6598 Langmuir 1999, 15, 6598-6600
Electrochemically Active Surface Zirconium
Complexes on Indium Tin Oxide
Susan K. VanderKam, Ellen S. Gawalt,
Jeffrey Schwartz,* and Andrew B. Bocarsly*
Department of Chemistry, Princeton University, Princeton,
New Jersey 08544-1009
Received January 28, 1999. In Final Form: May 11, 1999
Indium tin oxide (ITO) is a common transparent
conductor1 which is widely used as an electrode material
in, for example, organic light-emitting diode2-4 (OLED)
displays. It is generally acknowledged3,5-8 that inefficient
carrier injection from an ITO electrode into an organic
layer of an OLED can lead to device failure; it may be that
appropriate surface modification of ITO can be ac-
complished to enhance such carrier injection and, con-
sequently, device performance. Commercial ITO is usually
characterized1 according to its physical parameters,
including surface resistance, grain size, direct optical band
gap, and etch capabilities, but not by its chemical ones.
Indeed, despite the large number of reports concerning
device use of ITO,3,5-8 only few studies have focused on a
possibly key issue of ITO surface chemistry: surface
hydroxyl group density. It seems unlikely that interface
design involving these surface OH groups can be optimized
for device applications until this simple aspect of the
surface chemistry of ITO, at least, is better described.
Attachment of ferrocenyl compounds onto ITO via a
silyl9,10 or alkanecarboxylic acid tethering functionality11
has been reported as a method both to enhance the
electrochemical performance of ITO and to determine the
number of electrochemically reactive sites bound per
nominal unit area of ITO. Self-assembly of ferrocenylpyr-
role and -thiophene derivatives through hydrogen bonding
with surface OH groups has also been described.12 In each
case, electrochemical determinations indicated surface
coverage of ferrocenyl groups to be on the order of 10-10
mol/cm2 (attributed to a “monolayer”10,11). However, the
surface density of reactive OH functionality on the ITO
could not be estimated using these systems, since no
information is available on the stoichiometry of the
reaction between such functionality and the derivatization
reagents.
(1) Chopra, K. L.; Major, S.; Pandya, D. K. Thin Solid Films 1983,
102, 1-46.
(2) Tang, C. W.; VanSlyke, S. A. Appl. Phys. Lett. 1987, 51, 913-915.
(3) Forrest, S. R.; Burrows, P. E.; Thompson, M. E. In Laser Focus
World; PennWell Publishing Company: Tulsa, OK, 1995; Vol. 31, pp
99-107.
(4) Burrows, P. E.; Gu, G.; Bulović, V.; Shen, Z.; Forrest, S. R.;
Thompson, M. E. IEEE Transactions on Electron Devices; Institute of
Electrical and Electronics Engineers: New York, 1997; Vol. 44, pp 1188-
1203.
(5) Greenham, N. C.; Moratti, S. C.; Bradley, D. D. C.; Friend, R. H.;
Holmes, A. B. Nature 1993, 365, 628-630.
(6) Gautier, E.; Lorin, A.; Nunzi, J. M.; Schalchli, A.; Benattar, J. J.;
Vital, D. Proc. SPIEsInt. Soc. Opt. Eng. 1997, 3002, 104-107.
(7) Scott, J. C.; Carter, S. A.; Karg, S.; Angelopoulos, M. Proc. SPIEs
Int. Soc. Opt. Eng. 1997, 3002, 86-91.
(8) Antoniadis, H.; Miller, J. N.; Roitman, D. B.; Cambell, I. H. IEEE
Trans. Electron Devices 1997, 44, 1289-1294.
(9) Chen, K.; Herr, B.; Singewald, E. T.; Mirkin, C. A. Langmuir
1992, 8, 2585-2587.
(10) A similar study has been done for a cobalt complex. See, Herr,
B.; Mirkin, C. A. J. Am. Chem. Soc. 1994, 117, 6927-6933.
(11) Gardner, T. J.; Frisbie, C. D.; Wrighton, M. S. J. Am. Chem. Soc.
1995, 117, 6927-6933.
(12) Zotti, G.; Schiavon, G.; Zecchin, S.; Berlin, A.; Pagani, G.;
Canavesi, A. Langmuir 1997, 13, 2964-2968.
10.1021/la990086d CCC: $18.00 © 1999 American Chemical Society
Published on Web 07/13/1999
We have previously exploited the reactivity of surface
OH groups of metal oxides for surface functional group
quantification and modification using organometallic
reagents,13-16 and we have reported that bonding of
carboxylic acids to oxide surfaces can be stabilized using
zirconium alkoxide complex-derived interfaces.16,17 Be-
cause of the ease of ligand metathesis in these surface-
bound alkoxides, they represent a versatile interface for
formation of families of surface-bound materials from a
common, easy-to-prepare precursor.16,18,19 We now report
that these synthetic methodologies can be used to bond
a simple, electrochemically active ferrocenecarboxylate
derivative to the ITO surface via ligand metathesis at Zr
in a process that obviates tedious tethering group synthesis
and attachment. Happily, we find that the Zr complex
interface does not deleteriously affect the electrochemical
behavior of the ligated ferrocenecarboxylate species.
Importantly, because the stoichiometries of Zr complex
surface chemisorption and subsequent ligand metathesis
are known, electrochemical quantitation of surface com-
plex-bound ferrocenecarboxylate ligand groups provides
an indirect measure of ITO surface OH coverage.
Experimental Part
Reagents. ITO-coated (one side only) glass slides (Delta
Technologies) had a resistance <20.3 Ω/0. Tetra(tert-butoxy)-
zirconium (1, Aldrich) was vacuum distilled and stored under
nitrogen prior to use. Diethyl ether or THF was dried by
distillation from sodium benzophenone ketyl. Dry acetonitrile
(AN) was distilled from CaH2. All other reagents were used
without further purification, unless stated otherwise.
Cleaning Protocol for ITO-Coated Glass Slides.20 Slides
were cleaned first by ultrasonication in a solution of Contrad 70
detergent (Fisher) for 30 min. They were rinsed copiously with
deionized H2O and then rinsed again three times each in boiling
trichloroethylene, acetone, and boiling methanol. The cleaned
slides were dried at 250 °C overnight and were stored in a
desiccator prior to use.
Construction of ITO Electrodes. ITO-coated glass was cut
into 1 cm × 1.5 cm rectangles. Copper wire (20 gauge) was
attached to the top of each ITO side using single-component silver
epoxy (Epo-Tek, H31), and the ensemble was cured overnight at
250 °C. The Cu-wire/ITO junction and the top 0.5 cm2 of the slide
were covered with regular epoxy, leaving an active electrode
area of 1 cm2.
Preparation of [ITO]-[O]x-Zr(tert-butoxy)4-x (as a mix-
ture of 2 and 2′). Cleaned ITO-coated glass slides were exposed
to vapor of 1, as previously described, to give 2/2′ (see Scheme
1; IR: νC-H ) 2973 cm-1).17
Preparation of Ferrocenecarboxylate Derivatives 3 and
3′. ITO electrode samples of 2/2′ were dipped in a 10-3 M solution
of ferrocenecarboxylic acid (FcCOOH; Aldrich) in dry diethyl ether
under an inert atmosphere for 30 min and then rinsed thoroughly
to give 3/3′. Alternatively a 1 mM solution of FcCOOH in diethyl
ether was sprayed onto 2/2′ using N2; the solvent was then
removed by evacuation. The sample was then washed once by
(13) Miller, J. B.; Schwartz, J.; Bernasek, S. L. J. Am. Chem. Soc.
1993, 115, 8239-8247.
(14) Miller, J. B. Princeton University, 1992.
(15) Miller, J. B.; Schwartz, J. Inorg. Chem. 1990, 29, 4579-4581.
(16) Aronoff, Y. G.; Chen, B.; Lu, G.; Seto, C.; Schwartz, J.; Bernasek,
S. L. J. Am. Chem. Soc. 1997, 119, 259-262.
(17) VanderKam, S. K.; Bocarsly, A. B.; Schwartz, J. Chem. Mater.
1998, 10, 685-687.
(18) Purvis, K. L.; Lu, G.; Schwartz, J.; Bernasek, S. L. Langmuir
1998, 14, 3720-3722.
(19) VanderKam, S. K.; Lu, G.; Bernasek, S. L.; Schwartz, J. J. Am.
Chem. Soc. 1997, 119, 11639-11642.
(20) Burrows, P. E.; Shen, Z.; Bulović, V.; McCarty, D. M. J. Appl.
Phys. 1996, 79, 7991-8006.
Notes
Scheme 1. Reaction of ITO-Surface-Bound Zr
Alkoxides with FcCOOH
dipping into ether for 10 min to remove physisorbed FcCOOH,
and solvent was then removed in vacuo. DRIFT spectra were
recorded using a Nicolet 730 spectrometer.
Cyclic Voltammetric and Chronocoulometric Studies
of 3/3′. ITO electrodes coated with 3/3′ were tested electrochemi-
cally using a PAR 173 potentiostat equipped with a PAR 175
universal programmer and an X-Y recorder. The electrolyte
employed consisted of 0.1 M tetrabutylammonium perchlorate
(TBAP, Sachem) either in AN or in ethanol. A Ag/AgNO3 ref-
erence electrode and a large area Pt foil counter electrode
completed the cell configuration. All potentials are reported
versus SCE. Chronoamperometry was conducted at a constant
potential of 0.70 V versus SCE.
Results and Discussion
Surface-hydroxylated ITO on glass slides were first
treated with vapor of 1 to give [ITO]-[O]x-Zr(tert-
butoxy)4-x (2/2′).16 The slides then either were dipped into
a 10-3 M solution of FcCOOH (in Et2O or THF for about
5 min) and dried, or were sprayed with an aerosol of a 1
mM solution of FcCOOH in ether, dried, washed, and dried
again to give 3/3′ (Scheme 1, Figure 1). DRIFT analysis
of 3/3′ showed peaks attributed to the ferrocenecarboxylate
ligand at 1486 (m), as well as those at 1513 and 1400
cm-1, indicative of νasym and νsym of the zirconium car-
boxylate functionality.16 Smaller signals indicative of
tert-butoxy ligands were also noted at 2962 and 2926
cm-1. In a control experiment, reaction of ITO with a
solution of FcCOOH gave a material that showed a small
peak at 1486 cm-1 and also stronger peaks at 1169 and
1242 cm-1, but no absorption in the 1400-1500 cm-1 region
was noted (Figure 1).
Langmuir, Vol. 15, No. 19, 1999 6599
Figure 1. DRIFT spectra of 3 and 3′ compared with the product
of simple deposition of FcCOOH onto ITO, followed by solvent
wash.
The stoichiometry of deposition of 1 onto ITO in
ultrahigh vacuum (UHV) was found21 to be similar to that
on other oxide surfaces examined.13,16,18,22,23 Chemisorption
involves protolytic loss of primarily one tert-butoxide
ligand to give 2; a small amount of 2′, formed from a second
protonolysis step, may also be present at room temperature
(by XPS: C/Zr [≈300 K] ) 12.7; [≈430 K] ) 10.1; for 2,
expected C/Zr ) 12; for 2′, expected C/Zr ) 8)21 (Scheme
1). Reaction of analogues of either 2 or 2′ with carboxylic
acids gives dicarboxylates (3 and 3′, respectively; Scheme
1);18 apparently, reaction of species such as 3 with a third
equivalent of carboxylic acid is sterically unfavorable.18
Treated ITO electrodes coated with 3/3′ were rinsed
thoroughly to remove any weakly adsorbed FcCOOH. The
modified electrodes were then subjected to electrochemical
analysis to verify the presence of surface-bound ferrocen-
ecarboxylate derivatives and to ascertain their surface
loading. Cyclic voltammograms (CVs) of 3/3′-modified and
uncoated control electrodes were obtained in both AN/
TBAP and ethanol/TBAP electrolyte. The CV of the 3/3′-
modified ITO electrode showed a redox peak with E1/2 )
+0.55 V versus SCE (Figure 2a), which is reasonable for
a surface-bound carboxyferrocene derivative.11,24 The CV
of an unmodified electrode showed no redox activity in
the potential window of interest (Figure 2b). The proposal
that the ferrocenecarboxylate species is chemically bound
to the surface was substantiated by scan rate dependence
studies, which were done in an ethanol 0.1 M TBAP
electrolyte. The peak current was found to be linear with
scan rate (Figure 3), indicative of a surface-bound redox
active species.25,26 The peak-to-peak separation varied from
100 to 180 mV over the scan rate range 5-500 mV/s (Figure
3). These values differ from the zero peak-to-peak separa-
tion (independent of scan rate) theoretically predicted for
an ideal surface-confined redox couple.27 However, this
response is comparable to values measured for other ITO-
bound Fc systems.12 In part, the observed peak-to-peak
separation can be attributed to the relatively high
(21) Purvis, K. L.; Lu, G.; Schwartz, J.; Bernasek, S. L. Unpublished.
(22) Miller, J. B.; Bernasek, S. L.; Schwartz, J. J. Am. Chem. Soc.
1995, 117, 4037-4041.
(23) Lu, G.; Purvis, K. L.; Schwartz, J.; Bernasek, S. Langmuir 1997,
13 (3), 5791-5793.
(24) Wrighton, M. S.; Palazzotto, M. C.; Bocarsly, A. B.; Bolts, J. M.;
Fischer, A. B.; Nadjo, L. J. Am. Chem. Soc. 1978, 100, 7264.
(25) Laviron, E. J. Electroanal. Chem. 1979, 100, 263-270.
(26) Hubbard, A. T.; Anson, F. C. In Electroanalytical Chemistry;
Bard, A. J., Ed.; Marcel Dekker: New York, 1970; Vol. 4, pp 130-214.
(27) Laviron, E. J. Electroanal. Chem. 1981, 122, 37-44.
6600 Langmuir, Vol. 15, No. 19, 1999
Figure 2. (a) Cyclic voltammogram of 3/3′, measured in 0.1
M TBAP/acetonitrile at 100 mV/s. (b) Control cyclic voltam-
mogram of an untreated ITO electrode, measured in 0.1 M
TBAP/acetonitrile at 100 mV/s.
Figure 3. Scan rate dependence studies for oxidation of 3/3′,
measured in 0.1 M TBAP/ethanol.
resistance of the ITO electrode. However, the breadth of
the cyclic voltammetric waves, along with the nonlinear
dependence of the peak-to-peak separation, argues for a
combination of repulsive nearest neighbor interactions
and sluggish interfacial charge transfer.27 In a control
experiment, an ether solution of FcCOOH was sprayed
Notes
onto an ITO electrode. Solvent was removed, and the
electrode was washed and then analyzed by cyclic vol-
tammetry. No Faradaic current waves were observed. On
the basis of this measurement, there cannot be more than
10-12 mol/cm2 (our limit of detection) of ferrocene directly
attached to the ITO electrode. Apparently, therefore, the
Zr complex interface is required to ensure measurable
ferrocenecarboxylate attachment to the ITO surface.
The loading density of surface-bound ferrocenecarboxy-
late ligands of 3/3′ on ITO was determined by chrono-
coulometry.28 Curves obtained from each chronoamper-
ometric scan were integrated to obtain total charge (QT),
and an unmodified ITO electrode was used to determine
the interfacial capacitance charge at ITO for the analyzed
solution (Qc). The coverage of surface-confined ferrocen-
ecarboxylate ligands (Γ) on the ITO was then determined
according to eq 128 to be 1.01 × 10-10 mol/cm2. Integration
of the CV traces with respect to time gave comparable
values. Assuming that there are two ferrocenecarboxylate
carboxylate ligands in 3/3′,23 then the amount of 3/3′ on
the surface, per nominal unit area, is about 5 × 10-11
mol/cm2, comparable to the amount obtained by “self
assembly” of elaborated ferrocenyl derivatives.9-12 onto
ITO. These cyclic voltammetry studies show that the redox
properties of the FcCOOH-derived reagent have not been
significantly changed by its incorporation into a surface
Zr carboxylate complex: Apparently, the surface Zr(IV)
complex does not constitute an insulating barrier.
Q T Qc
Γ) - (1)
nF nF
We had previously demonstrated that attachment of
alkanecarboxylic acids to oxide surfaces could be stabilized
against removal by evaporation or solvent wash-off by
using zirconium alkoxide complex-derived interfaces.16,17
We had also shown that a variety of ligand types can be
introduced subsequently into the coordination sphere of
the Zr by simple exchange of residual tert-butoxy ligands
with a variety of carboxylic acids and phenols.16,18,19 Thus,
because 2 is easy to prepare, and because it is subject to
ligand exchange with a variety of species, this methodology
is versatile for rapid and variable surface modification of
ITO electrodes.
Acknowledgment. The authors thank Dr. Clark
Chang and Mr. David Watson for assistance with obtaining
electrochemical data. They also acknowledge financial
support from the National Science Foundation (to J.S.)
and the Department of Energy (to A.B.B.).
LA990086D
(28) Here, F ) 96 487 C/eq; n ) the number of electrons involved in
the electrode reaction (for Fc f Fc+, n ) 1); and Γ ) quantity of adsorbed
reactants in moles. Anson, F. C.; Osteryoung, R. A. J. Chem. Educ.
1983, 60, 293-296.