886

250

J. Electrochem. Soc.: E L E C T R O C H E M I C A L S C I E N C E A N D T E C H N O L O G Y

June I978

> 200

Summarizing, we have shown that the photoresponse of the conventional iron thionine system can be e n hanced with a slight modification of the solution. I n addition, an interesting pH dependence was observed. The finding presented here merits f u r t h e r exploration.

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Acknowledgments This work was supported, i n part, by a postdoctoral e n e r g y - r e l a t e d fellowship to J. M. Mountz from the National Science F o u n d a t i o n and the College of N a t u ral Sciences, Michigan State University.
Manuscript submitted Oct. 14, 1977; revised m a n u script received Feb. 13, 1978.

50

I,O

2.0

5.O pH

I 4.0

5.0

6.0

A n y discussion of this paper will appear in a Discussion Section to be published i n the December 1978 JOURNAL. All discussions for the December 1978 Discussion Section should be submitted b y Aug. 1, 1978.

Publication costs o~ this article were assisted by Michigan State University.

REFERENCES 1. G. P o r t e r and M. D. Archer, lnterd~scip. Sci,. Rev., 1, 119 (1976). 2. E. Rabinowitch, J. Chem. Phys., 8, 551, 560 (1940). 3. A. E. Potter, Jr. and L. H. Thaller, Sol. Energy, 3, 1 (1959). 4. L. J. Miller, Tech. Ser. Rep., AD 282, 878, U.S. Dept. of Commerce Washington, D.C. (1962). 5. W. D. K. Clark and J. A. Eckert, Sol. Energy, 17, 147 (1975). 6. D. E. Hall, J. A. Eckert, N. N. Lichtin, and P. D. Wildes, This Journal, 123, 1705 (1976). 7. N. N. Lichtin, in "Photochemical Conversion and Storage of Solar Energy," J. R. Bolton, Editor, Academic Press, New York (1977). 8. J. M. Mountz and H. T. Tien, Sol. Energy, To be published. 9. R. Gomer, Electrochim. Acta, ~(}, 13 (1975).

Fig. 2. The dependence of the photogalvanie response for the solution as a function of pH.

As to w h y the m a x i m u m photopotential should occur around pH 3.4, we have no ready answer, for this p h e n o m e n o n has not been studied. However, it appears that, since the species -TH2 + is generated b y light, it is evident from Eq. [1] that the observed photopotential should depend on the stability of the entity at the electrode surface. Conceivably the acetate ion acting as a ligand can somehow either alter the redox potential of the system or increase the rate of i n t e r facial electron transfer. Additional experiments using a v a r i e t y of ligands are of obvious interest.

Electrochemical Oxidation and Reduction of Thin Films of Prussian Blue

Vernon D. Neff

Department o~ Chemistry, Kent State University, Kent, Ohio 44242

We would like to communicate some interesting prel i m i n a r y results concerning the electrochemical behavior of thin films of P r u s s i a n blue. There are actually two well-characterized forms of P r u s s i a n blue (PB) which have the formulas K F e n I F e II(CN)6 and FenI4[Fen(CN)6]~ (1). The latter compound is prepared from a solution containing a large excess of ferric ion. I n addition to PB itself, two additional, closely related compounds are of interest. These are Everitt's salt K2FenFeII(CN)6, which is colorless, and Berlin Green F e m F e m ( C N ) ~ (2). All three compo~mds have the same basic cubic crystal structure consisting of iron ions bridged b y the cyanide groups, although subtle s t r u c t u r a l modifications m a y occur, depending on the stoichiometry (3, 4). The physical and chemical properties of these compounds have been reviewed by Robin and Day (5). We have discovered a method for preparing thin adherent films of PB on various metal and semiconductor substrates. The particular e x p e r i m e n t we wish to discuss is concerned with a thin PB film on a p l a t i n u m foil electrode. The film is obtained from a solution containing equimolar a m o u n t s of ferric chloride and potassium ferricyanide. A o n e - t o - o n e complex b e t w e e n ferric ion and ferricyanide ions forms
K e y w o r d s : e l e c t r o c h e m i c a l o x i d a t i o n , e l e c t r o c h e m i c a l reduction, ]Prussian b l u e films.

in such solutions (6). The solution must be freshly prepared because the complex will slowly polymerize and e v e n t u a l l y a colloidal precipitate of insoluble Berlin green is formed (7). A fresh ~olution 0.01M i n reagent grade FeC18 9 6H20 and 0.01M i n reagent grade KsFe(CN)6 was prepared in triply distilled water. A 1 cm~ p l a t i n u m foil electrode, with p l a t i n u m lead encased i n Teflon, was cathodized for 1 hr at 1 m A in a 1M HC1 solution. The electrode was placed in the ferric ferricyanide solution and, after several m i n u t e s a b l u e film was formed on the surface. The electrode was removed from the solution and rinsed thoroughly with distilled water. A cyclic v o l t a m m o g r a m of the PB electrode in quiet 1M KC1 solution is shown i n Fig. 1. The v o l t a m m o gram was obtained with a PAR Model 173 potentiostat equipped with a Model 175 voltage programmer. The interesting feature of this v o l t a m m o g r a m is that on the anodic side of the sweep (0.6V vs. SCE) the electrode is bright blue, whereas on the cathodic side (0.0V vs. SCE) it is colorless. F u r t h e r m o r e it is possible to switch rapidly b e t w e e n the blue and colorless states with the selecting switch on the potentiostat. The electrode reaction evidently occurs i n the film itself and corresponds to the u l t i m a t e reduction of PB to the colorless "Everitt's salt."

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VoL 125, No. 6

PRUSSIAN BLUE THIN FILMS

887

the simultaneous o x i d a t i o n of chloride ion and the f o r m a t i o n of s u r f a c e oxide on t h e p l a t i n u m . The details of these electrochemical reactions are c u r r e n t l y u n d e r investigation. M a n u s c r i p t s u b m i t t e d Sept. 29 1977; r e v i s e d m a n u s c r i p t r e c e i v e d Dec. 1, 1977.
m

E E

g
D 0

A n y discussion of this p a p e r will a p p e a r in a Discussion Section to be p u b l i s h e d in t h e D e c e m b e r 1978 JOURNAL. A l l discussions for the D e c e m b e r 1978 Discussion Section should be s u b m i t t e d b y Aug. 1, 1978.

Publication costs o~ this article were assisted by Kent State University.

.5 .4 ,3 .2
( V v s SCE)

.1

POTENTIAL

Fig. 1. Single sweep voltammogram of a thin film of Prussian blue on platinum foil in 0.1M KCI solution. The scan rate is 10 mV/sec.

A second o b s e r v a t i o n is concerned w i t h t h e o x i d a tion of the PB film at m o r e anodic potentials. A t a p o t e n t i a l of a p p r o x i m a t e l y 1.0V vs. SCE the film becomes green. I n this case the film has a p p a r e n t l y b e e n oxidized to B e r l i n green. A g a i n the color can be switched r a p i d l y b e t w e e n blue and g r e e n b u t t h e film begins to d e t e r i o r a t e after s e v e r a l cycles p r e s u m a b l y because of

REFERENCES 1. D. Davidson a n d L. A. Welo, J. Phys. Chem., 3~, 1191 (1928). 2. J. F. Duncan and P. W. R. Wigley, J. Chem. Soc., 1120 (1963). 3. J. F. K e g i n and F. D. Miles, Nature (London), 137, 577 (1~36). 4. A. Ludi and H. U. Gudel, Struct. Bonding (Berlin) 14, 1 (1973). 5. M. B. Robin and P. Day, Adv. Inorg. Chem. Radiochim., 10, 247 (1967). 6. J. A_. Ibers ~nd N. Davidson, J. Am. Chem. Soc., 73, 476 (1961). 7. D. E. Knapp, Ph.D. dissertation, K e n t S t a t e U n i versity, Kent, Ohio (1966).

DISCUSSION SECTION
T h i s Discussion S e c t i o n includes discussion of p a p e r s a p p e a r i n g in t h e J o u r n a l o f T h e ELectrochemical S o c i e t y , Vol. 124, No. 7, 9, and 12, J u l y , S e p t e m b e r , a n d D e c e m b e r 1977.
I~ ~ ......

Fabricating Patterns in Tin Oxide Film by Electrochemical Reaction B. J. Baliga and S. K. Ghandhi (pp. 1059-1060, Vol. 124, No. 7)

L F. Chang:l The t e c h n i q u e of f a b r i c a t i n g p a t t e r n s of tin oxide films b y electrochemiceal reaction has also been d e v e l o p e d in our laboratory. 2 We h a v e found t h a t the o v e r - a l l etching r a t e of tin oxide film is not significantly d e p e n d e n t on the concentration of HC1 in w a t e r as shown b y Baliga e~ al.3 However, w e w o u l d like to point out an i m p o r t a n t fact concerning the selection of a critical HC1 concentration. Since the o v e r - a l l etching process consists of two consecutive steps: (i) electrochemical r e d u c t i o n of tin oxide to tin (the d a r k coloration of m e t a l tin can be dir e c t l y observed d u r i n g t h e etching and a n a l y z e d b y i n t e r r u p t i n g the etching process); and (ii) etching of tin b y HC1, it is necesary to select the e l e c t r o l y t e composition such t h a t t h e r e d u c t i o n r a t e of t i n oxide (step i) is h i g h e r t h a n the etching r a t e of tin m e t a l (step ii). This selection g u a r a n t e e s that all the detail p a t t e r n s to be etched a r e etched a w a y w i t h no electrically isolated oxide regions formed on ~he glass substrate. We h a v e found that, for achieving best etching results, the concentration of HCI in w a t e r should be a p p r o x i m a t e l y 7%. A n etched p a t t e r n w i t h resolution on the o r d e r of 20 ~m is shown in Fig. i.
I IBM T h o m a s J. W a t s o n R e s e a r c h C e n t e r , Y o r k t o w n H e i g h t s , N e w Y o r k 10598. I. F. C h a n g , W. P. H o r n b e r g e r , a n d H. H. T a u b , IBM T e c h . Disclosure Bull., 16, 3463 (1974). ~B. J. B a l i g a a n d S. K. G h a n d i , This Journal, 124, 1059 (1977).

Fig. I. Etched pattern in tin oxide film on glass substrate by electrochemical reaction technique (the ruler indicates 0.05 mm per division).

During the course of our work, w e have also discovered some p r i o r a r t in the p a t e n t l i t e r a t u r e 4,5 d e scribing g e n e r a l m e t a l oxide etching b y e l e c t r o c h e m i cal reaction.
B. J. Baliga a n d S. K. Ghandhi:6 W e a g r e e w i t h Chang t h a t b e t t e r etching can b e achieved b y ensuring
R. F. S h a w , US P a t . 3,507,759 (1970). 5 R. E. Szupillo, US P a t . 3,616,349 (1971). General Electric Corporate Research & Development, Schenect a d y , N e w Y o r k 12309.

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