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O F T H E AMERICAN CHEMICAL SOCIETY Regicferrd in L’S PafenfOfJce
@ Copyrighi. 1979. b) fhe American Chemical Society
VOLUME 101, NUMBER17
AUGUST 15, 1979
Phthalocyanine Thin Films as Semiconductor Electrodes Fu-Ren Fan and Larry R. Faulkner* Contribution f r o m the Department of Chemistry, University of Illinois, Urbana, Illinois 61801. Received December 22, 1978
Metal-free, zinc, and nickel phthalocyanines ( H ~ P cZnPc, , and NiPc) have been studied electrochemically. The electrode assemblies involved a glass substrate overlaid by a gold contact layer, which in turn was covered by the phthalocyanine at nominal thicknesses of 40-3000 A. Interfacial capacitances were determined as functions of potential and frequency. Plots of capacitance vs. potential showed sharp rises for potentials more positive than 0.3 V vs. S C E and (for HzPc and ZnPc) peaks at more negative potentials. The capacities were linear with the inverse square root of frequency in the negative potential regime. Cyclic voltammetric studies of six nonlabile complexes of Fe(ll) were carried out. and chronocoulometry was used to measure their standard heterogeneous rate constants. The complexes with very negative standard potentials could be oxidized irreversibly on H2Pc but could not be reduced again. Systems with more positive standard potentials were reversiblq oxidized and reduced. The irreversible systems could be reduced on H2Pc at potentials more negative than 0.35 V vs. S C E when the electrode was irradiated by light at 6328 A. The observations have been rationalized by considering the phthalocyanines as relatively well behaved p-type semiconductor electrodes. Band edges and interfacial states have been mapped and the nature of interfacial charge transfer has been discussed in terms of Gerischer’s model modified by inclusion of surface states in the gap region. Abstract:
The phthalocyanines have received attention recently be- trochemical properties of ZnPc and H2Pc electrodes in solucause several are electrocatalysts for the reduction of molecular tions containing different redox couples are therefore pre~ x y g e n . l The - ~ mechanism of catalysis and the means for op- dictable,20-24provided that the electrode processes are not complicated by additional reactions such as chemisorption. timizing it are of primary interest. A related concern is the ability of solid phthalocyanine Our aim in the present study was to correlate the electrophases to engage as actual electrodes in electrochemical pro- chemical reactivities of several solution species with the relative of their energy levels and the known band edges and cesses. Several recent studies have borne on this p ~ i n t , ~ - ~ . ’ -positions ’~ and there is strong evidence that these materials are capable intermediate levels of phthalocyanine thin-film electrodes. of even reversible charge transfer. The degree to which elec- Metal-free, zinc, and nickel phthalocyanines in evaporated thin trochemical kinetics are influenced by the solid-state physics films have been used as electrodes, and measurements have of conduction in the phthalocyanine phases is largely unknown; been carried out by cyclic voltammetry, chronocoulometry, however, there are a few pertinent experiments. Meier et al. and impedance techniques. A very wide range of behavior has have shown that electrocatalytic activity of polymeric been observed, but virtually all of the results can be understood phthalocyanines correlates with conductivity,x and earlier work within the semiconductor model. from this laboratory showed that electrochemical performance of phthalocyanine electrodes was strongly influenced by am- Experimental Section bient factors controlling conduction.’ Alferov and Sevast’yaTris(3,4,7,8-tetramethyl-l ,IO-phenanthroline)iron( I I ) sulfate nov9 and Meshitsuka and Tamaru’O have reported photo(Fe(TMP)3S04) was obtained from the G . F. Smith Chemical Co. electrochemistry that seems to be based on semiconduction in and was recrystallized from distilled water. Tris(4,7-dimethylthese materials. Possibly related are our earlier observations I ,IO-phenanthroline)iron( II),tris( 1 ,IO-phenanthroline)iron(ll). that the reduction of oxygen is actually inhibited, rather than tris(2,2’-bipyridine)iron(I I ) , and Fe”EDTA were allowed to form being catalyzed, a t thin-film electrodes of zinc and iron directly in electrochemical test solutions by mixing stoichiometric phthalocyanines (ZnPc and FePc).’ W e suggested that the amounts of the ligands and ferrous sulfate. G . F. Smith Chemical Co. inhibitions might be understood by regarding the phthalocysupplied t h e I,l0-phenanthroline (0-ph), 4.7-dimethyl-l , I O phcnanthroline (DMP), and 2,2’-bipyridine (bpy), which were used anine films as p-type semiconductor electrodes with flat-band without further purification. Disodium EDTA was obtained from conditions near 0.0 V vs. SCE. Hach Chemical Co. and was recrystallized from water. Potassium The semiconducting properties of such films were anticiferriand ferrocyanides (reagent grade) were recrystallized twice from pated from reports already in the literature.] More recently, distilled water. The phthalocyanines were purchased from Eastman the properties of ZnPc and metal-free phthalocyanine (H2Pc) Kodak and were used without further treatment. have been illuminated in detail via studies of rectifying propPhthalocyanine thin film electrodes were prepared by evaporation erties and photovoltaic effects a t phthalocyanine/metal A chromium anchor according to the techniques reported earlicr.’~’~ junction^.'^ These materials are indeed p-type semiconductors layer (30-40 A) was first deposited through a mask onto a clean glass with a high density of intermediate energy levels. T k lec.bstrate, then gold at a 400 A thickness was directly overlaid in the 0002-78631791 IS01 -4779$01 .OO/O
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d Potential, Volt
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SCE
Figure 1. The dependence of the cyclic voltammogram for 3.00 mM ferrocyanide on Ii2l'c film thickness. All scans start at -0.4 \i i s . SCE and sweep n t 100 niV/s.
Medium is 1.0 M KNO,.
same pattern. Finally, the phthalocyanine was deposited (in a over the whole assembly.25The portion of the phthalocyanine serving as the electrode proper in electrochemical studies was that which directly overlay a gold disk of 0.20 cm2. The assemblies were stored in vacuo ( 5 1 0 W Torr) until they were to be used. The phthalocyanine electrodes were inserted into the solution only dccply enough to allow immersion of the gold disk. This procedure enabled us to reproduce the effective electrode area to -&IO% A coiled Pt wire was used as an auxiliary electrode. arid a saturated calomel electrode served as a reference. The solution was deaerated by purging with nitrogen, and it was kept under nitrogen during every mcasuremcnt. The pH values of the solutions were kept at 6.0 & 0.2 by adjusting with 1 N K O H or H ~ S O Jif, necesaary. If not otherwise mentioned. the experiments were performed in the dark. Cyclic voltammetric measurements were made with a Princeton Applied Research Model 173 potentiostat and custom-built waveform gcncrator or with a custom-built electrochemical system. Computer-based apparatus like that described earlier was employed for c h r o n o c o u l o ~ n e t r yN. ~o compensation of resistance was attempted. All impedance measurements were carried out with 1 M K N 0 3 electrolyte. The electrical circuit allowed the application of a variable potcntial at the phthalocyanine electrode with respect to the refcrence clcctrode. T h e impedance was measured between this working electrode and a large (-IO cmz) counter electrode. The applied potential was controlled potentiostatically, and the impedance was measured by a General Radio Model 1650A bridge with excitation bb an external a c generator. The apparatus was checked by a dummy cell having a configuration similar to that of the real cell. The quantities and the dissitneasured were the equivalent series capacitance, Cs, pation factor wR,C,, where w is the angular frequency and R, is the cquivalent series resistance. For most svstems. the dissipation factors were much less than unity, but factors on the order of unity were recorded for systems involving thick phthalocyanine films and low excitation frequencies. Impedance measurements were not changed by lifting the counter electrode partially out of the electrolyte; thus the counter electrode did not make significant .contributions to the capacitances reported below.
Results Cyclic Voltammetry. I n deaerated 1.0 M KNO3, cyclic voltammograms a t H l P c electrodes show a flat background response from $0.8 to - 1 .0 V vs. SCE. ZnPc and NiPc have similar working ranges. Figure 1 shows voltammograms of the ferri-/ferrocyanide
couple in 1 M KNO3 at HzPc electrodes having different thicknesses. In general, oxidation occurs readily, but reduction is very slow and cannot be activated by any overpotential in the studied range. The shapes of the voltammograins are essentially unchanged until the H2Pc films become so thin (
