346 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 F e b r u a r y 1987

sul t i n g fluxes are m u c h smaller. F i g u r e 2 s h o w s the re-
sult of c o m b i n e d sodium and potassium fluxes.)
The ion selectivity of a channel is usually considered in
t e r m s of a t i g h t filter, or b o t t l e n e c k , that d i s c r i m i n a t e s
largely on the basis of ion size, although factors such as
ionic h y d r a t i o n and polarizability in f lu e n c e the p r o cess
(2). This way of t h i n k i n g leads to the p a r a d o x of a con-
stricted pathway with a relatively large ionic conduct-
ance. (There is no correlation b e tw e e n ion selectivity and
the conductance.) The high rate of ion flow t h r o u g h the
s e l e c t i v e c h a n n e l s of e x c i t a b l e m e m b r a n e s , w h i c h in
some cases is not m u c h lower than the rate in free solu-
tion (2), is i n c o m p a t i b l e with a bottleneck type of selec-
tive channel. Also, the selectivity is unusual in that lith-
ium passes t h r o u g h the fast c h a n n e l almost as rapidly as
sodiu m , and t h e p o t a s s i u m c h a n n e l allows t h e larger
thallium ion to pass t h r o u g h at almost twice the rate. It is
a p p a r e n t that ion selectivity is m u c h m o r e c o m p l e x than
simple filtration. In the SCM, the selectivity arises
l a r ge l y from the k i n e t i c s of c h a n n e l o p e n i n g and is
influenced by various electrical double layer properties.
At the basis of all of the m e m b r a n e channel effects is the
r e l a t i v e s p eed w i t h w h i c h e l e c t r i c a l c h a n g e s can be
m a d e c o m p a r e d to chemical changes.
The i m p o r t a n c e of k i n e t i c p a r a m e t e r s in u n d e r s t a n d -
ing m e m b r a n e p r o p e r t i e s is u n d e r s c o r e d by th e r e c e n t
a p p l i c a t i o n of s i n u s o i d a l electric fields to the s o d i u m
c h a n n e l as d e s c r i b e d by t h e SCM (10). T h e c a l c u l a t e d
c o n c e n t r a t i o n c h a n g e s of t h e ions in the e l e c t r i c a l dou-
ble layer regions (i.e., t h e surface c o m p a r t m e n t s ) are
m a x i m a l at frequencies that are close to t h o se that have
b e e n observed. This indicates that the kinetic m e m b r a n e
parameters are good estimates of real properties and that
t h e y are n e e d e d to d e s c r i b e the t r a n s i e n t r e s p o n s e s of
m e m b r a n e s to c o m p l e x electrical signals.
Acknowledgments
Th e w o r k d e s c r i b e d in this p ap er was s u p p o r t e d by
C o n t r a c t N00014-83-K-0043 from the Office of Naval
Research.
Manuscript su b m i t t ed Feb. 7, 1986, revised m a n u s c r i p t
received May 19, 1986.
REFERENCES
i. A. L. Hodgkin and A. F. Huxley, J. Physiol. (London),
117, 500 (1952).
2. B. Hille, "Ionic Channels in Excitable Membranes,"
Sinauer, Inc., Sunderland, MA (1984).
3. M. Blank and J. S. Britten, Bioelectrochem. Bioenerg.,
5, 528 (1978).
4. M. Blank and W. P. Kavanaugh, ibid., 9, 427 (1982).
5. M. Blank, ibid., 10, 451 (1983).
6. M. Blank, ibid., 13, 93 (1984).
7. M. Blank, J. Theor. Biol., 51, 127 (1975).
8. M. Blank, Bioelectrochem. Bioenerg., 9, 615 (1982).
9. M. Blank, W. P. Kavanaugh, and G. Cerf, ibid., 9, 439
(1982).
10. M. Blank, and J. N. Blank, This Journal, 133, 237 (1986).

Electrochemistry of Aromatic Polyimides

Stephen Mazur, Paul S. Lugg, and Chaim Yarnitzky 1
Central Research and Development Department, E. I. du Pont de Nemours and Company, Experimental Station,
Wilmington, Delaware 19898

ABSTRACT
Polyimides derived from condensation of pyromellitic dianhydride with various diamines have been shown to be
electrochemically active. Films of these materials coated on the surface of solid electrodes, immersed in electrolyte solu-
tions of dipolar aprotie solvents undergo two distinct reversible redox processes, involving addition of one or two elec-
trons per repeat unit. These processes can be carried out completely and stoichiometrically for films as thick as 20 ~m.
Spectrophotometric studies and comparison with model compounds lead to the following conclusions: (i) ion permeabil-
ity, which is a necessary component of the electrochemical charging and discharging processes, is related to solvent swell-
ing and is, in turn, strongly influenced by the physical history of the polymer, (ii)redox activity involves localized molecu-
lar electronic states of the pyromellitic diimide group, (iii) there is no evidence for electronic interactions between
pyromellitimide groups along a given polymer chain, and (iv) spectroscopic evidence indicates that weak interactions
within the bulk of the polymer give rise to detectable inhomogeneities in optical or electrochemical properties of individ-
ual functional groups as a function of the charge on groups in their environment.

P o l y i m i d e s are c o m m e r c i a l l y i m p o r t a n t m a t e r i a l s
u s e d e x t e n s i v e l y as dielectric films and coatings in a
wide range of electrical applications (1). The most famil-
iar and b e s t - s t u d i e d e x a m p l e is the p o l y m e r d e r i v e d
f r o m p y r o m e l l i t i c d i a n h y d r i d e and 4,4'-oxydianiline,
PI(ODA). C o m m e r c i a l applications for this material gen-
erally require high t e m p e r a t u r e stability, high electrical
r e s i s t i v i t y and d i e l e c t r i c strength, low d i e l e c t r i c con-
stant, and low permeability towards ions. Notwithstand-
ing these generally recognized properties, it has recently
b e e n d e m o n s t r a t e d that the same m a t e r i a l can be m a d e
to t r a n s p o r t both ions and e l e c t r o n s at significant rates
u n d e r certain combinations of conditions (2, 5, 6).
Two factors are responsible for these conflicting char-
acteristics. First, t h e a r o m a t i c d i i m i d e g r o u p can func-
t i o n as an e l e c t r o n acceptor, u n d e r g o i n g two i n d e p e n -
d e n t o n e - e l e c t r o n r e d o x r e a c t i o n s m u c h like a q u i n o n e .
Second, the p o l y m e r is prepared by what a m o u n t s to
solid-state ch em i s t r y and has a very high glass transition
t e m p e r a t u r e . C o n s e q u e n t l y , such physical properties as
solvent swelling and ion permeability are sensitive to the
t h e r m a l and c h e m i c a l h is t o r y of the s a m p l e and can be
v a r i e d rather dramatically. The p r e s e n t report c o n c e r n s
an i n v e s t i g a t i o n of t h e s e p r o c e s s e s u si n g e l e c t r o c h e m i -
cal and spectroscopic methods.
The r e d o x p r o p e r t i e s of p o l y i m i d e s w e r e first recog-
n i zed by H a u s h a l t e r and K r a u s e (2), who r e p o r t e d reac-
tions of K a p t o n | film (a c o m m e r c i a l f o r m of PI(ODA))
w i t h a family of i n o r g a n i c r e d u c i n g agents (main g r o u p
metal-cluster anions, so-called Zintl ions). These authors
observed that Kapton | films immersed in
e t h y l e n e d i a m i n e solutions of t h e Zintl salts K4Sn9 or
K4SnTe4 r a p i d l y c h a n g e d from t h e n o r m a l y e l l o w - g o l d
color to dark g r e e n or purple, r e s p e c t i v e l y . T h e y
identified these colored species based on a c o m b i n a t i o n
of spectroscopic and chemical evidence as the radical an-
ion, PI(ODA)-, and dianion, PI(ODA) -2, states of the orig-
inal p y r o m e l l i t i m i d e group (scheme 1). The reaction was
v i e w e d as a c o m b i n a t i o n of e l e c t r o n t r a n s f e r from the
Zi n t l an i o n to t h e p o l y m e r with " i n t e r c a l a t i o n " of K §
c o u n t e r i o n s into t h e film. Th ei r a t t e m p t s to o b s e r v e t he
e q u i v a l e n t p r o c e s s e s u si n g e l e c t r o c h e m i c a l m e t h o d s
were apparently unsuccessful (3).
_ N-- *~ --N N-- 9 IL - - N ~ N-- Scheme 1

tOn leave from the Department of Chemistry, Technion-Israel

Institute of Technology, Haifa 3200, Israel. Pl Pl- Pl'a

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 Vol. 134, No. 2 AROMATIC POLYIMIDES 347

The initial objective of the present work was to under- Table I. Cyclic voltammetry of polylmides
stand the e l e c t r o n t r a n s p o r t properties of PI(ODA) and, (0.10 KPFJacetonitrile)
particularly, the distinction b e t w e e n c h e m i c a l and elec- E~
t r o c h e m i c a l r ed u ct i o n conditions. It was discovered that
e l e c t r o c h e m i c a l r e d u c t i o n can be a c h i e v e d for s u i t a b l y SCE)
p r e p a r e d p o l y i m i d e films. By studying the electrochem- " ~ ,,(00,) -0.73 -1.13
istry and optical absorption spectra for a representative
range of p o l y i m i d e s and c o m p a r i n g their properties with
t h o s e of mode] small m o l e c u l e s , it has b e e n p o s s i b l e to
a n s w e r s o m e basic q u e s t i o n s c o n c e r n i n g t h e n a t u r e of
'
t he e l e c t r o n i c states and m e c h a n i s m of e l e c t r o n trans-
port. The i m p o r t a n t role of ion transport and its relation PI(p-PD) -0.74 -1.12
to th e p h y s i c a l and c h e m i c a l state of the p o l y m e r have
also b e e n e x p l o r e d , h o w e v e r , our u n d e r s t a n d i n g of this
subject r em ai n s c o m p a r a t i v e l y less complete.
Results r e p o r t e d here are of potential relevance for ap- 0
plications of polyimides. For example, the kinds of elec-
P,(m-PO) -0.71 -1 10
t r o c h e m i c a l p h e n o m e n a described here may be i n v o l v e d
in c a p a c i t i v e polarization p h e n o m e n a (4). Moreover, t h e
s i m u l t a n e o u s transport of ions and electrons can provide
t ota l l y n e w ways to e x p l o i t or m o d i f y the material. An
e x a m p l e is the r e c e n t d e v e l o p m e n t of an e l e c t r o d e p o s i - (3 O ~'~"~ CH3
tion process for growing thin metallic interlayers within
N N P,<.so) -o.73 -112
a p o l y i m i d e film (5, 6).

Experimental
Materials.--Starting r e a g e n t s w e r e o b t a i n e d from
c o m m e r c i a l s o u rces and f u r t h e r purified as follows. Di-
a m i n e s w e r e t w i c e s u b l i m e d , as was p y r o m e l l i t i c
dianhydride. Phthalic a n h y d r id e was recrystallized from
acetic a n h y d r i d e and then v a c u u m dried. Solvents, N,N'-
d i m e t h y l f o r m a m i d e (DMF), N, N ' - d i m e t h y l a c e t a m i d e
(DMAc), and N - m e t h y l p y r o l i d o n e w e r e d i s ti ll e d over
CaH~. A c e t o n i t r i l e (AN) ( F i s c h e r s p e c t r o p h o t o m e t r i c
grade) was stored o v e r a c t i v a t e d m o l e c u l a r sieves and
filtered p ri o r to use. T h e p o l y a m i c acid of p y r o m e l l i t i c
d i a n h y d r i d e with 4 , 4 ' - d ia m in o d ip h e n y le th e r was kindly
p r o v i d e d by Dr. J. A. Kreuz, P o l y m e r P r o d u c t s Depart-
m e n t , E. I. du P o n t de N e m o u r s a n d C o m p a n y ,
Circleville, Ohio (DMAc solution, i n h e r e n t viscosity 1.35
dl/g). N e s a t r o n , i n d i u m / t i n - o x i d e - c o a t e d glass was ob-
tained from P P G Industries, Pittsburgh, Pennsylvania.
Synthesis and characterization.--4,4'- Diamino-2,2'-
b i p y r i d i n e was s y n t h e s i z e d a c c o r d i n g to th e p r o c e d u r e
of N e c k e r s (7). Th e b i s - p h t h a l i m i d e s w e r e p r e p a r e d as
follows: to 4 ml of DMAc was a d d e d 0.10 mol of the diam-
ine, w i t h stirring. P h t h a l i c a n h y d r i d e (0.25 mol) was
a d d e d to t h e solution, and stirring was c o n t i n u e d for
0.5h. Finally, 1 m l of acetic a n h y d r i d e and 1 ml of pyri-
dine w e r e a d d e d and the r e s u l t i n g s o l u t i o n stirred u n t i l
t he p r o d u c t had s e p a r a t e d as a p r e c i p i t a t e . T h e crystals
were suction filtered and washed with ether.
N , N ' - d i ( p h e n o x y p h e n y l ) p y r o m e l l i t i m i d e and N ,N '-
d i a m y l p y r o m e l l i t i m i d e w e r e p r e p a r e d s i m il a r l y using
2.1 m o l a r e q u i v a l e n t s of the p r i m a r y a m i n e per m o l e of
pyromellitic dianhydride. The identity and purity of the
p r o d u c t s w e r e c o n f i r m e d by high r e s o l u t i o n mass
s p e c t r o m e t r y and el e m e n t a l analyses (C, H, and N).
P o l y a m i c acids c o r r e s p o n d i n g to the p o l y i m i d e s sum-
m a r i z e d in T ab l e I w e r e p r e p a r e d as follows: one m o l a r
e q u i v a l e n t of the diamine was a d d e d to DMAc with stir-
ring. 1.02 molar equivalents of pyromellitic d i a n h y d r i d e
w e r e a d d e d slowly o v e r a 0.5h p e r i o d w i t h stirring. The
r e s u l t i n g s o l u t i o n was c a l c u l a t e d to be 10% solids by
w e i g h t . I n h e r e n t v i s c o s i t i e s r a n g e d f r o m 0.30 (0.5% in
DMAc) to 2.6 dl/g. These solutions were spin coated onto
c a t ho d e substrates and imidized as described in the text.
PI(BPyD) was similarly prepared using N-methylpyroli-
d o n e as solvent.
Methods.--Electrochemical i n s t r u m e n t a t i o n and cell
design were the same as d e s c r ib e d in Ref. (6). Unless oth-
erwise noted, all e l e c t r o c h e m i c a l potentials are reported
r e l a t i v e to the s a t u r a t e d c a l o m e l r e f e r e n c e standard.
Most m e a s u r e m e n t s w e r e m a d e u s in g a s il v e r- w i r e
p s e u d o - r e f e r e n c e e l e c t r o d e , w h i c h was c a l i b r a t e d by
r u n n i n g cyclic v o l t a m m e t r y of ferrocene (E ~ = + 0.307V
vs. SCE). E l e c t r o l y t e s , (CH~)~NPF6 (TMAPF6), KPF6,
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0
PI(BPyD) -0.63 -1,05
O O
. . c P, CBzPo~ -O.Sl -1.ol
k ]
Na(C6Hs)4B, and LiC104 were obtained from Alfa. LiC10~
was dried in a v a c u u m oven, all others were used w i t h out
further purification.
S p e c t r o e l e c t r o c h e m i c a l m e a s u r e m e n t s w e r e per-
f o r m e d using a cell similar in design to that described by
W i n o g r a d and K u w a n a (8). S p e c t r a w e r e r e c o r d e d on a
Cary Varian Model 2390 s p e c t r o p h o t o m e t e r .
Specific gravity m e a s u r e m e n t s were made by means of
a liquid gradient c o l u m n using CC14 and toluene. Thick-
ness of p o l y m e r film s a m p l e s was d e t e r m i n e d u sing a
Sloan D e k t a k Model IIa m e c h a n i c a l profilometer.
Results
Polymer chemistry, physical state, and ion perme-
ability.--Attempts to r e d u c e c o m m e r c i a l p o l y i m i d e film
directly at the surface of a cathode yielded generally dis-
a p p o i n t i n g results. A p i ece of K a p t o n | H film, 0.3 mil
thick, was sealed over t h e o p e n en d of a P y r e x t u b e 10
m m in d i a m e t e r by m e a n s of a h e a t - s h r i n k polyolefin
sleeve. A drop of m e r c u r y was d e p o s i t e d in t h e t u b e on
top of the p o l y m e r w h e r e it s e r v e d as the cathode. T he
t u b e was i m m e r s e d in e l e c t r o l y t e s o l u t i o n c o n s i s t i n g of
0.10M KPF6 in DMF. At an a p p l i e d p o t e n t i a l of -2.0V,
only a n e g l i g i b l e c u r r e n t was d et ect ed . H o w e v e r , after
m a i n t a i n i n g t h e s e c o n d i t i o n s o v e r n i g h t , a small r e g i o n
of the film had b eg u n to turn blue-green, indicative of the
f o r m at i o n of radical anion PI(ODA)-.
R e a s o n i n g that t h e rate of r e d u c t i o n m i g h t be l i m i t e d
by low mobility of the electrolyte cations in the film, dc
c o n d u c t i v i t y m e a s u r e m e n t s w e r e m a d e to o b t a i n an
e s t i m a t e of t h e ion p e r m e a b i l i t y . Th e p o l y m e r film (7.1
c m 2) was s a n d w i c h e d b e t w e e n t w o P y r e x flanges
f o r m i n g a m e m b r a n e b e t w e e n two i d e n t i c a l c o m p a r t -
m e n t s of an H-cell filled with 0.10M LiC104 in AN and
c o n t a i n i n g a pair of p l a t i n u m wire el ect r o d es. Th e cur-
rent was found to vary linearly with voltage over a range
of more than 50V, r e p r e s e n t i n g a resistance on the order
of 100 kl2, w h i c h w o u l d c o r r e s p o n d to a b u l k r e s i s t i v i t y
of a b o u t 109 l~ cm. A l t h o u g h this v a l u e is s u b s t a n t i a l l y
l o w e r t h a n t h e r e s i s t i v i t y of t h e dry p o l y m e r (ca. 10 TM
 348 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
cm), it is, n o n e t h e l e s s , too high to p e r m i t significant
faradaic c o n v e r s i o n s on th e t i m e scale of our
experiments.
By contrast, H a u s h a l t e r ' s and K r a u s ' c h e m i c a l reduc-
tions of K a p t o n | (1) w e r e r e p o r t e d to p r o c e e d r a p i d l y
(within seconds) despite the fact that this process also re-
quires p e r m e a t i o n of the cation (K+). Why t h e n was elec-
t r o c h e m i c a l r e d u c t i o n so m u c h slower? One i m p o r t a n t
difference was traced to the presence of e t h y l e n e d i a m i n e
in the Zintl salt solutions. P r i m a r y amines are k n o w n to
re a c t w i t h i m i d e s to yield partially a m i d i z e d p r o d u c t
( s c h e m e 2). We e x p l o r e d the p o s s i b i l i t y t h a t such par-
tially a m i d i z e d p o l y i m i d e m i g h t be significantly m o r e
p e r m e a b l e t o w a r d s e l e c t r o l y t e ions than th e original
h o m o p o l y m e r . DC c o n d u c t i v i t y of K a p t o n | was mea-
sured in the presence of ethylenediamine.
R'NH2 ~ - ~. lk jl CONHRt
O O Scheme
Figure 1 shows a plot of current vs. time for an electro-
lyte s o l u t i o n similar to that d e s c r i b e d above, b u t
i n c l u d i n g e t h y l e n e d i a m i n e (10% by volume). T h e m e m -
brane resistance r e m a i n e d constant at a value of 1 M~ for
a period of about 200 rain, after which it decreased stead-
ily (increasing current) to a p l a t e a u v a l u e of a p p r o x i -
mately 40 k~. At this point, the film r e m a i n e d intact, ap-
p e a r e d clear and h o m o g e n e o u s , b u t had lost the
c h a r a c t e r i s t i c y e l l o w color of K a p t o n | ( b e c a m e color-
less). After a longer period, the current c o n t in u e d to rise,
unt i l u l t i m a t e l y t h e c o n d u c t i v i t y c o r r e s p o n d e d to t h e
v a l u e of t h e e l e c t r o l y t e solution. The p o l y m e r had
u n d e r g o n e e x t e n s i v e d e g r a d a t i o n , l e a v i n g a fragile po-
rous residue. When e x p e r i m e n t s of this sort w e r e re-
peated at different voltages, it was found that the transi-
tion to t h e " p l a t e a u " c u r r e n t was a c c e l e r a t e d at h i g h e r
bias voltages.
The exact chemical composition of the p o l y m e r at the
p l a t e a u was not a s c e r t a i n e d ; n e v e r t h e l e s s , the qualita-
tive effects are certainly adequate to a c c o u n t for the dif-
f e r e n c e s b e t w e e n e l e c t r o c h e m i c a l and Zintl ion reduc-
tions. On t h e o t h er hand, b e c a u s e of the u n c e r t a i n t i e s
i n h e r e n t in studying the properties of partially degraded,
possibly h e t e r o g e n e o u s material, it was desirable to find
an a l t e r n a t i v e m e t h o d for p r e p a r i n g e l e c t r o c h e m i c a l l y
a c t i v e p o l y i m i d e samples. F o r t u n a t e l y , this o b j e c t i v e
c ould be a c h i e v e d by a p p r o p r i a t e c o n tr o l of c o n d i t i o n s
used for imidization of the polymer.
Tzme (sec)
768
512
(0
O--
384 E
[3
v
D PI(ODA)- to PI(ODA) -2
4~
(D
256 L
L for this sample (assuming one electron per repeat unit at
D
U each r e d o x couple) would be 12.0 -+ 1.8 m C/ cm 2. There is
128
0 duced by one or two electrons was further su p p o r t ed by
r~ ~ QD
~3
Fig. 1. DC current passed by a 0.3 rail Kapton membrane in 0.10M
KPF6 in acetonitrile containing ethylene diamine, 10% by volume. A
constant voltage ( - 2 . 0 V ) was applied between Pt electrodes.
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F e b r u a r y 1987
C o n d e n s a t i o n - t y p e polyimides are sy n t h esi zed by de-
hydration (imidization) of a p r ef o r m ed polyamic acid, as
illustrated in scheme 3. This may be a c c o m p l i s h e d either
by heating to t e m p e r a t u r e s in excess of 250~ or by the
a c t i o n of c h e m i c a l d e h y d r a t i n g agents. C o m m e r c i a l
p o l y i m i d e films are invariably processed at high temper-
atures, conditions that produce orientation and a low de-
gree of crystalline order (9, 10). It is likely that the latter
characteristics strongly influence the p e r m e a b i l i t y of the
product. Reasoning that solvent swelling and ion perme-
ability should vary inversely with the e x t e n t of order in
the neat polymer, we chose to investigate the properties
of films p r e p a r e d by c h e m i c a l d e h y d r a t i o n at a m b i e n t
temperature, w h er e the degree of s u p e r m o l e c u l a r order-
ing w o u l d likely be minimized.
R N N OC , ~ I ~ , , . ~ C O I H
1C)i
N o ~ ~ "~_/~CONNR
~. R- -R +2H20 Scheme 3
2 Films of polyamic acid (derived from ODA and PMDA,
i n h e r e n t viscosity 1.4 dl/g in DMAc) ranging from 0.2 to
20 a m in t h i c k n e s s were spin coated onto v a r i o u s disk
el ect r o d es, i n c l u d i n g glassy c a r b o n and N e s a t r o n
c o n d u c t i v i z e d glass. E x c e s s s o l v e n t was r e m o v e d by
heating at 80~ for 10 min leaving a clear, colorless, solid
film. D e h y d r a t i o n was effected by s o a k i n g the coated
e l e c t r o d e s in a 1:1 m i x t u r e (by v o l u m e ) of dry p y r i d i n e
and acetic an h y d r i d e for 2h. At the end of this period, the
films remained clear but had acquired the characteristic
y e l l o w color of P I ( O D A ) ? As d e s c r i b e d below, s a m p l e s
prepared by this p r o ced u r e proved to be quite amenable
to conventional electroanalytical techniques, in contrast
to the high t e m p e r a t u r e imidized film.
Our studies have m a d e use of c o m p a r i s o n s a m o n g a
range of different polyimides, all derived from pyromel-
litic a n h y d r i d e (Table I) and also a series of s i m p l e
d i i m i d e s , w h i c h s e r v e d as m o d e l s for the m o l e c u l a r re-
peat units (Table II).
Electrochemistry.--Figure 2 shows a typical cyclic vol-
t a m m o g r a m for a thin (0.24 ~m) film of PI(ODA), pre-
pared as described above. The two chemically reversible
processes are clearly defined. The eq u i l i b r i u m r ed o x po-
tentials, taken as the m i d p o i n t b e t w e e n anodic and cath-
odic c u r r e n t peaks, are E~ = - 0 . 7 3 V and E% = - 1.13V.
F o r p o t e n t i a l s p o s i t i v e of -0.6V, the p o l y m e r film re-
m a i n e d yellow, b e t w e e n -0.7 and -0.9V it appeared blue
[consistent with PI(ODA)- as described in Ref. (2)], and,
at potentials negative of -1.1V, it b e c a m e deep rose col-
ored ( co n si st en t with PI(ODA)-2). Essentially, the same
results were obtained with each of the other polyimides.
Quantitative details are summarized in Table I.
Complete stoichiometric conversions were achieved
d u r i n g the course of cyclic e x p e r i m e n t s , such as that
s h o w n in Fig. 2. Thus, for a t y p i cal e x p e r i m e n t with
PI(ODA), the integrated current u n d er each of the peaks
was as follows
Redox process Charge capacity (mC/cm z)
Cathodic Anodic
peak peak
PI(ODA) to PI(ODA)- 10.2 9.9
12.0 9.8
(0.10M KPF6/AN, area 7.07 cm 2, 5 mV/s, film thickness ap-
p r o x i m a t e l y 0.28 ~m). The t h e o r e t i c a l charge c a p a c i t y
a systematic error in the e x p e r i m e n t a l data due to a small
cathodic b a c k g r o u n d current at these potentials. There-
fore, we regard the a g r e e m e n t to be within e x p e r i m e n t a l
error. The c o n c l u s i o n that each c h e m i c a l r e p e a t unit
t h r o u g h o u t the bulk of the sample may be reversibly re-
s p e c t r o p h o t o m e t r i c studies to be described.
With t h i c k e r films, the same q u a l i t a t i v e b e h a v i o r was
o b s e r v e d . H o w e v e r , the t i m es r e q u i r e d to fully charge
an d d i s c h a r g e such s a m p l e s b e c a m e c o r r e s p o n d i n g l y
2Infrared transmission spectra revealed no significant differ-
ences between the thermally and chemically imidized films.
 Vol. 134, No. 2 AROMATIC POLYIMIDES 349

Table II. Cyclic voltammetry of model compounds e f f e c t s a p p e a r to b e m o s t p r o n o u n c e d f o r t h i c k e r f i l m s

(0.10M KPF~/acetonitrile) a n d a p p e a r to b e r e l a t e d to s w e l l i n g , d e l a m i n a t i o n , o r
o E~ ~ even partial dissolution of the dianionic form of the poly-
m e r . (A s o l u b l e , r o s e - c o l o r e d c o m p o n e n t w a s i n v a r i a b l y
PPI -1,33 -2.05 extracted into the DMF solutions when the potential was
N-phenylphthalimide m a d e m o r e n e g a t i v e t h a n E%). A l t h o u g h n o c a t h o d i c re-
O
d u c t i o n w a s o b s e r v e d w i t h LiC104/AN, a p o o r l y r e v e r s i -
b l e p a i r o f w a v e s w a s o b s e r v e d w i t h t h e s a m e s a l t dis-
s o l v e d i n d r y p r o p y l e n e c a r b o n a t e . W i t h h y d r o x y l i c or
even wet solvents only a single, totally irreversible cath-
N N DPB odic reduction was observed, with charge capacity much
-1.32 -1.93
1,4-dlphthalimidoyl- less t h a n t h e o r e t i c a l . I t is l i k e l y t h a t r a d i c a l a n i o n s n e a r
benzene
the surface of the cathode become protonated by these
s o l v e n t s a n d a r e t h e n i n c a p a b l e o f p a s s i n g e l e c t r o n s to

N--CH2CH2
o DPE
unreacted imide groups farther into the bulk.
Charging rates.--The r a t e s o f c h a r g i n g a n d
discharging were measured following an instantaneous
-1.42 -2.04
~ ~r V 1,2-diphthalimidoyl-
ethane change in the applied potential (chronoamperometry).
I d e a l l y , u n d e r c o n d i t i o n s of p u r e l y d i f f u s i o n - c o n t r o l l e d
currents, one may extract an empirical transport
c o e f f i c i e n t f r o m e x p e r i m e n t s o f t h i s s o r t (11). T h i s k i n d
O of analysis has been employed for a number of other
e l e c t r o a c t i v e p o l y m e r s a n d r e l a t e d s y s t e m s (12). T h e
-
~ ~ / "
~ "" "'
4,4'-diphthal- - 1 . 3 3 -2.O4 p h y s i c a l i n t e r p r e t a t i o n of s u c h a p a r a m e t e r is n o t a l w a y s
v ~ 6" imidoyldiphenylether o b v i o u s . I t m a y r e p r e s e n t t h e d i f f u s i o n c o e f f i c i e n t of t h e
l e a s t m o b i l e c h a r g e c a r r y i n g s p e c i e s , or s o m e c o m p o s i t e
property dictated by coupling of the various fluxes.
H o w e v e r , as p o i n t e d o u t i n t h e first s u c h s t u d y (13),
0 N N 0 m a n y p o s s i b l e c i r c u m s t a n c e s will c a u s e d e v i a t i o n s f r o m
the simple diffusion model.
DPPP -0.67 -1.27
In practice, our data for charging and discharging of
4,4 '~diphenoxyphenyl- t h e p o l y i m i d e s are i n c o m p a t i b l e w i t h a s i m p l e d i f f u s i o n
pyromel litimide
m o d e l e v e n w i t h i n r e s t r i c t e d t i m e d o m a i n s . F i g u r e 3a
s h o w s a t y p i c a l c u r r e n t t r a n s i e n t for t h e p r o c e s s :

011C 5 _C5H11 DAP -0.74 -1.43

di~n-amyl- 1500 . . . . , . . . . , . . . . , . . . .
~t~ V ~ pyromellitimide

l o n g e r ; t h u s , for s a m p l e s t h i c k e r t h a n a b o u t 5 ~m, it w a s
i m p r a c t i c a l to o b s e r v e c o m p l e t e c o n v e r s i o n d u r i n g t h e 1,25
c o u r s e of a l i n e a r s w e e p e x p e r i m e n t .
N o t s u r p r i s i n g l y , t h e c o m p o s i t i o n o f t h e e l e c t r o l y t e so-
l u t i o n w a s f o u n d to b e a f a c t o r in t h e e l e c t r o c h e m i c a l re-
s p o n s e . S o l u t i o n s w i t h KPF,~, CsPFG, or NaB(C~H~)4 as 750
s u p p o r t i n g e l e c t r o l y t e i n a c e t o n i t r i l e all b e h a v e d s i m i -
l a r l y . S i m i l a r b e h a v i o r w a s o b s e r v e d w i t h T M A P F ~ , al-
t h o u g h t h e r e v e r s i b i l i t y of t h e s e c o n d r e d o x p r o c e s s w a s 375
p o o r e r . W h e n D M F w a s e m p l o y e d as s o l v e n t , it w a s n o t
a l w a y s p o s s i b l e t o a c h i e v e c o m p l e t e r e d u c t i o n to t h e
dianion, and this step was frequently irreversible. These
, , , : . . . . I l , , ,

12.50 ~5.00 37.50 58.08

0.40 I I I I time (sec)

1500

I
;T 1125
I

==
0.0 750
(mA)

375

0 i I , , , , I , , , ,
1.25 2.50 3.75 5.00
-0.40 I I I I
-0.5 0.0 -1.0 -1.5 (time) ~
E (volts vs. A g / A g +) Fig. 3. (a, top) Chronocoulometry of PI(ODA) film, 0.2 I~m thick,
Fig. 2. Cyclic voltommogram of PI(ODA) film, 0.24 ~m thick, in 0.10M KPF~ in acetonitrile. Potential was stepped from - 0 . 4 0 to
0 . 1 0 M KPF6 in acetonitrile. The scan rate was 2 mV/s. The electrode - 0 . 9 0 V vs. Ag/Ag § at t = 0. (b, bottom) Data of Fig. 3a replotted ac-
area is 1.3 cm2. cording to Cottrell equation. The electrode area is 1.3 cm2.
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 350 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
PI(ODA) -~ PI(ODA)-. Figure 3b is the same data plotted
as function of t ~/~ (a Cottrell plot). It can be shown that
simple diffusion-limited charging of a film of finite thick-
ness should obey the Cottrell equation for suitably short
time domains (semi-infinite regime), and that the extrap-
olated intercept of this line should m e e t the origin (i = 0
at t = oo). Obviously, the idealized thin-layer m o d e l gives
a very poor description of the present data. In fact, it ap-
pears that over no s ig n i f ic a n t t i m e d o m a i n is the
charging process governed by simple diffusion.
T h e r e are several p o s s i b l e reasons for t h e s e c o m p l e x
c h a r g i n g kinetics. The e l e c t r o c h e m i c a l t r a n s f o r m a t i o n
from neutral p o l y m e r to a highly charged polyelectrolyte
is u n d o u b t e d l y a c c o m p a n i e d by changes in the e x t e n t of
s o l v e n t swelling as well as c h a n g e s in the a c t i v i t y and
mobility of electrolyte ions. Since the r e d o x state of the
p o l y m e r v a r i e s with d i s t a n c e from the c a t h o d e d u r i n g
t he c h a r g i n g p r o c e s s and this g r a d i e n t is c o n t i n u a l l y
c ha ng i n g , the r e s u l t i n g kinetics m a y be e x t r e m e l y
complex.
L a c k i n g any systematic m e a s u r e of the charging kinet-
ics, it was useful n e v e r t h e l e s s to c o m p a r e relative rates
as m e a s u r e d by two r e p r o d u c i b l e e x p e r i m e n t a l parame-
ters: Io, the initial current density observed following the
change of potential, and tl/2, the half-life for the process.
Ta ble III s u m m a r i z e s s o m e r e p r e s e n t a t i v e data from
w h i c h t h e f o l l o w i n g g e n e r a li z a ti o n s m a y be drawn. F o r
e l e c t r o l y t e c o n c e n t r a t i o n s less than 0.1M, tl/~ is clearly
dependent upon electrolyte concentration. For higher
c o n c e n t r a t i o n s t h e c o r r e l a t i o n is not so clear and it is
possible that transport b e c o m e s limited by electron mo-
bility at the higher electrolyte concentrations.
E v e n a l l o w i n g for the g r e a t e r film t h i c k n e s s e s ,
c h a r g i n g rates are f o u n d to be s o m e w h a t slower for
P I ( m - P D ) and PI(p-PD) t h a n for PI(ODA). This is note-
w o r t h y g i v e n t h e fact that, in t h e f o r m e r p o l y m e r s , t h e
intrachain distance b e t w e e n successive p y r o m e l l i t i m i d e
rings is considerably shorter than for the latter. It may be
t h a t i n t e r c h a i n i n t e r a c t i o n s are m o r e i m p o r t a n t in
c o n t r o l l i n g e l e c t r o n t r a n s p o r t t h a n intrachain. In this
c o n t e x t , we note t h a t t h e total bulk c o n c e n t r a t i o n of
p y r o m e l l i t i m i d e groups in t h e t h r e e p o l y m e r s does not
differ so greatly: 2.4M for PI(ODA), 2.17M for PI(m-PD),
and 2.48M for PI(p-PD). (These concentrations are calcu-
lated from the b u l k d e n s it ie s of the p o l y m e r s c o r r e c t e d
for swelling in AN.)
Optical absorption spectra.--Using c o n d u c t i v i z e d
glass el ect r o d es , optical a b s o r p t i o n s p e c t r a w e r e re-
corded of thin (less than 0.5 ~m) p o ly im i d e films in vari-
ous states of reduction. The electrode was maintained at
a fixed applied potential until the cell had reached equi-
l i br i u m at which point the s p e c t r u m was recorded. This
p r o c e d u r e was r e p e a t e d at 50 m V i n c r e m e n t s s p a n n i n g
the range of potentials from -0.60 to -1.30V vs. Ag/Ag +.
F i g u r e 4 shows results for s o m e r e p r e s e n t a t i v e
examples.
P r i n c i p a l a b s o r p t i o n m a x i m a for the t h r e e d i f f e r e n t
o x i d a t i o n states are well resolved. N e u t r a l PI(ODA) ab-
sorbs only weakly in the visible, including a small peak
at 380 nm, and n e g l i g i b l e a b s o r p t i o n at l o n g e r than 500
nm. The radical anion PI(ODA)-, w h ic h appears at po-
tentials b et ween -0.70 and -0.90V vs. Ag/Ag +, exhibits a
Table III. Charging rates (PI --~ PI-) for polyimide films
Film
thickness Electrolyte a Io
Polymer (~m) (M) (mA/cm2)
PI(ODA) 0.20 Na + 0.0l 0.20 26
PI(ODA) 0.20 Na + 0.10 0.35
PI(ODA) 0.23 Na + 0.20 0.26
PI(ODA) 0.20 Na+ 0.50 0.48
PI(ODA) 0.20 K+ 0.10 0.71
PI(ODA) 6.5 K+ 0.10 0.46 25.8
PI(m-PD) 6.89 Na + 0.10 0.51 24
PI(p-PD) 1.63 Na + 0.10 0.46 34
a NaB(C6H~)4 or KPF6 in acetonitrile.
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F e b r u a r y 198 7
strong band at 720 nm (e23,000) with a shoulder at 660 nm
(el8,000). Finally, the dianion PI(ODA) -2, which appears
between -I.0 and -I.30V, has a maximum at 555 nm
(e55,000) and shoulders at 524 nm (e46,000) and 400 nm
(e6,000). A well-defined isosbestic point may be noted at
585 nm for states intermediate between pure PI(ODA)-
and pure PI(ODA) -2. Spectra of the ions from PI(m-PD),
PI(MsD), and PI(BzPD) were virtually identical to those
of PI(ODA).
The spectrum of PI(ODA)- has a long-wavelength tail
extending well out into the near IR; however, there is no
evidence for a mixed-valence-type transition (charge
transfer transition between pairs of chromophores in dif-
ferent oxidation states). The same principal absorption
bands are observed for dilute solutions of the
monomeric analogs DAP- (el2,000 at 720 nm) and DAP -2
(e49,000 at 550 nm); however, these bands are substan-
tially narrower than observed for the polymeric ions, and
the subsidiary maxima were considerably weaker. [The
latter spectra agree well with those appearing in Ref (2).]
Discussion
On t h e basis of the f o r g o i n g results, it is possible to
draw s o m e c o n c l u s i o n s r e g a r d i n g t h e f o l l o w i n g issues:
the character of the electronic states associated with the
various redox states of the polymer, and the i m p o r t a n c e
of inter- and i n t r a - m o l e c u l a r i n t e r a c t i o n s in e l e c t r o n
transport.
Interactions between redox centers.--In c o m p a r i n g the
e l e c t r o c h e m i c a l p o t e n t i a l s s u m m a r i z e d in Tables I and
II, what stands out most notably is the lack of influence
of t h e d i a m i n e group. For t h e p y r o m e l l i t i m i d e deriva-
tives, each imide group accepts only one electron, but
this occurs at two d i s t i n c t r e d o x p o t e n t i a l s b e c a u s e of
strong coulombic repulsion between a pair of electrons
interacting through the pi-orbitals of a common aromatic
ring. Apparently, the diamine bridge has very little di-
rect influence, since the two potentials are virtually the
same for all of the polymers studied.
In the case of the bis-phthalimide derivatives, both im-
ide groups can accept one electron at the same potential
(ranging from -1.3 to -1.42V). As a consequence of their
separation in space, electron repulsion between these
ions is too small to create a measurable separation in E ~
At more negative potentials (ca. -2.0V) each imide group
accepts a second electron2 Slightly more positive poten-
tials are observed for the aromatic bridges probably due
to a modest inductive effect. Again, the similarity in be-
havior within the series suggests little interaction with
the diamine bridges.
Our analysis of the optical spectra is consistent with
the above conclusions. They do, however, provide a
much more sensitive measure of interactions between
the redox active groups. As noted previously, the wave-
length of principal absorption maxima for the polymer
radical anions and dianions are the same as observed for
the model pyromellitic diimides (DAP and DPPP). In
each case, the shoulders at shorter wavelength (660 nm
for the radical anion and 520 nm for the dianion) may be
tentatively assigned as higher vibronic transitions of the
same electronic states (720 and 550 nm, respectively).
(The separation between the two (1260 cm -I) does corre-
spond to a strong vibrational transition in the ground-
state IR spectrum.)
Our conclusion is that the electronic wavefunctions
corresponding to ground and first-excited states of the
t,/2 polymeric ions are strictly localized on the pyromellitic
(s) diimide group. Accordingly, the various redox states of
the polymer may be regarded as simple equilibrium mix-
tures of these localized molecular species. However, de-
4.0 spite the absence of direct electronic interactions be-
1.6 tween the pyromellitimide groups, there are several
2.2
4.8 indications of weaker, less specific interactions.
3At equimolar concentrations and equal scan rates, the peak
currents observed for each of the bis-phthalimide derivatives in
Table II were roughly twice as large as those observed for the
parent molecule, PPI. From this, it was concluded that the
bifunctional analogs accept two electrons at each potential.
 Vol. 134, No. 2 AROMATIC POLYIMIDES 351

- 1.'30 V :..l i i-+.2}_vi J ! i ~ J

A, _222.s ~ A ~ _~._..L.~_ .+__~__+_~ _~.-~
i~ ::1 i fl i i :i i i i i ] ~ '~
=II / i -~ T= ~-;-; ~ I
-~-~--~-.-~, ~--~ ~ - - r ! : : - ~ i - ......
: I:; i ~ ; ~ ] ! ; ! : : ! =
/, Ti T , -
1.2 . . . . T ~ !:, ~ IPI : "I" . ~ " , ! '
2:- -L--+- L-}| ..... : ~ + ~ -- " '

1.0 ..... ! ~- , ~- T : ~ : T--!-----;--~- - T ~........d --~

i i i ; ! I_ :
:!] ~ii : ] ,
-[-C i --- i T- .... ...... n,;
.~- - i - : ] , . :_- ~ . 0 V ......
.... i ~ ....... ---- ;:o,~'~v i ; :.....
.6 - 9 -" - ~
~II . + ..... : :+_i..i.

4 ........

,2 - - ~ !.-- -2 : -!---. .... ;

o . . . . . . . . . . . . . . . . . . . .

t . , [ ! i ~ r , i ,
' . "~- :i ! i
.6- i. . . . . - : . .A. . - : - T,- ( , A:__
~ g ~ - - -.~ _!
i - T
.42 ......... , . . + . ~ . ,. .. . !-;] ..... ! . . :_~___._~:~-.._.
, I / / ~ i ', :
I ". . . . . / / ' J A ~ i :
.2-" :0.60V ......
w
I1-7- , ~ ~ + I !
9 ' i //A~+ !:i
I ] ; .
ii I i :
400 i 6~0 ~ 8~0 t 1000 nm
, : ~ . : !

400 600 800 1000 nm

PI(BPvD)

:--~ i-.~ =,.~o~ +. .-!-i i

-/ , !iT

. " =o.9o,~

Fig. 4. Optical absorption spectra of polyimide films (ca. 0.2 ~.m)

equilibrated at potentials spanning E ~ and E%. The potential was
i! ~'~" " varied in 50 mV intervals. All spectra were obtained using 0.10M KPF6
in acetonitrile.

: !~:i iii : !

I-i +:L i 1:~ j ~ + + i i i

400 600 800 1000 nm

D i f f e r e n c e s b e t w e e n s p e c t r a for p o l y m e r i c a n d PI(ODA), the wavelengths of the absorption maxima

m o n o m e r i c p y r o m e l l i t i c d i i m i d e i o n s c a n b e a s c r i b e d to a g r e e w i t h t h o s e o f t h e m o n o m e r i c p y r o m e l l i t i m i d e ions.
"environmental" effects which may operate at various H o w e v e r , o n c l o s e r i n s p e c t i o n , it is n o t e d t h a t , d u r i n g
s t r u c t u r a l l e v e l s . A t t h e l e v e l o f b u l k p r o [ o e r t i e s , t h e ef- c o n v e r s i o n o f P I ( p - P D ) to P I ( p - P D ) - , t h e t w o m a x i m a as-
fective isotropic dielectric constant and polarizability of s i g n e d t o t h e r a d i c a l a n i o n (720 a n d 660 n m ) d o n o t m a i n -
t h e p o l y m e r p h a s e is l i k e l y to d i f f e r f r o m t h a t of t h e solu- t a i n t h e s a m e r e l a t i v e m a g n i t u d e as t h e e x t e n t o f c o n v e r -
tion in which the monomeric analogs were observed. On s i o n is i n c r e a s e d . T h e s a m e e f f e c t is e v e n m o r e
the molecular scale, individual chromophores may be p r o n o u n c e d for t h e d i a n i o n P I ( B P y D ) -~. A p e r t u r b a t i o n
influenced by the local concentration of ionic groups. of the transition moment induced by local electrostatic
For example, the transition dipole moment of a given f i e l d s c o u l d e x p l a i n t h e s e o b s e r v a t i o n s a n d is a l s o c o n -
chromophore might be influenced by the charge carried sistent with the differences between spectra of bulk
o n p r o x i m a l i m i d e g r o u p s w i t h i n t h e s a m e or o n n e i g h - polymer and dissolved model compounds. A quantita-
b o r i n g c h a i n s . E f f e c t s s u c h as t h e s e m a y b e e x p e c t e d t o t i v e a n a l y s i s o f t h e r e l a t i o n b e t w e e n a b s o r b a n c e a n d po-
v a r y w i t h t h e o v e r a l l r e d o x s t a t e ( e x t e n t of r e d u c t i o n ) of t e n t i a l h a s p r o v e n to b e a p a r t i c u l a r l y s e n s i t i V e p r o b e for
t h e s a m p l e . I n fact, m o r e c a r e f u l s c r u t i n y o f t h e s p e c t r o - t h i s k i n d o f effect.
scopic data reveals some examples of this kind of F o r a m i x t u r e o f n o n i n t e r a c t i n g c h r o m o p h o r e s i n elec-
variation. trochemical equilibrium with one another, the variation
Spectra of PI(p-PD) and PI(BPyD) in various states of of absorbance at any wavelength with applied potential
r e d u c t i o n a r e s h o w n i n Fig. 4b, c. A s i n t h e c a s e o f m a y b e d e r i v e d f r o m a c o m b i n a t i o n of t h e N e r n s t e q u a -
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 352 J. Electrochem. Soc.: ELECTROCHEMICAL SCIENCE AND TECHNOLOGY February 1987

O.t,?.O i \l i J i z i i OJO

0.0~ + \
0.08

0.072 ~*\ \ ,x PICODA) 0.06

PI(p-PD)
O.04.B 0,04

0.024
0.02

0.000
f(A) f(A) ooo
-0.024
--0.02

-0.048
-0.04

-0.072
+~o x ,,',,,~ -0.06
~ 76~nm
-0,096
-0.08
-0.~,0 r I i i i r i i I
-0.90 -0,86 -0,82 -0,7S -0.74 -"0.70 -0.66 -0.62 -0.88 -0.54 -0.50 -0.10 i I I I I I I I l
-O,SO -0,76 -0.72 -0.68 -0.64 -0.60 mO.~ ~.52 -0.48 -0.44 -0.40

0,140 I 4 I I I I I
0.!40 E

0.1!,2
0.112
+

0.084 0.084

0.056 0.056

0,028 0,028

f(A) 0.000 f(h) oooo

-0.028 -0.028

-0.056 -0.056
+
0 585 nm
\
-0.084. -0.00/* 0 520 nm
+ 520
-0.112 -0.t'12 + 550

--0.'~.0 I . . . . . . . . . -0.140 I I I
, , , , ,
-1,35 -1,31 -,.27 -,.23 -,.,, -,.,5 -,., -~.07 -,.03 -0., -o.,s -1.30 -I.25 -1.20 -1.15 -,.to -,.os - oo -0.05 -0.90 -0, -0.80
r (v vs AS/AS+) E (V v, Ag/Ag+)
Fig. 5. Optical absorption data plotted according to Eq. [4] for the first and second redox couples of PI(ODA) and PI(p-PD). Solid lines represent
linear least squares fit to the data, and dashed lines are theoretical plots calculated for redox potentials as determined by cyclic voltammetry.

t i o n a n d t h e B e e r - L a m b e r t law. T h e s i t u a t i o n is p a r t i c u - one or more of the physicochemieal parameters that

larly simple for a wavelength where only one oxidation
state has a significant extinction coefficient. Fortunately,
t h i s c o n d i t i o n is a v e r y g o o d a p p r o x i m a t i o n f o r a b s o r p -
t i o n m a x i m a c o r r e s p o n d i n g to t h e a n i o n r a d i c a l a n d
d i a n i o n s t a t e s of t h e p o l y i m i d e s . T h e r e l e v a n t e q u a t i o n s
a r e s u m m e r i z e d as f o l l o w s
E = E ~ + RT/nF In [I]/[I-]
[I ] = A J e L = [I-]max -- [I]
[I-]ma• = [I] + [I ] = A x " a X / e x L
f(k) = RT/nF i n [(Ax . . . .
w h e r e k c o r r e s p o n d s to t h e a b s o r p t i o n m a x i m u m for t h e
s p e c i e s I-, A~ is t h e a b s o r b a n c e m e a s u r e d w h e n t h e cell
is e q u i l i b r a t e d a t s o m e p o t e n t i a l E, A~ max is t h e
a b s o r b a n c e for c o m p l e t e c o n v e r s i o n to I , a n d E ~ is t h e
s t a n d a r d h a l f - c e l l p o t e n t i a l f o r t h e I / I - c o u p l e (L is t h e
o p t i c a l p a t h l e n g t h ) . T h u s , b y p l o t t i n g f(X) (Eq. [4]) vs. E ,
one should obtain a straight line with slope of -1.00 and
an X-intercept of E ~
The appropriate plots were generated for each of the
s i x p o l y i m i d e s at w a v e l e n g t h s c o r r e s p o n d i n g to t h e ab-
sorption maxima of the ionic species (720,660,550, and
520 n m ) . R e p r e s e n t a t i v e e x a m p l e s a r e s h o w n i n Fig. 5. I n
all c a s e s , t h e p l o t s w e r e l i n e a r a n d t h e i n t e r c e p t s a g r e e d
w e l l w i t h v a l u e s o f E~ a n d E% d e r i v e d i n d e p e n d e n t l y
f r o m c y c l i c v o l t a m m e t r y . H o w e v e r , i n all c a s e s , t h e
slopes deviate from the theoretical value (-1.00) ranging
f r o m - 0 . 3 1 for t h e 660 n m b a n d o f P I ( B P y D ) , to - 0 . 8 0 for
t h e 720 n m b a n d o f P I ( O D A ) - . ( F o r a n y g i v e n p o l y i m i d e ,
t h e s e d a t a w e r e h i g h l y r e p r o d u c i b l e a n d w e r e s h o w n to
b e i n d e p e n d e n t o f w h e t h e r t h e d a t a a r e c o l l e c t e d i n or-
d e r o f i n c r e a s i n g or d e c r e a s i n g p o t e n t i a l . T h e s t o i c h i o -
m e t r i c n u m b e r , n, w h i c h a p p e a r s i n E q . [4] w a s e s t a b -
l i s h e d to b e 1 b y e a r l i e r c o u l o m e t r y . )
Deviation of the experimental absorbance plots from
the theoretical slope may be attributed to a dispersion in
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c h a r a c t e r i z e t h e i n d i v i d u a l c h r o m o p h o r e s . T h a t is, a sys-
t e m a t i c c h a n g e in e i t h e r t h e e x t i n c t i o n c o e f f i c i e n t or t h e
r e d o x p o t e n t i a l s as a f u n c t i o n of t h e e x t e n t o f r e d u c t i o n
w o u l d r e s u l t i n d e v i a t i o n s o f t h i s sort. D i s p e r s i o n i n t h e
r e d o x p o t e n t i a l s is m o s t e a s i l y v i s u a l i z e d , s i n c e t h e p o -
t e n t i a l r e q u i r e d to a d d a n e l e c t r o n to a g i v e n r e d o x s i t e
w i l l t e n d to b e i n c r e a s e d b y c o u l o m b i c r e p u l s i o n f r o m
[1] charges on neighboring sites. (This kind of effect has
[2] b e e n p r e v i o u s l y r e c o g n i z e d (14) f o r i n t r a - c h a i n r e p u l -
s i o n , a s i t u a t i o n a n a l o g o u s to t h e d i s p e r s i o n i n i o n i z a t i o n
[3] c o n s t a n t s for p o l y b a s i c a c i d s . ) I n t h e p r e s e n t i n s t a n c e ,
e i t h e r i n t r a - or i n t e r - c h a i n c o u l o m b i c r e p u l s i o n s m a y b e
A~)/Ax] = E ~ - E [4] responsible. The magnitude of the dispersion in E ~
needed to account for the most extreme example.
P I ( B P y D ) / P I ( B P y D ) - , w o u l d b e -+120 m V . T h e c y c l i c
v o l a m m e t r y w a v e s for t h e p o l y m e r s t y p i c a l l y e x c e e d t h e
theoretical widths by at least this amount; however,
t h e s e p a r a m e t e r s a r e t o o s e n s i t i v e t o o t h e r f a c t o r s to b e a
reliable measure. On the other hand, the fact that no such
d i s p e r s i o n is e v i d e n t f r o m cyclic v o l t a m m e t r y of t h e cor-
responding model bis-phthalimides suggests that inter-
chain interactions are the dominant influence for the
bulk polymers.
Electron and ion transport.--In the absence of direct
e l e c t r o n i c i n t e r a c t i o n s b e t w e e n r e d o x c e n t e r s , it is c l e a r
t h a t t h e m e c h a n i s m f o r b u l k e l e c t r o n t r a n s p o r t is
pairwise redox exchange reactions between proximal
pyromellitimide groups (electron hopping). The general
l a c k o f s e n s i t i v i t y to t h e n a t u r e o f t h e b r i d g i n g d i a m i n e
group suggests that intra-chain electron transfer plays
n o s p e c i a l role. H o w e v e r , it m u s t b e e m p h a s i z e d t h a t t h e
c h a r g i n g c u r r e n t s t h a t w e m e a s u r e d are n o t i n d e p e n d e n t
of ion mobility. Consequently the latter conclusion must
b e r e g a r d e d as t e n t a t i v e u n t i l t h e t r u e e l e c t r o n m o b i l i t i e s
can be measured. (An intrinsic electron diffusivity can
be measured under conditions of a fixed ion concentra-
t i o n gradient; (steady-state conditions). An example of
this sort of measurement can be found in Ref. (6).)
 Vol. 134, No. 2 AROMATIC POLYIMIDES 353

Th e r e l a t i o n s h i p b e t w e e n e l e c t r o c h e m i c a l c h a r g i n g Press, New York (1984).

processes and ion permeability has b e e n clearly demon-
strated. T h e details of the p o l y m e r ' s p h y s i c a l state that
d i c t a t e this p r o p e r t y are not well u n d e r s t o o d . As w i t h
earlier e x a m p l e s of electroactive polymers (13), a correla-
tion has been noted b e t w e e n the solvent swelling charac-
teristics of the polyimides and the ion p e r m e a b i l i t y (15).
T h e r m a l l y imidized PI(ODA) swells very little in the sol-
v e n t s e m p l o y e d in this study, w h i le the c o r r e s p o n d i n g
chemically imidized films swelled by as m u c h as 100% in
D M F (36% in AN). Work in progress is directed at under-
standing these p h e n o m e n a .
Acknowledgment
R o b e r t J. Clifton and Gloria T. Worrell p r o v i d e d valua-
ble technical assistance.
M a n u s c r i p t s u b m i t t e d April 9, 1986; r e v i s e d manu-
script received J u n e 17, 1986.
E. I. du Pont de N e m o u r s a n d C o m p a n y assisted in
meeting the publication costs o f this article.
REFERENCES
1. "Polyimides, Synthesis, Characterization, and Applica-
tions," Vol. 1 and 2, K. L. Mittal, Editor, P l e n u m
2. R.C. Haushalter and L. J. Kraus, Thin Solid Films, 102,
161 (1983).
3. R. C. Haushalter, Private communication.
4. G. S a m u e l s o n and S. Lytle, This Journal, 131, 2717
(1984).
5. S. Mazur, U.S. Pat. 4,512,855.
6. S. Mazur and S. Reich, J. Phys. Chem., 90, 1365 (1986),
and in " I n t e g r a t i o n of F u n d a m e n t a l P o l y m e r Sci-
ence and Technology," L. A. Kleintjens and P. J.
Lemstra, Editors Elseviers, London (1985).
7. K. Zhang and D. C. Neckers, J. Polym. Sci., 21, 3115
(1983).
8. N. Winograd and T. Kuwana, J. Electroanal. Chem., 7, 1
(1974).
9. T. P. Russell, H. Gugger, and J. D. Swalen, J. Polym.
Sci., PoIym. Phys. Ed., 21, 1745 (1983).
10. M. Kochi, H. Shimada, and H. Kambe, ibid., 22, 1979
(1984).
11. A. T. Hubbard, Crit. Rev. Anal. Chem., 3, 201 (1973).
12. S o m e representative e x a m p l e s are: K. Shigehara, N.
Oyama, and F. C. Anson, J. Am. Chem. Soc., 103
(1981); J. L e d d y and A. J. Bard, J. Electroanal.
Chem., 153, 223 (1983); and C. R. Martin, I.
Rubenstein, and A. J. Bard, J. Am. Chem. Soc., 1{}4,
4817 (1982).
13. F. B. Kaufman et al., J. Am. Chem. Soc., 102, 483 (1980).
14. J. B. Flanagan et al., ibid, 100, 4248 (1978).
15. L. E. Manring, Unpublished results.

Decomposition Potentials of Crystalline Silicon as Related to

the Photocurrent Stability of p-n Junction Silicon
Semiconductor Electrodes
Yoshihiro Nakato, Tetsuya Ueda, Yoshihiro Egi, and Hiroshi Tsubomura*
Laboratory for Chemical Conversion of Solar Energy and Department of Chemistry, FacuLty of Engineering Science,
Osaka University, Toyonaka, Osaka 560, J a p a n

ABSTRACT
The use of highly doped n § or p+-type silicon layers as electrodes allowed us to measure the onset potentials, Uox, of
anodic currents c o r r e s p o n d i n g to the oxidation of Si in aq u eo u s solutions of various pH's. The Uox value obtained is
0.8-1.1V m o r e positive than the t h e r m o d y n a m i c r e d o x potential e(SiO2/Si) for the Si oxidation, indicating that this elec-
trode reaction has a large activation energy. No definite current peak corresponding to the formation or the re-oxidation of
surface silicon hydride was observed when scanned up to a potential ca. 1V more negative than the thermodynamic redox
potential e(Si/SiH4) for the Si reduction, or scanned backward, showing that the Si reduction also has a large activation en-
ergy. From these results it is concluded that Si electrodes must be stable when used for the reaction of redox systems hav-
ing the standard redox potentials close to or somewhat more negative than Uo• Since U,,xis located at nearly the same level
as the t h er m o d y n am ic hydrogen evolution potential e(H+/H2), this leads us to understand that Si electrodes are stable for
use in hydrogen evolution either in the dark or by illumination. The U,,~values and the flatband potentials U~o for n-Si were
nearly parallel to each other, and showed nonlinear dependence on pH.

S e m i c o n d u c t o r p h o t o e l e c t r o c h e m i c a l (PEC) cells have
attracted m u c h attention in relation to solar energy con-
version. This m e t h o d has an a d v a n t a g e in t h a t solar en-
ergy can be c o n v e r t e d directly into storable chemical en-
ergy (1-11). In addition, it has a m e r i t in that low cost
s e m i c o n d u c t o r m a t e r i a l s s u c h as p o l y c r y s t a l l i n e (12),
g r a n u l a r (11), and pin-hole c o n t a i n i n g (10) films can be
used effectively.
T h e m a i n difficulty in the s e m i c o n d u c t o r P E C cells
lies in the c h e m i c a l instability of the s e m i c o n d u c t o r elec-
trodes in a q u e o u s electrolyte solutions. A l t h o u g h silicon
has an ap p r o p r i at e bandgap for solar e n e r g y c o n v e r s i o n
and is widely used in solar cells of both solid- and PEC-
types, its n a t u r e of b e i n g q u i c k l y c o v e r e d w i t h an insu-
lating o x i d e layer m a k e s its e m p l o y m e n t in P E C cells
difficult. Th e t h e r m o d y n a m i c s t a n d a r d r e d o x p o t e n t i a l
e~ for the Si o x i d a t i o n is h i g h l y n e gat i v e,
-0.857V vs. n o r m a l h y d r o g e n e l e c t r o d e (NHE) (13). The
t h e r m o d y n a m i c standard r e d o x potential e~ for
t he Si r e d u c t i o n is +0.102V vs. N H E (13), l e a d i n g us to
* Electrochemical Society Active Member.
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predict that Si is also unstable for use in electrodic pro-
cesses such as h y d r o g e n evolution.
A l t h o u g h t h e o x i d a t i o n and r e d u c t i o n r e a c t i o n s of Si
are very i m p o r t a n t in solar energy t e c h n o l o g y as well as
all o t h er silicon d e v i c e t e c h n o l o g i e s such as t r a n s i s t o r s
and LSI's, no detailed studies have been m a d e on them.
We h a v e f o u n d that the o n s e t p o t e n t i a l s of a n o d i c cur-
r en t s c o r r e s p o n d i n g to the o x i d a t i o n of Si can be mea-
s u r e d by u si n g h i g h l y d o p e d n § or p+-Si layers as elec-
trodes. The onset potentials for the Si-reduction cur r e nt
h a v e also been i n v e s t i g a t e d . S u c h e x p e r i m e n t s are im-
possible with normal, m o d e r a t e l y d o p ed n- or p-Si elec-
t r o d e s b e c a u s e t h e y form p o t en t i al barriers at the elec-
trode-solution interfaces and show rectifying
current-potential curves. The onset potentials for the Si
o x i d at i o n and r ed u ct i o n w h i ch are influenced by kinetic
factors s h o u l d give a t h e o r e t i c a l basis for d e t a i l e d
discussions on the electrode stability. In the present pa-
per we will report and discuss the m e a s u r e d onset poten-
tials as c o m p a r e d with the t h e r m o d y n a m i c ones. T he
flatband p o t e n t i a l s UFB for n-Si e l e c t r o d e s and t h ei r pH