Epitaxial Electrodeposition of Copper(I)

Oxide on Single-Crystal Gold(100)

Eri c W. Bohannan, Mark G. Shumsky, and
Jay A. Swi tzer*
University of MissourisRolla, Department of
Chemistry and GraduateCenter for Materials
Research, Rolla, Missouri 65409-1170
Received May 18, 1999
Revised Manuscript Received J uly 14, 1999
Introduction
Si ngl e-crystal fi l ms are i mportant for devi ce appl i ca-
ti ons, as the i ntri nsi c properti es of the materi al of
i nterest can be expl oi ted rather than i ts grai n bound-
ari es. The abi l i ty to si mpl y and i nexpensi vel y prepare
epi taxi al fi l ms wi th a desi red ori entati on al l ows the
sel ecti on of the fi l m ori entati on that most enhances the
property of i nterest. For exampl e, i t woul d be desi rabl e
to sel ect the ori entati on of a materi al that exhi bi ts the
hi ghest i oni c mobi l i ty
1
or to sel ect the pl ane of a
materi al that shows the hi ghest degree of catal yti c
acti vi ty.
2
Recentl y, we reported that epi taxi al thi n fi l ms
of -Bi
2
O
3
can be el ectrodeposi ted from an al kal i ne
tartrate sol uti on onto si ngl e-crystal Au at a temperature
of 65 C.
3
Thi s cubi c pol ymorph of Bi
2
O
3
has been shown
to have the hi ghest oxi de i on mobi l i ty of any known
materi al .
4
I n the present work we use el ectrodeposi ti on
to prepare epi taxi al fi l ms of copper(I ) oxi de (Cu
2
O) on
a si ngl e-crystal Au(100) substrate. Cu
2
O i s a p-type
semi conductor that has been el ectrodeposi ted previ ousl y
on a vari ety of substrates.
5-8
We have previ ousl y shown
that the ori entati on of el ectrodeposi ted Cu
2
O fi l ms i s a
functi on of the pH of the al kal i ne l actate sol uti on and
that the deposi ti on current i s l i mi ted by a Schottky-l i ke
barri er that forms between Cu
2
O and the deposi ti on
sol uti on.
9
We have al so shown that, under certai n
gal vanostati c condi ti ons, the worki ng el ectrode potenti al
spontaneousl y osci l l ates,
10,11
formi ng a Cu/Cu
2
O l ayered
nanostructure that shows a negati ve di fferenti al resi s-
tance (NDR) feature duri ng perpendi cul ar transport
measurements.
12
The NDR feature shi fts wi th a 1/L
2
dependence on the Cu
2
O l ayer thi ckness, suggesti ve of
quantum confi nement of carri ers i n the nanoscal e
Cu
2
O.
13
These l ayered nanostructures were deposi ted
on pol ycrystal l i ne substrates. However, i t woul d be
desi rabl e for devi ce appl i cati ons to deposi t these struc-
tures as epi taxi al fi l ms on si ngl e-crystal substrates. I n
the present work, we expl ore the epi taxi al growth of
pure Cu
2
O onto si ngl e-crystal gol d. I n subsequent work,
we wi l l study the deposi ti on of Cu/Cu
2
O l ayered nano-
structures on si ngl e-crystal substrates.
The underpotenti al deposi ti on of monol ayers of metal s
on si ngl e-crystal substrates has been studi ed qui te
extensi vel y.
14
Li ttl e work, however, has been done on
the el ectrodeposi ti on of epi taxi al semi conductor fi l ms
wi th thi cknesses i n the mi crometer range. El ectrochemi -
cal atomi c l ayer epi taxy has been used for the formati on
of CdSe monol ayers on Au(111).
15
Epi taxi al CdTe fi l ms
can be el ectrodeposi ted from aqueous sol uti on onto I nP-
(111) si ngl e crystal s.
16
Large area epi taxi al thi n fi l ms
of CdSe
17
and quantum dots of Cd(Se,Te) have been
prepared on evaporated Au(111) fi l ms.
18
Epi taxi al CdS
nanocrystal s have been prepared on graphi te by a
combi ned el ectrochemi cal /chemi cal method.
19,20
We show i n the present work that el ectrodeposi ted
fi l ms of Cu
2
O grow epi taxi al l y on Au(100) si ngl e crys-
tal s. The crystal structures of Au and Cu
2
O are shown
i n Fi gure 1. Cuprous oxi de i s pri mi ti ve cubi c, space
group Pn3m, wi th a l atti ce parameter of 0.427 nm. Au
i s fcc, space group Fm3m, wi th a l atti ce parameter of
0.4079 nm. The l atti ce mi smatch ((a
fi l m
- a
substrate
)/
a
substrate
) between the two materi al s i s 4.7%. The epi -
taxi al Cu
2
O fi l m grown on Au(100) shows a hi gh degree
of structural perfecti on, wi th no rotati on of the Cu
2
O
wi th respect to Au.
Experimental Section
The deposi ti on sol uti on was prepared by addi ng 450 mL of
5 M NaOH to 60 g of Cu(I I ) sul fate pentahydrate and 150 mL
of 85+%l acti c aci d, resul ti ng i n a dark bl ue sol uti on. The fi nal
pH of the sol uti on was adjusted to pH 9.0 wi th 5 M NaOH.
HPLC-grade water (Al dri ch) was used to prepare the 5 M
NaOH. Al l other chemi cal s were reagent grade, purchased
from Al dri ch. The worki ng el ectrode consi sted of an el ectropol -
i shed Au(100) si ngl e-crystal purchased from Monocrystal s Co.
The Au crystal had a di ameter of 10 mm and a thi ckness of 1
mm. A gol d wi re was fi tted around the edge of the crystal to
* To whom correspondence shoul d be addressed. E-mai l :
jswi tzer@umr.edu.
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2289 Chem. Mater. 1999, 11, 2289-2291
10.1021/cm990304o CCC: $18.00 1999 Ameri can Chemi cal Soci ety
Publ i shed on Web 08/17/1999
serve as the el ectri cal contact duri ng deposi ti on. The counter
el ectrode was a l arge area copper wi re. A constant cathodi c
current densi ty of 0.01 mA/cm
2
was appl i ed to the worki ng
el ectrode wi th an EG&G Pri nceton Appl i ed Research model
273A potenti ostat/gal vanostat for a peri od of 40 000 s, gi vi ng
a nomi nal Cu2O fi l m thi ckness of 0.5 m. Thi s current densi ty
corresponds to a deposi ti on rate for Cu2O of approxi matel y 0.12
/s, assumi ng a 100% current effi ci ency for deposi ti on. Ap-
pl i cati on of current densi ti es hi gher than about 0.1 mA/cm
2
i n thi s sol uti on gi ves ri se to osci l l ati ons i n the potenti al
coi nci dent wi th the deposi ti on of a Cu/Cu2O l ayered nano-
structure on the worki ng el ectrode.
10-12
To deposi t pure
cuprous oxi de, i t i s necessary to appl y current densi ti es bel ow
thi s threshol d val ue. The sti rred deposi ti on sol uti on was
mai ntai ned at a constant temperature of 30 C wi th a Fi sher
model 9100 ci rcul ator. X-ray di ffracti on (XRD) experi ments
were performed wi th a Sci ntag 2000 di ffractometer usi ng Cu
KR radi ati on. Azi muthal and ti l t scans were obtai ned by the
use of a texture goni ometer accessory that had been fashi oned
i n-house for the Sci ntag 2000.
Results and Discussion
Fi gure 2 shows the 2 X-ray pattern for the el ectrode-
posi ted Cu
2
O fi l m on si ngl e-crystal Au(100). Onl y the
(200) and (400) peaks for the fi l m and the substrate are
observed. The (200) Cu
2
O peak i s greater than a
thousand ti mes more i ntense than any other Cu
2
O
refl ecti on, i ndi cati ve of a strong out-of-pl ane texture.
Rocki ng curves performed on the (200) refl ecti ons of
both Au and Cu
2
O gave ful l -wi dth at hal f-maxi mum
(fwhm) val ues of 0.6 and 0.7, respecti vel y, i ndi cati ng
that the fi l m had onl y a sl i ghtl y greater mosai c spread
than the substrate. An epi taxi al rel ati onshi p mi ght be
i nferred from Fi gure 2, as the Cu
2
O appears to fol l ow
the ori entati on of the Au substrate. However, there i s
a compl i cati ng factor. Under the presentl y used deposi -
ti on condi ti ons the ki neti cal l y preferred growth di recti on
for Cu
2
O i s [100]. Hence, even a Cu
2
O fi l m grown on a
pol ycrystal l i ne substrate wi l l show a strong (100) tex-
ture. To show that the Cu
2
O fi l m trul y has grown
epi taxi al l y on the Au substrate, i t i s necessary to show
both i n-pl ane as wel l as out-of-pl ane ori entati on.
To determi ne the i n-pl ane epi taxi al rel ati onshi p
between the fi l m and substrate, i t i s necessary to bri ng
other refl ecti ons, besi des the (100), i nto the Bragg
condi ti on. Thi s i s accompl i shed by ti l ti ng the sampl e,
through the use of a goni ometer, to the ti l t angl e ()
between the pl anes of i nterest. Gi ven that the angl e
between the (100) and (110) pl ane i s 45 and the (100)
pl ane i s ori ented paral l el to the surface i n our sampl e,
must be 45 i n order to bri ng the (110) refl ecti on i nto
the Bragg condi ti on. Setti ng 2 equal to the refl ecti on
of i nterest, i n thi s case the (220) refl ecti ons of Au and
Cu
2
O, and rotati ng the sampl e provi des an azi muthal
() scan. Azi muthal scans run at a successi on of di ffer-
ent ti l t angl es can be used to gener ate a thr ee-
di mensi onal pol e fi gure for the crystal of i nterest. Fi gure
3 shows the (220) pol e fi gures for both Au and Cu
2
O.
The pol e fi gures were obtai ned by setti ng 2 equal to
the angl e of maxi mum di ffracted i ntensi ty for the
materi al of i nterest (2 ) 64.58 and 61.34 for Au and
Cu
2
O, respecti vel y) and obtai ni ng azi muthal scans at
ti l t angl es from 0 to 60. Four-fol d symmetry i s observed
i n both cases, wi th a maxi mum i ntensi ty at ) 45,
and wi th no rotati on of the Cu
2
O wi th respect to Au.
The pol e fi gure shows that the fi l m has a strong i n-pl ane
ori entati on i n addi ti on to the out-of-pl ane ori entati on
that was measured i n the 2 scan. I f the fi l m had a
random i n-pl ane ori entati on but a strong out-of-pl ane
ori entati on (i .e., a fi ber texture), the 4-fol d symmetry
woul d not be seen. I nstead, a ri ng wi th maxi mum
i ntensi ty at a ti l t angl e of 45 woul d be observed i n the
pol e fi gure.
Fi gure 4 shows a pl ot of the l ogari thm of i ntensi ty vs
azi muthal angl e, , for the (220) refl ecti ons of Au and
Cu
2
O both obtai ned at a ti l t angl e, , of 45. Consi stent
wi th the rocki ng curve measurements, the average
fwhm val ues for the azi muthal scans were 1.1 and 1.4
for Au and Cu
2
O, respecti vel y. The basel i ne of the Cu
2
O
azi muthal scan i s essenti al l y i denti cal to that of the Au,
i ndi cati ng a mi ni mal presence of pol ycrystal l i ne Cu
2
O
i n the fi l m.
Figure1. Crystal structures of Au and Cu2O. Au i s fcc, space
group Fm3m, wi th a l atti ce parameter of 0.4079 nm. Cu2O i s
pri mi ti ve cubi c, space group Pn3m, wi th a l atti ce parameter
of 0.427 nm. I n the Cu2O structure, the l arge spheres are
copper and the smal l spheres are oxygen. The l atti ce mi smatch
between the two materi al s i s 4.7%.
Figure 2. 2 X-ray pattern for a 0.5 m thi ck Cu2O fi l m
el ectrodeposi ted on si ngl e-crystal Au (100). Onl y the (200) and
(400) refl ecti ons for the fi l m and substrate are observed. The
mi nor peak marked wi th an asteri sk i s from the (200) Au
refl ecti on and i s due to Cu K radi ati on.
2290 Chem. Mater., Vol. 11, No. 9, 1999 Communications
Another measure of the structural perfecti on of the
epi taxi al Cu
2
O fi l m i s a ti l t scan. These were obtai ned
by setti ng the azi muthal angl e, , equal to the angl e of
the fi rst of the four maxi ma observed for Cu
2
O and Au
i n Fi gures 3 and 4. Leavi ng fi xed, was vari ed from
0 to 70 and the di ffracted i ntensi ty was observed for
the (220) refl ecti ons of Au and Cu
2
O, i ndependentl y. The
fwhm val ues for the ti l t scans were i denti cal for Au and
Cu
2
O, wi th a val ue of 1.4, i ndi cati ng that, wi thi n the
resol uti on of our i nstrument, the Cu
2
O fi l m and Au
substrate are of comparabl e qual i ty, despi te the l ack of
stri ct commensuri sm between fi l m and substrate.
Thi s study has shown that epi taxi al fi l ms of Cu
2
O can
be el ectrodeposi ted on si ngl e-crystal Au(100). The epi -
taxi al fi l ms are of hi gh qual i ty and are not rotated wi th
respect to the Au substrate. A questi on that remai ns to
be answered i s how the si gni fi cant l atti ce mi smatch of
4.7% i s accommodated i n thi s epi taxi al system. The
experi mental l y determi ned l atti ce parameter of the
Cu
2
O fi l m (0.426 nm) i s wi thi n experi mental error of
the l i terature val ue for Cu
2
O (0.427 nm),
9
showi ng that
the bul k of the fi l m has not been strai ned i nto commen-
suri sm wi th the substrate. These resul ts do not rul e out
the possi bi l i ty of a strai ned pseudomorphi c Cu
2
O fi l m
growi ng to a very thi n cri ti cal thi ckness before rel axi ng
to the bul k structure. Moni tori ng the growth of the
epi taxi al fi l m i n real ti me wi th a scanni ng tunnel i ng
mi croscope and usi ng cross-secti onal transmi ssi on el ec-
tron mi croscopy shoul d provi de i mportant detai l s about
the i nterface between the two materi al s.
Prel i mi nary resul ts for the el ectrodeposi ti on of Cu
2
O
on the other l ow-i ndex faces of Au reveal that i ni ti al
growth of the fi l m i s epi taxi al wi th no rotati on rel ati ve
to the substrate. However, as the fi l m becomes thi cker,
the ki neti cal l y preferred [100] growth di recti on pre-
domi nates. Thi s shoul d provi de a conveni ent means to
study the i nterpl ay between the thermodynami cs of
epi taxi al growth and the ki neti cal l y preferred growth
di recti on of Cu
2
O. Epi taxi al el ectrodeposi ti on of other
oxi des, such as ZnO,
22
Tl
2
O
3
,
23,24
PbO
2
,
25
and AgO
26
shoul d al so be possi bl e. El ectrodeposi ti on provi des a
si mpl e and i nexpensi ve means for the deposi ti on of hi gh-
qual i ty epi taxi al fi l ms that coul d be used for devi ce
appl i cati ons, wi th our speci fi c i nterest bei ng the Cu/
Cu
2
O l ayered nanostructure system.
13
Acknowledgment. Thi s work was supported by
Offi ce of Naval Research Grant N00014-96-1-0984,
Nati onal Sci ence Foundati on Grants CHE-9816484 and
DMR-9704288, and the Uni versi ty of Mi ssouri Research
Board.
CM990304O
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J . Electrochem. Soc. 1996, 143, 2741.
Figure3. (220) pol e fi gures for (A) Au (2 ) 64.58) and (B)
Cu2O (2 ) 61.34). No other maxi ma are observed i n ei ther
pol e fi gure except for those occurri ng at )45. The pol e fi gure
extends to ) 55.
Figure 4. Azi muthal scans for the (220) refl ecti on of (A) Au
(2 ) 64.58) and (B) Cu2O (2 ) 61.34) both obtai ned at )
45. The expected 4-fol d symmetry i s observed, wi th no
rotati on of the Cu2O fi l m wi th respect to the substrate. The
average fwhm for the Au peaks i s 1.1, whi l e the average for
the Cu2O peaks i s 1.4.
Communications Chem. Mater., Vol. 11, No. 9, 1999 2291