acct~

surface soience
ELSEVIER Applied SurfaceScience81 (1994)387-398

The electrochemical faceting of copper in 85% aqueous

o-phosphoric acid by using a potential reversal technique
A. Hern~ndez Creus, R.M. Souto, S. Gonz~lez, M.M. Laz, R.C. Salvarezza 1,
A.J. Arvia ,,1
Departamento de Quimica Fisica, Universidad de La Laguna, Tenerife, Spain
Received5 April 1994;acceptedfor publication14 August 1994

Abstract

The electrochemical faceting of differently prepared polycrystalline Cu specimens in 85% H3PO4 solution at 25°C was
investigated using symmetric square-wave periodic-potential routines. The electrochemical characteristics of electrofaceted
specimens were followed by Tl upd voltammetry and complemented by scanning electron microscopy observations.
Depending on the experimental conditions the electrochemical faceting involves a preferred crystallographic orientation at
the specimen surface and an increase in surface roughness. Electrofaceting at grain domains without a significant increase in
surface roughness occurs preferentially at high frequencies, whereas Cu islands with a marked increase in surface roughness
are produced at low frequencies. The interpretation of the overall effect is given in terms of the likely reaction mechanism
already established for the Cu/Cu(II) and Cu/Cu(I) electrodes, including further kinetic aspects of the Cu(I) disproportiona-
tion reaction in the solution.

1. Introduction attention has been paid to the application of these

techniques to other low cost, more commonly found
The electrochemical faceting of metals based upon metals of a wider practical interest.
the application of different periodic-potential rou- In this work a phenomenological approach to Cu
tines is an attractive procedure for developing tex- faceting is presented. Cu faceting is produced apply-
tured metal surfaces [1-6]. This procedure was ex- ing the potential reversal technique to polycrystalline
tensively employed to modify the surface topography Cu electrodes in 85% aqueous o-phosphoric acid.
of noble-metal electrodes by applying either a peri- Attention to this solution has been paid because of
odic potential to these electrodes immersed in an its common use for Cu electropolishing [8]. Results
aqueous environment [7] or by electroreducing a show that the development of textured Cu electrode
noble-metal hydrous oxide layer previously accumu- surfaces is accompanied by changes in the topogra-
lated by using an adequate potential routine [5]. Less phy which can be followed through both scanning
electron microscopy (SEM) and underpotential depo-
sition (upd)/anodic stripping voltammetry of TI(I)
* Correspondingauthor. ions on faceted Cu specimens [9]. Electrofaceting at
1VisitingProfessor,INIFrA, UniversidadNaeionalde La Plata, grain domains without a significant increase in sur-
La Plata, Argentina. face roughness occurs preferentially at high frequen-

0169-4332/94/$07.00 © 1994 ElsevierScienceB.V. All rights reserved

SSD1 0169-4332(94)00288-6
388 A. Herndndez Creus et al. /Applied Surface Science 81 (1994) 387-398

cies, whereas Cu islands with a marked increase in taining H3PO 4 solution mounted with a conventional
surface roughness are produced at low frequencies. Luggin-Haber capillary tip arrangement. The Cu(II)-
Cu electrofaceting can be explained by extending ion concentration of this solution was controlled by
the conventional mechanism earlier discussed for the the Cu electrodissolution charge passed during the
Cu electrode reactions in aqueous solution [10-18] anodization of a Cu rod. The standard potential of
taking into account the heterogeneity of the polycrys- the Cu/Cu(II) electrode was E = 0.104 V versus
talline Cu electrode surface, the Cu(I)/Cu(II)/Cu(O) SCE at 25°C. Potentials in the text are referenced to
equilibria in the solution, and the relative contribu- the SCE scale. The working solution consisted of
tion to faceting of mass-transport processes in the 85% HaPO 4 as described for Cu electropolishing [8].
bulk of the solution and Cu atom diffusion on the Runs were made at 25.0 + 0.1°C.
electrode surface. The voltammogram of each Working electrode
was first recorded at 0.01 V s-1 between the anodic
and the cathodic switching potentials, E a = - 0 . 6 5 V
2. Experimental details and E c = 0.10 V, respectively, to establish the poten-
tial windows adequate for faceting.
Cu was electrochemically faceted in a conven- Electrochemical faceting proceeded by applying
tional three-electrode Pyrex glass cell. Experiments during a certain time (t) in the 10 min < t < 24 h
were performed on differently prepared Cu working range a symmetric square-wave periodic potential
electrodes. (SWPP) between a lower ( - 0.75 < E / < - 0 . 3 0 V)
One type of working electrode was made from and an upper (0 < E u < 0.15 V) switching potential
polycrystalline (pc) 99.9% purity Cu rods which at a frequency in the 0.25 Hz < f < 5 kHz range. The
were machined in such a way that the active elec- cathodic (~'/) and anodic (~'u) half-period ratio was 1
trode area was the base of a small cylinder. This type (~'/= ~'u = T) and ~" ( 7 = 1 / 2 f ) was set in the 0.1
of electrode was used as a horizontal disc either in ms < r < 2 s range.
contact with a stagnant solution or as a rotating disc The voltammetric characteristics of TI(I) upd on
electrode supporting a hanging electrolyte column untreated and faceted Cu electrodes were followed at
[19] at the rotation speed to = 500 rpm. Each elec- 0.01 V s - i as a reference potential sweep rate. For
trode was first mechanically polished, then thermally this purpose the following solution was used, 5 ×
treated as indicated elsewhere [20], and finally, sub- 1 0 - a M T12SO 4 + 5 x 1 0 - 5 M H2SO 4 + 0.2M
jected to electropolishing in stagnant H3PO 4 ( p = Na2SO4, with E c = - 0 . 7 3 V and E a = - 0 . 3 0 V.
1.71 g c m -3) for 5 - 1 0 min at 0.3 A cm -2 and at SEM micrographs of treated Cu electrodes were
room temperature. The Cu surface finishing was obtained by using a Hitachi S-450 equipment with an
checked through conventional reflection microscopy. electron beam energy ranging from 20 to 25 keV.
Thereafter, these electrodes are called electropol-
ished Cu electrodes.
Cu electrodes were also prepared by electrodepo- 3. Results
sition at constant potential ( E d) from either aqueous
0.3M CuSO a + 0.01M H2SO 4 + 0.007M KNaC4H 4 3.1. Cyclic voltammetry of Cu in 85% H3PO 4 -
06 (E d = - 0 . 2 V and E d = - 0 . 6 V) at room tem- electrofaceting potential range
perature or aqueous 0.58M CuCN + 1.5M KCN +
0.75M KOH at constant current (Id) (0.05 < I d < 0.1 A voltammogram of electropolished Cu speci-
A) and 45 ° [21]. A Cu (0.2 cm in diameter) or a Pt mens in 85% aqueous o-phosphoric acid run at 0.01
( ~ 0.126 cm in diameter) sphere was used as sub- V s -1 from E ¢ = - 0 . 6 5 V upwards (Fig. 1), shows
strate. a marked current increase related to the Cu elec-
The counter electrode was a large-area Cu plate trodissolution at E > - 0 . 1 V, where E is the ap-
facing the working electrode surface. The reference plied potential. The reverse potential sweep from 0.1
electrode was either a saturated calomel electrode V to E ¢ - - - 0 . 6 5 V shows a diffusional limiting
(SCE) or a Cu electrode immersed in Cu(II)-ion-con- current from E < 0.07 V downwards, which is due