952 Chem. Mater.

2001, 13, 952-959

Epitaxial Electrodeposition of Copper(I) Oxide on

Single-Crystal Copper
Julie K. Barton, Alexey A. Vertegel, Eric W. Bohannan, and Jay A. Switzer*
Department of Chemistry and Graduate Center for Materials Research, University of
MissourisRolla, Rolla, Missouri 65409-1170
Received September 5, 2000. Revised Manuscript Received December 6, 2000

Epitaxial thin films of copper(I) oxide (Pn3m, a ) 0.427 nm) were electrodeposited onto
[110]-, [111]-, and [100]-oriented single-crystal copper (Fm3m, a ) 0.3615 nm) by reduction
of copper(II) lactate in solution. Cu2O films grown on Cu(110) and Cu(111) exhibited both
an out-of- and in-plane orientation following that of the substrate as measured by 2θ and
azimuthal X-ray scans, up to a thickness of 0.8 µm. X-ray diffraction studies showed that
Cu2O films deposited onto Cu(100) grow initially with a near-[111] orientation up to a critical
thickness, beyond which film growth is primarily in the [100] direction. The films were found
to be both in- and out-of-plane oriented throughout, as measured by azimuthal X-ray scans.
In situ 2θ X-ray measurements showed a critical thickness for growth in the [100] direction
of about 360 nm. As determined from scanning electron microscopy images, the Cu2O films
deposited onto Cu(100) grew with triangular facets consistent with the [111] orientation
prior to the critical thickness, and then as pyramidal islands over the initial triangular layers
above this thickness. A proposed interface model of Cu2O(111) over Cu(100) yields a low
mismatch and a high number of atomic contact points per unit area, offering a possible
explanation for the initial [111]-oriented deposition.

Introduction substrate is dependent on the solution pH.12 In addition,

scanning electron microscopy (SEM) images revealed
Electrodeposition is a simple and inexpensive tech- that these films grow with a faceted microstructure
nique for preparing epitaxial films. We have recently corresponding to the out-of-plane orientation of the film,
electrodeposited epitaxial thin films of δ-Bi2O3, Cu2O, yielding four-sided pyramids or triangular structures for
PbS, Tl2O3, Fe3O4, and a Cu2O/PbS heterojunction onto [100]- and [111]-oriented films, respectively.12 Lee et al.
single-crystal Au.1-7 However, little work has been done deposited Cu2O onto Pt from a weakly acidic solution
with epitaxial electrodeposition onto substrates other and reported a film with a [111] out-of-plane orienta-
than Au. In the present work, it is shown that this tion.13 In both experiments, geometric facets grew with
technique may be extended to the deposition of epitaxial no particular orientation within the plane of the film.
thin films of Cu2O onto single-crystal Cu. In other studies, we have shown that the deposition
Cu2O is a p-type semiconductor that has been elec- current for the Cu2O is limited by a Schottky-like
trodeposited previously on a variety of substrates.8-11 barrier that forms between Cu2O and the deposition
In previous studies of the electrodeposition of Cu2O solution.12 We have also shown that under certain
films, we have demonstrated that the out-of-plane galvanostatic conditions the working electrode potential
orientation of a film deposited on a polycrystalline spontaneously oscillates,14,15 forming a Cu/Cu2O-layered
nanostructure that shows a negative differential resis-
* E-mail: jswitzer@umr.edu. tance (NDR) feature during perpendicular transport
(1) Switzer, J. A.; Shumsky, M. G.; Bohannan, E. W. Science 1999, measurements.16 The 1/L2 dependence of the NDR
284, 293. feature on the Cu2O layer thickness suggests quantum
(2) Bohannan, E. W.; Jaynes, C. C.; Shumsky, M. G.; Barton, J. K.;
Switzer, J. A. Solid State Ionics 2000, 131, 97. confinement of carriers in the nanoscale Cu2O.17 Al-
(3) Vertegel, A. A.; Shumsky, M. G.; Switzer, J. A. Angew. Chem., though these layered nanostructues have, at present,
Int. Ed. Engl. 1999, 38, 3169.
(4) Bohannan, E. W.; Shumsky, M. G.; Switzer, J. A. Chem. Mater.
only been deposited on polycrystalline substrates, it
1999, 11, 2289.
(5) Vertegel, A. A.; Shumsky, M. G.; Switzer, J. A. Electrochim. Acta (12) Golden, T. D.; Shumsky, M. G.; Zhou, Y.; Vanderwerf, R. A.;
2000, 45, 3233. Van Leeuwen, R. A.; Switzer, J. A. Chem. Mater. 1996, 8, 2499.
(6) Nikiforov, M. P.; Vertegel, A. A.; Switzer, J. A. Adv. Mater. 2000, (13) Lee, J.; Tak, Y. Electrochem. Solid-State Lett. 1999, 2, 559.
12, 1351. (14) Bohannan, E. W.; Huang, L.-Y.; Miller, F. S.; Shumsky, M. G.;
(7) Vertegel, A. A.; Shumsky, M. G.; Switzer, J. A. Chem. Mater. Switzer, J. A. Langmuir 1999, 15, 813.
2000, 12, 596. (15) Switzer, J. A.; Hung, C.-J.; Huang, L.-Y.; Miller, F. S.; Zhou,
(8) Mukhopadhyay, A. K.; Chakraborty, A. K.; Chatterjee, A. P.; Y.; Raub, E. R.; Shumsky, M. G.; Bohannan, E. W. J. Mater. Res. 1998,
Lahiri, S. K. Thin Solid Films 1992, 209, 92. 13, 909.
(9) Chatterjee, A. P.; Mukhopadhyay, A. K.; Chakraborty, A. K.; (16) Switzer, J. A.; Hung, C.-J.; Huang, L.-Y.; Switzer, E. R.;
Sasmal, R. N.; Lahiri, S. K. Mater. Lett. 1991, 11, 358. Kammler, D. R.; Golden, T. D.; Bohannan, E. W. J. Am. Chem. Soc.
(10) Rakhshani, A. E.; Varghese, J. Thin Solid Films 1988, 157, 1998, 120, 3530.
87. (17) Switzer, J. A.; Maune, B. M.; Raub, E. R.; Bohannan, E. W. J.
(11) Tench, D.; Warren, L. F. J. Electrochem. Soc. 1983, 130, 869. Phys. Chem. B 1999, 103, 395.

10.1021/cm000707k CCC: $20.00 © 2001 American Chemical Society

Published on Web 01/18/2001
Electrodeposition of Copper(I) Oxide Chem. Mater., Vol. 13, No. 3, 2001 953

would be desirable for device applications to deposit

these structures as epitaxial films on single-crystal
substrates. A study of the deposition and growth
behavior of Cu2O on Cu single-crystal substrates may
prove a useful starting point to developing epitaxial Cu/
Cu2O-layered nanostructures.
A significant amount of work has been done concern-
ing oxide growth in the monolayer range on copper
substrates. Gewirth et al. have made in situ observa-
tions of oxide growth on Cu(111) in both aqueous and
native environments, and found epitaxial Cu2O(111) to
form in both cases.18 Gewirth et al. have also studied
oxygen adsorption on a Cu(100) surface and reported a
(x2 × x2)R45° adlattice.19 Ikemaya et al. studied
aqueous oxide formation on Cu(100) and Cu(111) sub-
strates, with results agreeing with those reported by
Gewirth et al. They suggested coincidence lattices of (6
× 6)Cu2O(111)//(7 × 7)Cu(111) and (6 × 6)Cu2O(100)-
[001]//(5 × 5)Cu(100)[011], respectively.20
Little research has been done on the electrodeposition
of bulk Cu2O films on copper substrates, and research
on the electrodeposition of epitaxial Cu2O on Cu grown
to thicknesses in the micron range has yet to be
reported. Santra et al. electrodeposited Cu2O films onto
polycrystalline copper from a copper lactate solution and
studied the microstructural effects of solution pH and
film annealing temperature, reporting an optimum
solution pH of 9.2-9.3.21 In the present work, we extend
our study of epitaxial electrodeposited films to that of Figure 1. 2θ X-ray patterns of 0.7 µm thick Cu2O films
Cu2O on low-index Cu single-crystal substrates. Films deposited on (A) Cu(111) and (B) Cu(110). Both films followed
grown to a maximum thickness of 0.8 µm on Cu(110) the orientation of the Cu substrates.
and (111) exhibited orientations of [110] and [111],
respectively, whereas films deposited on Cu(100) grew situ XRD experiments, the deposition solution was kept at a
constant temperature of 30 °C with a Fisher model 9100
with an initial orientation of [111], transforming after circulator, and constant stirring was applied. X-ray diffraction
a certain thickness into a [100] orientation. All films (XRD) experiments were performed with a Scintag 2000
exhibit epitaxial growth with respect to the Cu sub- diffractometer using Cu KR radiation. Azimuthal and tilt scans
strate. were obtained through the attachment of a texture goniometer
accessory to the Scintag 2000.
Due to the limiting conditions of the in situ XRD set up,
Experimental Section
deposition for these experiments was performed at approxi-
The deposition solution was prepared by adding 450 mL of mately 25 °C. In situ measurements of films grown on Cu-
5 M NaOH to 90 g of Cu(II) sulfate pentahydrate and 150 mL (100) were made with the above-described potentiostat/
of 85+% lactic acid. The solution was adjusted to pH 9.0 with galvanostat and Scintag instruments, again with a large area
further additions of aqueous 5 M NaOH. Water was HPLC- copper wire functioning as the counter electrode. The deposi-
grade (Aldrich), and all other chemicals were reagent-grade tion solution was approximately 0.5 mm in height above the
(Aldrich). Working electrodes consisted of 1 cm diameter Cu- substrate, so as to minimize the absorption of X-rays by the
(110), Cu(111), and Cu(100) single crystals purchased from the copper lactate solution. The small volume of liquid required
Monocrystals company. A copper wire fitted around the edge reconstitution every 30 min. Approximately every 10 min, 2θ
of the crystals served as the electrical contact during deposi- scans were run, from 2θ ) 34-51.5°. Micrographs of the
tion. A large area copper wire was used as the counter deposited films were obtained with a Hitachi model S4700 cold-
electrode. In all experiments, a constant cathodic current field emission scanning electron microscope.
density of 0.03 mA/cm3 was applied to the working electrodes
with an EG&G Princeton Applied Research model 273A Results and Discussion
potentiostat/galvanostat. The deposition rate was 0.037 nm/
s. Deposition times ranging from about 5000 to 80 000 seconds, A. Deposition of Cu2O on Cu(111) and Cu(110).
yielding films in the thickness range of 0.2-3.0 µm. Parts A and B of Figure 1 show 2θ X-ray diffraction
Prior to deposition, the Cu electrodes were electropolished patterns for films grown on Cu(111) and (110), respec-
in a 67 vol % orthophosphoric acid aqueous solution at a tively. Only those Cu2O peaks corresponding to the
potential of 1.45 V versus SCE. Immediately before deposition, orientation of the substrate are observed, indicating a
the electrodes were treated with a drop of 0.1 M HClO4 to
strong out-of-plane orientation for both films. The
remove any native oxide present. With the exception of the in
patterns in Figure 1 are of films grown to a thickness
of 0.7 µm; however, 2θ scans of films over a thickness
(18) Chu, Y. S.; Robinson, I. K.; Gewirth, A. A. J. Chem. Phys. 1998,
110, 5952.
range of 0.35-0.8 µm yielded the same results.
(19) Cruickshank, J. R.; Sneddon, D. D.; Gewirth, A. A. Surf. Sci. Evidence for in-plane texture was obtained from pole
1993, 281, L308. figures for all films. The Bragg (θ), tilt (χ), azimuthal
(20) Ikemaya, N.; Kubo, T.; Hara S. Surf. Sci. 1995, 323, 81.
(21) Santra, K.; Chatterjee, S. P.; Gupta, S. Sol. Energy Mater. 1999, (φ), and rocking (ω) angles used in the X-ray measure-
57, 345. ments are shown in Figure 2. In generating an azi-
954 Chem. Mater., Vol. 13, No. 3, 2001 Barton et al.

Figure 2. Schematic of the experimental setup used to

determine the in- and out-of-plane orientation of epitaxial films
by X-ray diffraction. The out-of-plane orientation is determined
in the Bragg-Brentano configuration by standard θ-θ scans.
The out-of-plane mosaicity is determined by rocking the
sample about the ω-axis. Rotating the sample 360° about the
φ-axis results in a two-dimensional azimuthal scan. Construct-
ing azimuthal scans for a series of tilt angles, χ, results in a
three-dimensional pole figure, in which the epitaxy of the film
has been determined for all crystallographic planes of the
substrate.

muthal pattern of an [hkl]-oriented film, the X-ray

source-detector system is set to a 2θ value corresponding
to some other plane (h′k′l′). The sample is then tilted
about the χ-axis until the (h′k′l′) planes are brought into
the Bragg condition. The angle of tilting, χ, corresponds
to the angle between the (hkl) and (h′k′l′) planes.
Rotation of the sample along the perpendicular φ-axis
results in an azimuthal scan. A series of these azimuthal
scans run over a range of tilt angles results in a three-
dimensional pole figure. The pole figure of a perfectly
epitaxial film should yield zero intensity at all values
of χ other than that corresponding to the angle between
the (hkl) and (h′k′l′) planes.
The values of 2θ used here were experimentally
determined as the angle of maximum diffracted inten-
sity for the reflection of interest. For all pole figures,
azimuthal scans were run at every 1.0° tilt as the
sample was tilted from χ ) 0-80°. In generating the
(220) pole figure for the [111]-oriented Cu2O film, the
X-ray detector was first set to a 2θ value of 61.35°,
corresponding to the (220) Cu2O peak. A value of 2θ ) Figure 3. Contour plots of pole figures of Cu2O films
36.57° was chosen for the (111) pole figure of the (110)- deposited on (A) Cu(111) and (B) Cu(110). Part A is a (220)
oriented film, corresponding to the (111) Cu2O peak. For pole figure with a theoretical tilt angle of χ ) 35.3° for the
both films, the theoretical tilt angle for maximum (111) plane of Cu2O, and part B is a (111) pole figure, also
with χ ) 35.3° theoretically. In both figures, experimentally
intensity is χ ) 35.3°, corresponding to the angle
determined tilt angles (displayed in figure) agree reasonably
between the (110) and (111) planes. well with this calculated value.
The pole figures for the (111) and (100) Cu2O films
are shown in contour form in parts A and B of Figure and these correspond to grains that have grown aligned
3, respectively. Figure 3 shows an apparent 6-fold with the substrate. Our results show that the film is
symmetry with a maximum intensity at χ ) 36.8°, twinned, but we do not know if this twinning occurs on
agreeing reasonably well with the theoretical tilt angle the substrate or if it is due to faulting during growth.
of 35.3˚. The 6-fold pattern is actually two sets of 3-fold Figure 3B shows a 2-fold symmetry with a maximum
patterns, rotated 180° about an axis perpendicular to intensity at χ ) 37.0°, with no observed rotation of the
the plane of Figure 3A. This pattern suggests that film relative to the Cu substrate. The peaks in Figure
although the (111) plane of the film is parallel to the 3B are greater than 6000 times more intense than the
(111) plane of the Cu substrate, individual crystalline background, while those in Figure 3A are only several
grains in the film appear to have grown either aligned 100-1000 times greater than the lowest background.
with, or opposite to, the in-plane direction of the The small increase in background intensity observed at
substrate. This agrees with results from previous work- angles of χ below 37° in Figure 3A is due to copper
ers.18 One set of peaks is more intense than the other, fluorescence.
Electrodeposition of Copper(I) Oxide Chem. Mater., Vol. 13, No. 3, 2001 955

Figure 5. Ex situ 2θ X-ray patterns of four Cu2O films

deposited on Cu(100), to thicknesses of (A) 0.2, (B) 0.4, (C)
Figure 4. Models for epitaxial growth of Cu2O on (A) Cu- 0.7, and (D) 2.6 µm. The patterns indicate that initial growth
(111) and (B) Cu(110). The Cu atoms from the Cu substrate is in the [111] direction but becomes dominated by growth in
are dark, and the Cu atoms from the Cu2O film are light. The the [100] direction as film thickness increases. Insets in parts
solid lines indicate proposed coincidence unit cells. Part A A and B show the Cu2O(111) and (200) peaks at a higher
shows one of the two possible epitaxial relationships, defined magnification.
as Cu2O(111)[1 h 10]//Cu(111)[1
h 10]. A coincidence lattice may
also be formed by rotating the Cu2O(111) plane by 180°. Part
B shows an epitaxial relationship of Cu2O(110)[001]//Cu(110)-
[001]. In both cases, a coincidence lattice is formed by six Cu
atoms in the Cu2O plane to seven Cu atoms in the Cu plane
and results in a mismatch of 1.22%.

Parts A and B of Figure 4 shows possible epitaxial

relationships of the bulk Cu2O films to the Cu(111) and
Cu(110) substrates, respectively. The dark circles rep-
resent the Cu atoms of the Cu substrate, and the light
circles represent the Cu atoms of Cu2O. For Cu2O over
Cu(111), the film and substrate are aligned such that
the [110] direction of Cu2O is either parallel or anti-
parallel to the [110] of the Cu. The epitaxial relation-
ships are thus Cu2O(111)[1 h 10]//Cu(111)[1
h 10] and Cu2O-
(111)[11h 0]//Cu(111)[1h 10]. As seen in Figure 4A, a
coincidence lattice can be formed by six Cu atoms in
Figure 6. In situ 2θ X-ray patterns for a film grown on Cu-
the Cu2O plane to every seven Cu atoms in the Cu (100). Results agree with ex-situ measurements, indicating
plane. The misfit for this coincidence is 1.22%, compared that the film grows primarily in the [111] direction to a critical
with the calculated unit cell misfit of 18.1%. Figure 4B thickness, after which growth is primarily in the [100] direc-
shows a Cu2O(110)[001]//Cu(110)[001] coincidence lat- tion. The (200) peak for Cu2O first appears at a thickness of
tice, again with six Cu atoms from Cu2O to every seven 360 nm, indicating that this is approximately the critical
Cu atoms in the Cu plane. It should be noted that parts thickness above which growth is primarily in the [100]
direction.
A and B of Figure 4 are derived from XRD measure-
ments of the Cu2O film, which only take into account B. Deposition of Cu2O on Cu(100). Several films
the bulk of the material and do not say anything of the were deposited onto [100]-oriented Cu single crystals,
first monolayers of the Cu2O film. These models do, to thicknesses ranging from 0.2 to 2.6 µm. Results of ex
however, agree with results obtained by other work- situ 2θ X-ray diffraction scans are shown in Figure 5.
ers.18,20 These patterns indicate that, contrary to the expected
956 Chem. Mater., Vol. 13, No. 3, 2001 Barton et al.

Figure 7. Contour plots of pole figure diffraction scans of Cu2O films deposited on Cu(100) to thicknesses of (A) 0.2, (B) 0.4, (C)
0.7, and (D) 2.6 µm. All figures are (220) pole figures, with a theoretical tilt angle of χ ) 35.3° for the (111) out-of-plane orientation
of Cu2O and χ ) 45° for the (100) out-of-plane orientation of Cu2O. Parts A and D, corresponding to (111) and (100) growth,
respectively, result in tilt angles (displayed in the figure) which agree reasonably well with these calculated values. Plots of films
of intermediate thickness yield patterns that do not correspond to either the (111) or (100) orientations. Tilt angles in part C have
values of χ1 ) 30.1°, χ2 ) 38.6°, and χ3 ) 46.1°.

growth of Cu2O(100), the Cu2O film is initially domi- direction becomes significant is less than or equal to 360
nated by growth in the [111] direction and only after nm.
some critical thickness begins to be dominated by To determine the epitaxial behavior of Cu2O films on
growth in the [100] direction. At a film thickness of 0.2 Cu(100), the (220) pole figures shown in Figure 7 were
µm, only the Cu2O(111) peak is clearly visible. As the acquired. According to the 2θ X-ray patterns, the 0.2
film thickness increases, the (200) peak becomes visible, µm thick film should show a maximum pole figure
and its intensity increases faster than that of the (111) intensity corresponding to the (111) plane, that is, at a
peak. The ratio of the (111) to (200) peak intensities tilt angle of χ ) 35.3°. Similarly, the pole figure for the
decreases from 7.7 to 0.62 as the film thickness in- 2.6 µm thick film should yield a maximum intensity
creases from 0.2 to 2.6 µm, indicating that at a thickness corresponding to the (200) plane at χ ) 45°. Figure 7A
of 2.6 µm, the film is dominated by [100]-oriented shows 12-fold symmetry with maximum peak intensities
crystals. The ratio of the intensity of the Cu2O(111) peak at χ ) 36.1°, with a deviation of about (1.9°. This
to the Cu(200) peak remains approximately constant for symmetry is to be expected, as one can line up the
thicknesses between 0.7 and 2.6 µm, whereas the Cu2O- triangular pattern of the Cu2O(111) planes over the
(200) peak increases by nearly 40% relative to the Cu- square-patterned Cu(100) planes four ways, thus yield-
(200) peak, indicating that the growth rate in the [111] ing a pole figure with four sets of 3-fold patterns.
direction has decreased to a value close to zero after a Parts B and C of Figure 7 are plots of the intermediate
thickness of ≈0.7 µm. In situ XRD experiments were thicknesses of 0.4 and 0.7 µm, respectively. Figure 7B
also conducted, and results agree with those obtained shows six distinct peaks and several indistinct peaks
from the ex situ measurements. The in situ 2θ X-ray at tilt angles ranging from χ ) 32.4°-39.0°, indicating
diffraction results are shown in Figure 6. The Cu2O- the same 12-fold symmetry as that seen in Figure 7A.
(200) peak becomes visible at a thickness of 360 nm, There is also an observable, though not very intense,
showing that the thickness at which growth in the [100] 4-fold pattern at χ ) 45.8°, indicating that growth in
Electrodeposition of Copper(I) Oxide Chem. Mater., Vol. 13, No. 3, 2001 957

but after a certain thickness is dominated by growth in

the [100] direction.4 In the case of deposition onto Cu-
(100), the film grows initially in the [111] direction due
to the influence of the substrate as described above.
However, as the film thickness increases, the kinetically
preferred growth in the [100] direction begins to domi-
nate. In addition, it does not appear that [100]-oriented
crystals nucleate instantaneously on the [111]-oriented
film, but rather that the growth direction of the film
slowly tilts away from the [111], so that the [111] axis
is no longer perpendicular to the substrate. This kind
of growth has been observed in the chemical vapor
deposition (CVD) of diamond films grown at higher than
optimum temperatures.22 It is reported by Wild et al.
that the initially deposited diamond films are (100)-
oriented, but as growth continues, the texture axis of
Figure 8. Proposed model for the epitaxial growth of Cu2O- the film tilts away from the [100] direction, resulting
(111) on Cu(100). The Cu atoms from the Cu substrate are in pole scans similar to those obtained here. Growth
dark, and the Cu atoms from the Cu2O film are light. The solid along near-low index directions such as the [100] or
lines indicate the proposed coincidence unit cell, which is
hexagonal. The epitaxial relationship of Cu2O(111)[112 h ]//Cu- [111] can also be interpreted as growth along high Miller
(100)[001] yields a mismatch of 3.57% along the Cu2O[112 h ]// index directions that are tilted several degrees relative
Cu[001] direction. This proposed model results in over twice to their low-index counterparts. Clausing et al. observed
as many contact points per square centimeter as that of Cu2O- such an orientation for a diamond film, reporting a (17
(100) on Cu(100). 3 0) texture for which the (100) planes are tilted 9° from
parallel to the substrate.23
the [100] direction has begun. Figure 7C shows what The pole figure results shown in Figure 7 may now
appears to be a 4-fold pattern at an average of χ ) 30.1°, be better understood, because as planes tilt away from
a combination of two 4-fold patterns at χ ) 38.6°, and parallel to the substrate, the tilt angles at which they
another 4-fold pattern at χ ) 46.1°. These two figures are observed in the pole figures will also change. The
indicate that at the intermediate thicknesses, a trans- angle, R, to which the (111) planes are tilted relative to
formation from a [111] to a [100]-oriented Cu2O film is the surface of the substrate can be calculated from the
taking place. As in Figure 3, Cu radiation caused a X-ray pole figures. In this specific case it appears that
slight increase in background intensity at low tilt angles the (111) planes are tilting such that one apex of the
for Figure 7A-C, where peak intensity is low. The pole triangular (111) plane points downward to the sub-
figure in Figure 7D shows 4-fold symmetry, with a strate. It can be shown that for each set of tilted (111)
maximum intensity at χ ) 46.1°, with no rotation of the planes, one of the (110) planes requires a smaller degree
pattern relative to that of the Cu substrate, indicating of tilting, and two require greater tilting to enter into
that the film is primarily [100]-oriented and strongly the Bragg condition than for the case in which the (111)
epitaxial. planes are parallel to the substrate. The angle between
Figure 8 shows one of the four possible alignments of the (110) and (111) planes is 35.3°, and so a pole figure
the Cu2O (111) over the Cu(100). Three similar patterns for this situation will result in a 3-fold pattern for which
can be obtained by rotating the Cu2O(111) plane every one peak is located at χ < 35.3° and two at χ > 35.3°.
90° over a span of 360°. The Cu atoms of the Cu As stated above, there are four ways in which (111)
substrate are dark, and the Cu atoms of Cu2O are light. planes may align above (100) planes, and so the pattern
The directions of alignment were obtained by XRD repeats itself four times, yielding a pole figure like that
azimuthal scans, and result in a Cu2O(111)[112 h ]//Cu- shown in Figure 7C. The similarity between the tilt
(100)[001] coincidence lattice. The calculated mismatch angles observed in parts B and C of Figure 7, both of
for this coincidence is 3.57% along the [112h ] Cu2O which contain (100)-oriented crystals, indicates that
direction. The number of coincident points per unit area although growth does continue in the near-[111] direc-
as calculated from this model is 1.4 × 1014 points/cm2. tion beyond a film thickness of 0.4 µm, the increase in
This value is roughly 2.3 times the value of 6.1 × 1013 tilting away from the [111] direction is very slight. It
points/cm2, as obtained for the previously mentioned (6 therefore appears that the angles observed for the 0.7
× 6)Cu2O(100)[001]//(5 × 5)Cu(100)[011] model.19,20 µm film represent the critical angles to which the (111)
Again, this model is determined by XRD, and the planes tilt occur before growth begins in the [100]
orientation of the first monolayers of the film is un- direction. A value of R ) 5.47° has been calculated from
known. If this model can be applied to the first mono- the pattern observed in Figure 7C, which yields a
layers of growth, then the significant increase in contact calculated χ1 ) 29.8° and χ2 ) 38.3°. These values agree
points per unit area may be a primary driving force well with the experimentally determined (pole figure)
behind these somewhat surprising results.
As mentioned in the Introduction, we have previously
(22) Wild, C.; Koidl, P.; Mueller-Sebert, W.; Walcher, H.; Kohl, R.;
found that Cu2O deposited onto polycrystalline sub- Herres, N.; Locher, R.; Samlenski, R.; Brenn, R. Diamond Relat. Mater.
strates from a solution of pH 9.0 grows with a kinetically 1993, 2, 158.
preferred [100] orientation.12 The same result is seen (23) Clausing, R. E.; Heatherly, L.; Specht, E. D. Diamond and
Diamond-like Films and Coatings. In NATO Advanced Studies Institute
on single-crystal gold substrates with orientations other Series, Serial B (266); Clausing, R. E., Horton, L. L., Angus, J. C., Koidl,
than (100). Growth initially follows that of the substrate P., Eds.; Plenum: New York, 1992; p 611.
958 Chem. Mater., Vol. 13, No. 3, 2001 Barton et al.

Figure 9. SEM images of Cu2O films deposited on Cu(100) grown to thicknesses of (A) 0.2, (B) 0.4, (C) 0.7, and (D) 2.6 µm. The
transformation from growth in the [111] direction to the [100] can be visualized by the change from a film dominated by triangular
facets to those of squares. Throughout the transformation, the facets remain oriented within the plane of the film surface.

values of χ1 ) 30.1° and χ2 ) 38.6°. This tilting of the To visualize the transformation occurring in these
(111) planes by this amount is equivalent to saying that films, SEM images were taken of the Cu2O films at
growth is now occurring in the [554] direction, resulting different stages of growth and are shown in Figure 9.
in a near-[111] orientated film. The SEM image of a 0.2 µm film (Figure 9A) reveals
The significance of the tilting of the (111) planes, or crystals of indistinguishable shape, with diameter, D,
the corresponding growth along high-Miller index direc- ranging from approximately 65 to 90 nm. The image of
tions, as it relates to the nucleation of (100)-oriented a 0.4 µm film (Figure 9B) shows a combination of
crystals is not yet understood. The driving force for the triangular and rectangular crystals, with Dtri ) 150-
transformation may be the relief of strain due to lattice 390 nm and Drect ) 40-150 nm. The number of visible
mismatch. It is known that the atomic structures of high rectangles is very small compared to that of the tri-
Miller index surfaces can be described in terms of angles, agreeing with previous results that the film is
terraces and steps.24 This is much like Wild’s observa- primarily [111]-oriented. At a thickness of 0.7 µm
tion that the tilting of the growth axis in the diamond (Figure 9C), the rectangular crystals have increased in
films away from the [100] direction resulted in a size and number, corresponding to the increased growth
roughened surface, with steps between adjacent (100) in the [100] direction. The shape has also changed from
facets.22 In our system, it is possible that the develop- rectangular to square. The visible triangles have also
ment of steps may provide the nucleation sites for (100)- increased in size, but by a much smaller percent.
orientated growth. It is well-known that epitaxial Average crystal sizes are Dtri ) 260-480 nm and Dsqr
growth of GaAs on Si single-crystal substrates often ) 90-240 nm. The images agree with 2θ and pole figure
requires the miscutting of the Si crystal to create steps X-ray data indicating that these thicknesses are trans-
that serve as nucleation sites for the initial GaAs formation regions during which primary growth is
layer.25 changing from the [111] to the [100] direction. As can
be seen in Figure 9D, at a film thickness of 2.6 µm, only
(24) Somorjai, G. A. Introduction to Surface Chemistry and Cataly- squares are visible. Once again, this agrees well with
sis; Wiley: New York, 1994.
(25) Fischer, R. J.; Chand, W. F.; Kopp, W. F.; Morkoc, H.; Erickson, the earlier XRD results, which indicated that the thicker
L. P.; Youngman, P. Appl. Phys. Lett. 1985, 47, 397. film is predominantly [100]-oriented. The crystals visible
Electrodeposition of Copper(I) Oxide Chem. Mater., Vol. 13, No. 3, 2001 959

at this point appear to be much more uniform in both grows primarily in the near-[111] direction up to a
size and shape, with an average size on the order of 400 critical thickness (≈360 nm) after which the growth
nm. It is important to note that these images reveal not occurs in both the near-[111] and [100] direction. At
only geometric facets, but that these facets are aligned some thickness above 0.7 µm, nearly all growth appears
in the same direction within the plane of the film, to be in the [100] direction. At a thickness of 2.6 µm,
indicating that the films are truly epitaxial. It is not the Cu2O film is predominantly [100]-oriented and is
clear from the images whether the film begins growth epitaxial with the Cu substrate. It is suggested that the
in only the [111] direction, or is simply dominated by higher rate of growth in the [100] direction combats
growth in that direction. It does appear, however, that what may be the initial energetic driving force for
as the [100] direction becomes more dominant, some growth in the [111] direction, resulting in an ultimate
crystals continue to grow in the [111] direction, as change in film orientation. It is further suggested that
indicated by the increased size of the triangles from 0.4 this change manifests itself by nucleating growth in
to 0.7 µm. Evidence of any tilting of the (111) planes high index directions, resulting in a slight tilting of the
cannot be seen from these images, as no cross-sectional (111) planes relative to the substrate. This tilting
view was available. Cross-sectional transmission elec- appears to increase to a maximum angle of approxi-
tron microscopy (TEM) may prove ideal in gaining clear mately 5.5°. Further research will focus on obtaining a
insight into the mode of film growth. better understanding of the mechanism of this trans-
formation.
Conclusions
Epitaxial films of Cu2O were electrodeposited onto
Cu(111), (110), and (100) single crystals by reduction Acknowledgment. This work was supported by the
of copper(II) lactate in alkaline solution. X-ray studies National Science Foundation (CHE-9816484, DMR-
of films grown on Cu(111) and (110) indicated that Cu2O 9704288, DMR-0071365, and DMR-0076338), the Foun-
films grew epitaxially, with orientations following that dation for Chemical Research, and the University of
of the Cu substrates. MissourisRolla OURE program.
Surprising results of both X-ray and SEM studies of
films grown on Cu(100) indicate that the Cu2O film CM000707K