/electrolytic protocol founded an emerging new collaboration with Dr. Borgesen’s group at SUNY Binghamton.

One Step from Au to Pt via Surface Limited Redox Replacement (SLRR) of Pb

UPD

DEPARTMENT OF SYSTEMS SCIENCE AND INDUSTRIAL ENGINEERING

Recent Advances in UPD Assisted Epitaxial Growth of Metals and

Multilayer Structures

Nikolay Dimitrov - Invited Talks:

Fred Wafula, a Ph.D. student in the PI’s group, received in 2011 the Chemistry Department Award for Outstanding Achievements in Teaching and was nominated for the Binghamton University Award for Excellence in Teaching.