Professional Documents
Culture Documents
TRANSFER IN ORGANIC
SEMICONDUCTORS
ENERGY AND CHARGE
TRANSFER IN ORGANIC
SEMICONDUCTORS
Edited by
Kohzoh Masuda
Osaka University
Toyonaka, Osaka
Japan
and
Marvin Silver
University of North Carolina
Chapel Hill, North Carolina
v
PREFACE
Kohzoh Masuda
Marvin Silver
(Editors)
Contents
I. INTRODUCTION
Opening Address 3
H. Akamatu
UV Excitation of Anthracene 31
M. Kawabe
K. Masuda
S. Namba
vii
viii CONTENTS
III. THEORY
Green Function of an Exciton Coupled with
Phonons in Molecular Crystals 61
K. Iguchi
IV. CRYSTALLIZATION
Glass-Forming Photoconductive Organic Compounds.I.
Phase Change and Single Crystal Growth of 1,3-
Diphenyl-5-(p-Ch1oropheny1)-Pyrazo1ine 77
K. Kato
M. Yokoyama
Y. Shirota
H. Mikawa
M. Sorai
H. Suga
S. Seki
VI. SUPERCONDUCTIVITY
The Problem of Superconductivity in Organic and
Organo-Metallic Compounds 145
W.A. Little
H. Akamatu
Ohka, Yokohama
I am more than happy to meet together with you and to discuss our
common interests, the enrgy transport and the charge transport in
organic molecular crystals. We are grateful to NSF and JSPS for
the sponsorship of this meeting. I must express my thanks to Dr.
Silver the coordinator of U.S. side and to Dr. Masuda the organiz-
er of Japanese side, for taking trouble of promoting this meeting.To
such a meeting as this, of a group of specialists, I have nothing
to say as an opening address. However, if it is needed I would
like to do it in very few words.
It is more than twenty years ago when the electrical conduc-
tion in organic solids attracted our interests. In 1960 we met
together in Durham, North Carolina, and discussed on anthracene
crystal just as we do in this meeting. At that time, organic cry-
stals meant a new field of investigation and we were excited facing
to this field.
Since then,many things have been known and many informations
have been accumulated concerning not only homo-molecular crystals,
but also inter-molecular compounds. After TCNQ had been found by
the people of du Pont, a new field of ion-radical salts has been
opend. Our knowledge of organic solids has been improved very much
Is it still a new field even to-day? I think it must be a main
problem to be discussed in this meeting. If it is, what do we mean by
a new field? Probably it has two meanings as you know. One is a
virgin field of investigation to which we can apply principles or
methods that we have and used successfully in other cases. The
other means a field of investigation which demands quite a new
principle or a new theory. After nearly twenty years investiga-
tion, "anthracene" seems still requiring a theory for itself.
It seems me that there are two trends of approach to the pro-
blem. One is a way of physicists, I mean a stand-point of more
3
4 H. AKAMATU
ORGANIC INSULATORS
7
8 M. POPE AND W. WESTON
CII
- 10 5
"E
u
<t
-
t?
>- 10 7
I-
CJ)
Z
l.LJ
Q
I-
Z J() 9
l.LJ
a::
a::
:::>
u
10" I I I I I I I , ! , I , ", , , , ! II ~
~
10 too 1000 o
~
m
VOLTS (V) >
Z
o
Fig. 1. Voltage dependence of hole current density through a 230g thick anthracene ~
crystal. Electrodes: O.lM Ce4+ in 7.5M H2S04 (anode) and H20 (cathode). ~
m
Electrode area is 1.6 X 10- 2 cm 2 • ~
oz
o<
~
»
Q
m
o
m
."
16 m
Z
o
m
Z
14 ()
m
o
"T1
12 ()
:I:
»
;0
0 10 Q
m
0 o
m
)( 8 Z
en
::::j
<ll.\cxr -<
<3 6
• • • •
0 8 12 16 20 24 28 32
17.4
VOLTS (V)
Fig. 2. Voltage dependence of average excess total charge density, (n tot ) ~ 6~/~o' in a
230g thick anthracene crystal. Electrodes: O.lM Ce 4+ in 7.5M H2S04 (anode) and
H20 (cathode). Measured value of ~ is 53 s-l; calculated value of 7 r ~ 5 X 10- 11
3 _ l o t
cm s .
~
20
16
o
o
-;; 12
C!l.laf
<J 8
~
VOLTAGE DEPENDENCE OF CHARGE DENSITY 13
10-4 r----------~-----r--~r__.--r_~,_,_,
-6
10
-
'"'E
0 -7
S 10
..,
-8
>-
.... 10
en
z
w
10 9
0
....
Z
W
fr: -10
fr:
:::> 10
0
-II
10
-12
10
100 1000
REFERENCES
(10). M. Pope and W. Weston, Mol. Cryst. and Liq. Cryst. (to be
published) •
(11). P. Avakian and R.E. Merrifield, Mol. Cryst., 1, 37 (1968).
(12). J.S. Bonham and L.E. Lyons, Aust. J. Chern., 26, 489 (1973).
(13). L. Onsager, J. Chern. Phys., ~, 599 (1934).
(14). N.E. Geacintov and M. Pope in Proc. 3rd Int. Photocond. Conf.
Stanford 1969, ed. by Pe11, Pergamon Press Ltd. 1970.
(15). W. Meh1 and B. Funk, Phys. Lett., 25A, 364 (1967).
GEMINATE CHARGE-PAIR RECOMBINATION IN MOLECULAR
CRYSTALS*
17
18 C. L. BRAUN AND R. R. CHANCE
Table I
Experimental Slope to Intercept Ratios (5/1) and
Zero Field Quantum Yields (Pol· b
Free Carrier 5/1 (la-Scm/Volt) ~o x 105
Electrons (Fig. la) 3.21 + 0.12 8.75
Holes (Fig. 2c) 3.02 "+ 0.08 9.l6 a
a The extrinsic contribution to the hole photocarrier
quantum yields was estimated to be less than 3%.
b
The absolute error in the Po values is estimated
to be about +25%.
GEMINATE CHARGE-PAIR RECOMBINATION 19
1.5
v
Q
X
o
-.oJ
W 1.0
>=
~
::::> LO
I-
z
<I:
::::>
o ELECTRONS
5 10 15 20 25
APPLIED FIELD (KVlCM)
1.5
v
0
x ~
0
-.oJ
W
>=
~
::::>
I-
Z
<I:
::::>
0
Q5
5 10 15 20
APPLIED FIELD (KV/CM)
Figure 2. Hole Quantum Yields at 255 nm. Curve c is
for a virgin sample while in curve d trapped electrons
reduce the low-field free hole yield.
20 C. L. BRAUN AND R. R. CHANCE
15
>.....
1ft
5 10
I
o
~ 5
(/)
-
20
1- d POOLE FRENKEL
4 6 8 10
APPLIED FIELD (104 \vCM)
ANTHRACENE CRYSTAL
The treatment for the charging of the deep traps with carriers
was carried out by the illumination of the light at 395 nm under the
application of the high field for about one hour. The carriers
generated in the surface were injected into the crystal and some of
them were trapped in the course of transit process. The polarity
of the trapped carriers was prescribed by the polarity of the illu-
minated electrodes. After the charging treatment many trapped
u,2S
Hole
1-- - - - -5n02 Electrode tC?Ui Electron
1-_ _ _ _ _ 5n02 Electrode
~
_ - l 104§.
'" -
.
0«
103~
:;: _~-.;;:---;102 ~
>
-c=7_..c-~-r-tlOl i
~~~~:::;;:::::;;;;:.".
~
- -----"<--il00 &.
t---
A Hole I
'\
./'
-.~ ., 5n02 Electrode
--
~.
~\
-' \,
..,f
~ .
'- ' '
\
:~""
'-...,
~. V, V"'\,,~\
- '~
I I I 1 I I I I I II
BOO 1200
Electron xKf28
5n02 Electrode
~~
~
102~
:J;2
I '~
1O~
c:
~
Jl§
'" ~
trum of the hole photo current enhanced by the detrapping for the
trapped holes were composed of three region, that is, below 1.5 eV,
1.5 eV-2.S eV and 2.5 eV-2.9 eV. The spectrum below 1.5 eV is
interpreted by the direct optical release of the trapped holes from
hole-trapping level at about 1 eV as discussed by Adolph et al.[l]
The structure of the spectrum from 1.5 eV to 2.5 eV is the same as
that of the singlet-triplet absorption spectrum in anthracene crys-
tal. [6] Therefore, it is explained by the indirect release of the
trapped holes by the interaction of them and triplet excitons.
Further, the peak at about 2.8 eV is considered to be due to the
interaction of the trapped holes and singlet excitons.
1 eV 1 eV
d n trap
- k nT n trap (2)
d t
o 0
000
200
50 100 150 200
Time (sec)
Table 2
Inj~cting
Contacts Hole Electron
Adolph etal
(1964)
hole
1.1 eV
51 ;Ii - trapped
hoie /
/
0.95 eV
Many etol
electron 51 .Tl - trapped
(1969) electron
Ours
1.0eV 1.0.1&.ll eV
(1973) non 51 .Tt - trapped S, .1i - trapped
hole electron
References
[1] J.Ado1ph, E.Ba1dinger and I.Granacher; Phys. Letters ~ (1964)
224.
[2] A.Many, J.Levinson and I.Teucher; Mol. Cryst. 5 (1969) 273.
[3] U.Itoh, K. Takeishi and H.Anzai; J.Phys.Soc.Japan ~ (1973)
810.
[4] U.Itoh; J.Phys.Soc.Japan 35 (1973) 514.
[5] U.Itoh and H.Anzai; submitted to J.Phys.Soc.Japan.
[6] P.Avakian, E.Abramson,R.G.Kep1er and J.Caris; J.Chem.Phys. 39
(1963) 1127.
[7] V.Ern, H. Bonchriha, J.Fourny and G.De1acote; Solid state
Comm. 9 (1971) 1201.
UV EXCITATION OF ANTHRACENE
Toyonaka,Osaka, Japan
31
32 M. KAWABE, K. MASUDA, AND S. NAMBA
~
u 2Or---------------------------------~
III
x
)(
en
c:
l<
•
445 nm
425
x •
...... o 405 x x •
x
•
x x
t' 10 x x )( I
x Xx x x xx
x x o
x
• • •o o o
• 0
0
a
0 100 200 300
TEMP. (K)
The third term in the integral is due to the light reflected back
into the crystal from the front-inner surface of the crystal.
In this case it is assumed that 90 % of the light which is incident
upon the inner surface is reflected back into the crysta1 2 ) and the
reflected light from the back surface is neglected because most of
the short-wavelength fluorescence is reabsorbed before reaching the
back surface of the sample. Using the room temperature values of
a o 3 ), aI, a(w)4) and g(w), the integral of equation (3) is calcula-
ted to be 0.67 for the fluorescence of 405 nm. The total fluores-
cence Ir which suffers more than one reabsorption is
O,67B
I. Ir i , 1-0,67B
(4)
1.
(5)
-
as f11ows,
~
·2 6 r - - - - - - - - - - - - - - - - - - - ,
:::J
Jj
.s5
>
I-
in
z4
UJ
I-
z o
;:3
u
z •
~ 2
Vl
gl
UJ
....
Ii.
5 10 15 20
INCIDENT PHOTON DE N SIT YOO<fCn'\2 sec')
-n1 = (9)
"c
:J
.ci
L-
~
>-
f0-
Ul
Z
u.J
fo-
Z
~
u.J
u
(a) z
ts
VJ
u.J
ex:
0
:::>
--I
lJ..
400 420 440 460 (nm)
C
:J
.ci
L-
a
>-
~
til
z
u.J
fo-
(b) ~
u.J
U
Z
u.J
U
VJ
w
ex:
0
:::>
-'
lL
WAVELENGTH
REFERENCES
INFRARED
1. INTRODUCTION
2. EXPERI~NTALS
H2Pc, CuPc, CoPc, ZnPc, NiPc, PtPc, PdPc and SnPc were synthesiz-
ed following the method of Linstead 3 ) or by heating the phthalo-
37
38 K. YOSHINO, K. KANETO, AND Y. INUISHI
200K
E
t
::>
4
u
o
'0
-a 2
10
c..Pc sor9" c~
§8 -- 42K I - -'2K
,
D
II -- 77 K - - 77 K
-6 ----- JOO K - -lOOK
!:
;;
c
.. 4
'€
§.. 2
£
0
07 08 12 13
10
; '. •50
" ... ~.
PIP\: ~" cryS~I
D 8 42K
:0 10 II
!: 6 20 K
.
~
~
c
, ~500 \" 7 7 '"
1301\
" ........
..;; .... 273 1\
0
10
....... 18 K
"nQI"
CuPc cry,.t.oI "'
5 8 - - 42 K
..
~
.§
- - - 85 K
-- 12K
6 - -100 K
?: --150 K
~
f 4 230 K
"5
..~
"II
2
E
~ --..
• Q04 106 Ul8 116 118
_'Or-----------------------------------~
~
HzI't 4 2~
~ --0'*""'9
.! ...•.. ofter heoln;1
~O
~
~
i Q~--=-)-----="j~~-------,-L---------,L--
700 800 'lOO
wove lenglh
1000
ImJll
10 ....--------------------,
CuPc 4.2 K
...,apOfat~d thin film
"
\
\,,20
\
'"
..............
116 118 120
way. ""9th ()J)
~10r-------------------~------------------~
.~
--- 42K
" SnPc PoI..,orat.d
~ 8 - - 77K
., thon f 'lm
- - 120K
:;6 ----. 190 K
.
'w;
c
'£ 4
- -260 K
310 K
c
o
'w;
III
~
~~OO~-------900~~~-----IJ
OOO
------~~'~~--------'2~OO
way. I.ngth (m f' )
~IOO
" ZnPc
of Ruby loser
~
C
t 10
o"
u
o
s:
Q.
'I 10 100
loser intensity (orb. unit)
REFERENCES
I. INTRODUCTION
45
46 N. ITOH AND T. CHONG
I-hydronaphthyl
very stable
radical
C-radical
Naphthalene 2-hydronaphthyl
4.0
radical
I-dibenzo-cyclo-
1.0
hexadienyl radical
C-radical
Anthracene 9-dibenzo-cyclo-
very stable
hexadienyl radical
9-Dibenzo
cyclohexa- 2.32 - O.Oll
dienyl radical
Wave Length(nm)
600 550 500
3
Emission + Absorption
-u
---- bf'
'5
.d 2
;
.....
f£1
calculated by Pawley 17) and the Raman spectrum 18) of the naphtha-
lene crystal, indicating that the lattice vibrations are not dis-
torted very much by the presence of the radical. The detailed
analysis of the spectrum is in progress.
REFERENCES
Toyonaka, Osaka
53
54 K. MASUDA AND S. NAMBA
I08r--------------,
o
o
o
CONCENTRATION [n/m']
space
a(A) b(A) c(A) P group
- - - - - - - - - - - - - - -- - -
HrPc 19.9 4.72 14.8 122°12' Pz1/.
Ni-Pc 19.9 4.71 14.9 121°54' Pz110
eu-pc 19.6 4.79 14.6 120°36' Pz1/.
Zn-Pc 19.22 4.87 14.52 120°02' Pz1/.
CONTRIBUTION OF FREE RADICALS TO ELECTRICAL CONDUCTIVITY 55
Ie I relCl
(t I
:;:
~
>-
~2 5
w
z
w
~ I
~2J
t- . .
~
o
w
>
0::
W
<J)
i§ 15
1.5 2.0 2 .5
E STIMATED ACT I VATIO N ENERGY l eV)
2.82 I 19.62
Calc. I 67.28
can be evaluated as
2E = I - 2P (3)
REFERENCES
MOLECULAR CRYSTALS
Kaoru Iguchi
(2)
where
(3)
where
= [(-1.f..L«(Wl~>
7l:0 1i, n!
(5)
in symbolic notation. After a calculation we have
([wJ) =0,
~ -1 Z ... ( n- t ,1
«(W) )/2! = (F) = (1)
N fC(~)"'l.iA~t+.BKi{l-~r(i)ltt /-1&,)1
tBU){1- ~)(r(-i51~tl-#t.)},
where t;, (6)
,''''---',,, ,,----,
I t
, '\
,
•
•
Fig.l Feynman diagram of contractions in eq. (8) •
y
1
([W]4) = 3xZ.l.x< F~ ,
and generally
where
Ek = f#( -to Nlt C2(p{ Vj/ii.~~g. -Cij -r 1 )/-tstk~ i.
Dl~ = C~i)/N(-tJl~8-)~, D~ = C~~)/N(tQtg.)~
(12)
Expanding the complicated exponential function in the right-hand side
of eq.(ll) and reassembling we have
i G-k ( t)~I'(i. EJ( t/1\..) ~~
= H'(~!
~ rco s..o
Dr, ~ir ! ii((v;
s!
-+ 1t ~L'>{i(r5t -s5l+ )t}J
,I<, tg (13)
Pk
== {,;oo(D~t/DJj)
00
In rGl«t)~( i. E t/~)dt
• eo
iG-,iE) =
-eo
~I<
= 21t r {iTtJ7TL~e?tp{
}dt·tJXp
E- E -kS
it(rJl n+ 1
-SJ'-/(,)J
o it -}
Dr J)s 1i.;{ii.;+l)S (16)
where 1. means a pair of rand 5, and Rfj = ".., i ;'
Then we have l"! S•
where ..e-set means a set of /.. 's, and j numbers the wave- vectors of
'"i
phonon, and I (.Q-set ) = R I~ flor an i-set. The poles of Grk(E) ,ive
the possible energie~ of exciton after a long elapse of time, For
each .i-set the energy is given as :
E= EK+tr(SQ;-rQ;!)j
= EK +N-1I.. (C~(~)A~i)i'" J~(S-l")twi -(S+ r){£j(- fti"~)1 .
J
•
.J (18)
The quantity fl.5ikq is the increase of energy by virtual phonon-creat-
ion process ; f.1<~ E/(.S"'~ and -t\Slk is the decrement by the phonon-
annihilation process; f/( +1i~~ fl<~f ~ The resultant increase of phon-
on energy is (s - r)h~ , and (s + r)(Ek-fk-l'~ ) is the resultant decrea-
se of free-exciton e2-ergy, and s + r is the number of relevant phon-
ons. The term C (q}A is the energy shift due to the exciton-
phonon interaction. T~3-s our method includes the multiple scatter -
ing processes until infinity, though not perfectly. Also we see the
effect of hopping term is onl y the replacement of Kq by C(q).
We shall compare our result with 1;;.h~se by other workers. By the
equation-of-motion method of Zubarev ~ 5 with the first.-order decoupl-
ing approximation, the Green function with energy argument is obtai-
ned as -1 -1
G-I«(E) = (21'C.) (E -£/( -MK(E» (19)
66 K.IGUCHI
-tID
(20)
where E+= E + 0, and the selt Energy ~ is given as :
(22)
Then we have, for t >0 ,
G-:(t) = -i ~r(-i.El(.tl-k)
~ _i~p(-L(£k+M.tEic)}tk- (23) tk(t,c)t/1').
We see that EI<TMi~) is equal to Ek in eq. (n), and we may say the
equation -of-motion method is of lower order in approximation than our
perturbation expansiom method. Also the factor exp(-~t/i'i) means
the exponential decay of probability to find the exciton in the k-state
though our eq. (15) indicates a c01'lplicated oscillatory behavior.
By the calculation of Takeno oJ the pole of Gk{E) is obtained 'is the
root of the following equation :
E; - Ek = Mk (E ) = 1: Og) ( ii + 1 + i7j. }
t N I E- E/( - -#1cJg. E- fl<+-i1- 4J1- •
(24)
The approximate zero-phonon and one-phonon ene:rgi¢s are:
Eo = t/(-t Cfgj)/N*'wo .•
J ~
which corresponds to E - •
q
REFERENCES
Shozo Takeno
Kyoto, Japan
69
70 s. TAKENO
To begin with, we consider a system of identical atoms. Let
Ef and lfif be the natural energy eigenvalue and the corresponding
eigenfunction of an atom at a site i specified by quantum number
f. Also, let atf and aif be creation and annihilation operators of
an electron in the state~if; Any two a's belonging to different
atomic sites are taken to be commutable with each other. We take
the Hami1tonain of the system to be of the form
tC:I~f~ ~+t[ I
if itwrr<ff',V(ijJI f".f>a.; 4I1,a~"~/ .. i'l
& 'H'
<fIV(E)f')Q."- a.f'
-OJ Ii
(1)
Here, V(ij) and V(i) denote the Coulomb interaction between the i
and j atoms and the interaction of the i atom with an external
field, reSjective1 Y• The definition of the matrix elements are
<ff'IV(ij) f"f"'> f=srW:C")~~(~)V'(1Jl~crU'f"'(J) d.W1dtj and
<fIV(i) If'> = ffq:C,\lVtli)Yi.f' 't1,)tl'i.ln what follows we take into
account only two of energy states of a given atom, the ground
state and an excited state under consideration, which are denoted
by f=O and f=l, respectively. We introduce exciton operators At
and Ai by the equations
A+i = a+
i la io = cri + an d Ai = a+ a
io i1 = cri ' (2)
where it.
(OiK " Oi'" O'i' ) with o:t~ <Six.:t. O"i' =
are the Pauli
operators. Several relations useful for later calculations are
listed below:
(4)
(5)
(6)
(7)
or
FRENKEL EXCITONS IN A TWO-LEVEL-ATOM MODEL 71
where
1:( ij) -< Il IV'GiJI II') - .2.<OI/"'U;)/ 01 /,"1- <00 /TOi) 100>,
(9)
a~ =(nil-niO)Eni/2. (11)
(12)
-+
is the expectation value of ~i with respect to the quantized
atomic wave function
(13)
with
~
i 0, w~),
n,=(2v*,
~
(14)
72 s. TAKENO
r
where
* * * -1
where y(Wi)=-(dwi/dt)(w) • These equations are exactly
equivalent to Eq. (14), ~ut in the form (16) and (17) we have a
simple physical interpretation. The atomic dipole moment responds
to an applied field ft according to a driven po1arizationZwave
equation, with t2e feature that the coupling constant -2~ w*n
and the term -2~ w~nilT(ij)p. are proportional to the popuiation
difference n , reversitg signJ when n i passes through zero.
Equation (17t is simply a statement of conservation of energy.
There is one further immediate consequence of writing the equations
in this form: Multiplying Eq.(16) by dPi/dt from the ri~ht, sub-
stituting Eq.(17) and neglecting the time variation of wi and the
non-commutativity of Pi and dPi/dt, we get after integrating:
(' It~. \~
d:tJ../ +
ttl-/) ~
Wi
...1 ~.a
ri 1- wt~ I'll -,)l Wi,
a~.l
I (18)
..
recast into the form
(20)
REFERENCES
-@ 9"It- ii-@
CI 0 CH, ,N
N
© (1)
77
78 K. KATO ET AL.
PHASE CHANGE
a) crystal
o§
C)
.,
.<= b) glass
~ 1----.>.-,
165 1
J
215
Temperature (·C)
U 30
SI
250
r<'l
......
E
..
~1.0 20 ~
u ..,
15 ~
en
c
i 10 ,g
t .
E
..i·
5 ~
n.
o.95L...~""""~50r--~"'-'-TnIOOn'--'--""""'II5Ol;;;-'
Temperature ('el
/
(when he:ted above)
\mp. 130 C / "
( when cooled Without)
a seed crystal
\,
I
when cooled below mp )
and ke~t between supercooled liquid
( 130-80 C in the
presence of a seed 1
transition )
cr stal crystal or without a ( temperatu;e
y ~ seed for a long time 16.5-21.5 C
,/
~ ( when warmed above 80'C ) /
with a seed crystal
glass
(belOW transition)
temperature
a) single crystal
b) glassy state
600
Wavelength (nm)
EXPERIMENTAL
T
t
Fu
t
60 100 1!50
Temperature ,-C)
REFERENCES
Tokushima, Japan
85
86 S. KANDA, A. SUZUKI, AND K. OHKAWA
~ LJ tJ tJ l:J tJ LJ
- - N- - - N--
'C-C/
S"" 's
water t
Cu* Cu'"
Cu*
Cu* Cu* Cu*
Fig.2 Supposed pattern of the reaction mechanism for stereospecific
R-DTOA-Cu
N N N N N
C C N@N CC N@N C CNli)N CCN@N CCN@N C
N N ~ N N
~ ~ ~ ~ ~
C C N<i)N CCN(i)N CCN@N CCN@N CCN@N C
~
C C N@N CCN
~(i) ~
Nee N' Nee N
~<i> ~
Nee N@N C
~ ~ C ~ ~
Fig.3 The top-view of the stereospecific two-dimensional net-work
model with dimer structure of copper acetate type; this is not
approved(see text). Double circles indicate pairs of two copper
ions.
......s
"
's
"
Fig. 4 The proposed molecular model of stereospecific dithiooxam-
ide copper coordination polymers. Unevenness of its plane is indi-
cated by arrowhead affixed to nitrogen atom.
SEMICONDUCTIVE COORDINATION POLYMERS 89
Literature Cited
1) S.Kanda,H.A.Pohl, "Organic Semiconducting Polymers," Chapter 3,
J.E.Katon, Edited, Marcel Dekker, New York, N.Y., 1968.
2) S.Kanda, S.Kawaguchi, J.Chem.Phys., 34,1070(1961).
3) S.Kanda, J.Chem.Soc. Japan, Pure Chem.Sect.,( Nippon Kagaku
Zasshi), 83, 560 (1962).
4) S.Kanda: J.Chem. Soc.Japan, Ind.Chem.Sect.( Kogyo Kagaku Zasshi),
71,1426(1968).
5T H.Kobayashi, T.Haseda, E.Kanda, S.Kanda, J.PhyS.Soc.Japan,18,349
(1963) --
6) S.Kanda, A.Suzuki, K.Ohkawa,Ind.Eng.Chem.Prod.Res.Develop.,12,88
(1973). --
7) P. J.Wheatley, J. Chem. Soc. ,1965,396.
8) T.A.Scott,Jr., E.L.Wagner, J.Chem.Phys., 30,465 (1959).
B.Milligan,E.Spinner, J.M.Swan,J.Chem.Soc., 1961, 191~
P.E. Fielding
91
92 P. E. FIELDING
4
We have recently published the results of an investigation
carried out some years ago on the thermal stability and radiation
damage in the phthalocyanines. The results of immediate interest
concern the effect of growth conditions on the concentration of free
spins (g = 2.003) which is taken to be a measure of the impurity
content. A diamagnetic phthalocyanine such as H2 (pc) with a free
spin concentration of ·less than 1015 spins/grm. was sublimed during
different experimental runs. The temperature gradient along the
sublimator tube was varied as also was the time taken to grow
crystals of a reasonable size ( 20 x 3 x 1 mm). The results are
shown in Table 1. In another experiment samples were sublimed at
different temperatures, the duration of each run was recorded, and
comparison samples were taken from growth regions which were at the
same temperature. See Fig. 1 for the results of typical experiments.
These series of experiments show that such purification procedures
can dramatically increase the concentration of free spins and that
relatively low free spin concentrations occur in BH2(pc) crystals
when the starting materials sublimed at above 500 DC in nitrogen and
the crystals grown at a relatively high temperature of 450 DC. \\Ie
have shown 4 that absorbed oxygen is not responsible for these
results which are thought to be due to decomposition products
trapped in the crystals. Repeated sublimations would not lead to
any increase in the purity. Varying the nature of the entrainer
gas does not appear to reduce the decomposition as Day and PriceS
have shown that BH2(pc) grown in a 1:9 N2 :H 2 entrainer gas mixture
still contained an appreciable free radical concentration.
6 19 20
Barbe and \.festgate report trap concentrations of 10 -10
trapping centers/cm 3 in SH2(pc), a concentration comparable to that
of the free spins reported in our work. If we accept that these
two parameters are directly related to the same impurity species
then it appears necessary to find some alternative way to prepare
single crystalline B(pc) in which the trap concentration is much
Table 1
Sublimations performed in a nitrogen atmosphere
Subliming Temp. (DC) Growing Temp. (DC) Spin Concentration
600 525 1.0
390 9.0
582 488 2.0
545 468 2.4
360 8.7
496 420 1.6
360 4.8
450 351 10.0
19
100 units equals 10 spins per grm of H2Pc
GROWTH AND PURIFICATION OF PHTHALOCYANINE POLYMORPHS 93
1650
550
u 500
""'
0
QI
...
~
450
...
CIS
QI
~
QI
Eo<
400
4.3
5.5
350 13.5
~~--L-~~--~~--L-~~~~~--~0.3
o 15 30
Distance (em) from initial position of sample in furnace
o
4.80A
os ;G',SX
(a)
~"
/ a- 26.2X
(b)
Table 2
Honigmann 's Ashida's Honigmann's B-CuPc
aIIa - CuPc
ex 60% H2SO4
-
~tbr CuPc trielinie
ale - CuPe
ex 96% H2SO4
° 26.2 25.92 26.4
a(~) 19.61
b(A) 3.8 3.790 3.8 4.80
c (A) 24.0 23.92 24.2 14.74
8(°) 93.9 90.4 90.1 121.51
y(O) 95.6
Z ... 4 4 4 2
GROWTH AND PURIFICATION OF PHTHALOCYANINE POLYMORPHS 95
(a)
(b)
~~
J V \../1.
(c)
35 30 20 15 s
28
This b// form was prepared by first heat treating the mica in
a vacuum, (5 x 10-5 torr) at 300°C for 1 hour. The substrate temg-
era turf was then lowered to 150°C and Cu(pc) filmsoof between 500A
to 900A thick were deposited at the rate of 20-30 A/minute. Under
these conditions oriented polycrystalline regions grow in about 30
minutes such that the b axis of the Cu(pc) lies at either ±60o to
the b .axis of the mica.
/'\
1.7
'/
\ 1. 7
(a) 1.5 I 1'1
(e)
1.3 I II ~e
1.1 I ae V '"'"\../ 1\
.9 I \
.7 J I- ....... ./
/
b \
....... / if II \
»
.5 b II
1\ ..\. / \
II)
!:= .3
Qj J ./
""
r-i
<II .7 r
....... .6
()
i \/\ t~ .I
1\ (d)
o
P-
.5 f, !~
L j \
./
j ~
(b) .4 if \\ r
./- r-,
lL \ r ~\
.3
.2 IlL
V ~
\
\
,
\
1
fj V
\
\
19 18 17 16 15 14 13 19 1 .7 16 .514U
v x 10
-3 (em)
-1 -3 -1
v x 10 (em)
References
1. Fielding. P.E. and MacKay. A.G •• Aust. J. Chem •• 1964. 11. 750.
2. Fielding. P.E. and Stephenson. N.C •• Aust. J. Chem ••
1965. 18. 1691.
3. MacKay. A.G •• Ph.D. Thesis. University of New England. 1968.
4. Boas. J.F •• Fielding. P.E •• and MacKay. A.G •• Aust. J. Chern ••
in press.
5. Day. P •• and Price. M.G •• J. Chem. Soc.(A). 1969. 236.
6. Barbe. D.F •• and Westgate, C.R., Solid State Commun.,
1969. I, 563.
7. Hamann. C•• phys. stat. sol. 1968, ~ 311.
8. Lucia, A.E., and Verderame, F.D., J. Chem. Phys.,
1968. 48, 2674.
9. Ashida, M., Uyeda, N•• and Suito, E•• Bull. chem. Soc. Japan.
1966, 12., 2616.
10. Kirk, R.S •• Mol Cryst. 1968, 5. 211.
11. Honigmann, B., Lenne. R.u •• and Schradel. R•• Z. Krist.,
1965. 122, 185.
12. Abkowitz. M•• and Sharp, J.H •• J. Phys. Chem., 1973. ~ 477.
v. TRANSPORT IN AMORPHOUS STATE AND POLYMERS
MOBILITY MEASUREMENTS IN POLYMERS BY PULSED ELECTRON BEAMS
1 INTRODUCTION
101
102 Y. INUISHI, K. HAYASHI, AND K. YOSHINO
2 EXPERIMENTAL METHOD
',~::"'/ ..--,
~ 10 5 ...
't. . .... ;::~ 8 :E~
......
- ~6
,;;:~
3!:: ~
~-
(0) E * 0.2 My/em. hor,zontol !ICOI.
:---
\11-
o
I mSf'C Idly.
.... " .
2~,.!
a:
, " " ~ .,. 1 ....
. ~'tk . : . ..._... . O-'~_'----~~~~-L~~~~~O
o 0.3 O.S 0.7 0 .9 1.1
.
RECIPROCAl APPliED FIELD
.. I/E (em/MV)
: *._. :-. . . . : .:
(b) E 01.4 MYlem, h",., zan I 01 scal.
I l'uc/dlY transit time on the reciprocal
of the applied field.
. . . . . .
./ .
( c) E o 1.6 MV/c .n. h"rlzonioi scol.
I I's.c/d,y
...
.....
:E~
30 • U(CTROM
• HOlf I MVy
I.I .. ~ 6
...
+...... ... . .
-u :E-
,;::: ¥
..
_:1"20
~o. /. / !:1
.....
\li-
z •
..
\11-
. . . . . ~ 10
o. / PET 2!~
~/ T.300·K
- .....
0 0
( d) E " .& Mv/em,hOr,zonlol scol. 0 4 8 12 16
1 1J"f'(, /d t ~ THICKNESS
d ("",)
PE T 9 IJm
• 1.8 MV/em
° 1.5 MV/em
5
~..0 . x 1.8 MV/Cm
~ 2
....
• 0
o 1.5 MV/em
."
\ '\\'~
~
1/1
~ 10- 4
N
E
u \x • °\0.25 eV
5 o~ '. \
~x \.,
o
~ 0.30e~ '\.
LOr- 0 ELECTRON 00 0 oX .~
x HOLE 0 / 0 ; ; 0 -00 -
1C~X~ \ HOLE'"
x:1i x-x-
/' 0 0
x10-10
l&J~
1:
C)ID 1A."t.= 9.2 0 .. x
a:~
'"'0
:1: ....
em2/y 0 x'x
\ 0\ .
fi
~C~x~·32 ..,
U;:, 'l'. = 35 IAsee
o dx'xC.
ou 5
~7 0.5 gOxx
2MMA "\
uo 01' XX
l&J- /')X IAh Th =1.2 X 10- 9
.... "
.... ~ 8f emYY
80 .Ix
IX 'h=10IAsee
.
PET 12 101 m 300 oK
1.0 ST } ELECTRON
• "SALOW
;--,;;--.
•••• _e_
o FAST} HOLE
/) SLOW
;j 0
0
o
o
0.2
...<lC"'lI-
"",'If'" r-300'K
REFERENCES
EXPERIMENTAL
109
110 K.OKAMOTO, S. KUSABAYASHI, AND H. MIKAWA
vacuum (10- 7 - 10- 8 mmHg). A 500 W xenon lamp was used as the light
source, and it was monochromatized by a grating monochromator.
RESULTS
I. Photoconductivity of Poly-N-vinylcarbazole
Log iph versus liT plots gave straight lines over the whole
temperature range (20 - 160°C). In 35 kV/cm the activation energy
of the photocurrent (~Eph) was 0.07 - 0.15 eV in the visible region
and 0.18 - 0.22 eV in the UV region. The latter is larger than the
former by about 0.09 eV. In 150 kV/cm, ~ Eph in the UV region was
PHOTOCONDUCTIVITY OF POLY -N-VINYLCARBAZOlE 111
Iif>
$ ,
13),....
c::u ,
.
"-
;:I
f.)
.BI
0
0
..c; •
~
•
IrP
2.0
,...
..
S 1.0
~ ..
,...
S 2.0
..,u
t
1:1
:I
0.5 .j ~
<II
.0
1.0 j.
g 0.3
~
:I
g fil
.0
0
..c: 0.2 0 0.5 ~
~ ..c:
~
0.3
0.2
The comonomer used does not have any large ~-electron system.
The copolymer rich in VCz showed photoconductive properties similar
to those observed in PVCz. As is shown in Table I, however, the
photocurrent of the copolymers was smaller in magnitude by a factor
of 5 - 50 than the photocurrent of PVCz. The photo current decreased
in all spectral region, irrespective of the polarity of the illumi-
nated electrode. The alternate VCz fumaronitrile(FN) copolymer
does not show any photoconductivity. On the other hand, the photo-
current in the PVCz film doped with polystyrene(PS) decreased by
only a factor of 1.5 - 2.5 as compared with the photocurrent in an
undoped PVCz film.
(A)
OMTP doped film
(I)ip~. Small S.C.Effect
(2)ip~. Large S.C.Effect
(3) i p~
PVCz fi 1m
il
3
2 (6)UV Spectrum
,
I
I
•/ ~.
If
I, ,
It ~
I, •
I' ,
,:" ,~
10- 11
*
I,
/,
"
,........,.
I'
(3~
\~"",~/fa..." (5)
'~
-~-~ ......
\
.........
,..,\
I
: lv.....,
\,/ \ (6)
\
3
2
10-13~------~----~-:~__~______~____~____~______4 -__
Discussion
I Carrier Generation.
already produced (or a trapped carrier), and (b) the field near the
surface which may act as part of a diffuse double layer.
II Carrier Migration.
(a) (b)
carriers can move primarily along the chain from a carbazy1 group
to another adjacent carbazy1 group, through the overlap of the /L-
electron systems of carbazy1 rings in the same polymer chain. This
carrier migration process is supported by the correlation between
the crystallinity and the photocurrent and also by the significant
decrease in the photocurrent in the copolymer of VCz with a small
amount of another monomer, which severs the overlap of the 'Il-e1e-
ctron systems of carbazy1 rings in the same polymer chain, thereby
significant hindering the migration of the carriers.
REFERENCES
1) This paper is the summary of our works which have been reported
in the following papers.
K.Okamoto, S. Kusabayashi and H. Mikawa, Bull. Chem. Soc. Japan,
46,1948 (1973); ibid., 46, 1953 (1973); ibid., 46, 2324 (1973);
ibid., 46, 2883 (1973); 46, 2613 (1973); ibid., 41, No.1 (1974)
in presS; A. Kimura, S.-Yoshimoto, Y. Akana, H.lHirata, S. Ku-
sabayashi, H. Mikawa and N. Kasai, J. Po1ym. Sci. A-2, 8, 643
(1970); s. Yoshimoto, Y. Akana, A. Kimura, H. Hirata, S~ Kusa-
bayashi and H. Mikawa, Chern. Commun. 1969, 987.
2) H. Bauser and W. K1opffer, Chern. Phys. Lett., 7, 137 (1970);
Ko11oid Z. Z. Po1ym, 241, 1026 (1970). -
3) W. K1opffer, J. Chem. Phys., 50, 2337 (1969).
4) L. E. Lyons, "Physics and Chemistry of the Organic Solid State",
Vol. 1, ed. by D. Fox, M. M. Labes and A. Weissberger, Inter-
science Publishers, New York (1963) p. 392.
SENSITIZED PHOTO CURRENT IN DYE-DEPOSITED POLY-(N-VINYLCARBAZOLE)
INTRODUCTION
EXPERIMENTAL
121
122 H. KOKADO, Y. OKA, AND E. INOUE
PVK alone ~
~ ~
PVK/rhodamine B
-r V y-\
PVK/pyronine G ~
• •
1 min.
1'y ~
Fig.2 Illustration of photocurrent curves (not in scale)
10- 10
1
1
10- 1 10-11
"""
<Xl
'-'
Eo<
Z 3 3
~ 10- 1
p
u
0
Eo<
0
:z::
P-o
10-1 10- 13
1 10 100 1 10 100
APPLIED VOLTAGE (V) APPLIED VOLTAGE (V)
(a) (b)
l
(1) (2) (3) (4)
air
1.5 j
ip(positive)
~: ~ (\~(\~f\~{\---=--
(a)
(xl0 12 A)
l.....-L.-_
0.5
ip (positive) 0 (b)
(xlOll A)
0.5
0.5
0
0.5
ip (nega tive) 1.0 f (c)
(xlOll A)
1.5 1 1
xlO xlO
T
XIO
-
--
(1) Dye + hv Dye· (excitation of dye)
(2) Dye* + Te ~ Dye+ + Te- (charge transfer to PVK)
-
(2') Dye* + °2 Dye+ + 02- (charge transfer to oxygen)
(3) Dye+ + PVK Dye + PVK+
Dye + PVK + hole (hole injection)
REFERENCES
J. Mort
I. INTRODUCTION
127
128 J. MORT
2 x 10-9 AlOIV.
o 10m sec/div.
10 5
FLUX
I photons / cm 2 sec 1
-'"
u
• 3.lx 10 14
'"
......
>
t:;. 1)110 14
10 3
w <> 3.1 x 10 13
~
<t 0 3.lx 10 12
0:
0 3.1 x 10 II
w
(!)
0:
<t
:r
u
en
0
10 2 #
101L---------L-~------------~------------J
<.> /
'"
t!
II>
>
......
E
<.> /
~
I-
.J
I
Ql
0
~ 10- 8 I • HOLES }
PRESENT WORK
I o ELECTRONS
I .. HOLES
6 ELECTRONS
1 GILL(5 )
I 163 % BY WEIGHT
TNF
~
10-9~~~~----~----~------~----~-----J
o 0.2 0.4 0.6 0.8 1.0 1.2
TNF: PVK l MOLAR RATIO)
(c) Trinitrofluorenone
U • Polycrystalline TNF
QI (Single Discharge)
-
III
...... 104
III
6 Polycrystalline
0
> (Initial Discharge)
IIJ
I-
• Amorphous TNF
ct (Single Discharge)
It:
IIJ
C>
o Amorphous TNF
3 (I nitial Discharge
ct 10
It:
:J:
U
!!!
0
10 2 I 10 100 1000
E (vip.)
ACKNOWLEDGEMENTS
REFERENCES
W. D. Gill
INTRODUCTION
137
138 W. D. GILL
Since the densities of both the uncomplexed TNF and the total
TNF increase rapidly with increasing TNF concentration, the TNF:PVK
data alone was not sufficient to distinguish which TNF density was
active in electron transport. This question was resolved by making
drift mobility measurements over a range of concentrations of TNF
dispersed in a non-complexing polyester matrix. The electron mobil-
ities were found to have the same magnitudes and field dependence as
was measured for comparable ~ TNF concentrations in the TNF:PVK
system. This result established that in TNF:PVK all the TNF molec-
ules whether complexed or uncomplexed are active in the hopping
process. At low TNF concentrations an exponential dependence of
p/R 2 versus R, where R is the average separation of TNF molecules,
is evidence for intermolecular hopping transport of localized elec-
trons. The localization parameter for electrons is a = 0.56 X 10 8
cm- l .
Temperature (OC)
300 200 150 100 50 25 0
10-2~~--~~--~~---r----~----r----r--~100
\~
\~
\~ I
'\1
\ I
\. \~
lrr1
~:"1 '\
1\
~
- ~!\\ en
:>
Liquid" \ \ -..
I\.
I
\\ \ N
E
(.)
I \ \ c
I \ 3-
10-4 I \ \ 10- 2
Tmelt=17~C \ \
U
\
QJ
\
en
:>
-..
N
E
\ \
~
c
\ \
::s..
10- 5
\",
\ Amo'Phous so!;d
\ z.
Activation Energies
\ &\,
\
.- \ & .....
Eo(ev)
.,.
Sample
\
TNF:PVK 0.67-0.71' F=O\\ F=105 V/cm
'\\ .
TNF:Polyester -0.70*
TNF (quenched) 0.63*
TN F (liquid) 0.35
TNF (crystal) 0.10
·Field·dependent E=Eo-fjF%
\
\
\
\ \
lrr7~----~----------------~------------~
2.0 3.0 4.0
SUMMARY
Mobilities have also been studied for pure TNF in the liquid,
amorphous solid and crystalline states. In single crystals the
magnitude of the mobility is fairly t~ical of values observed in
other molecular crystals being 0.06 em IV-sec at 22 0 C. The trans-
port mechanism is by hopping of small polarons or possibly a trap-
controlled drift process. In the disordered states of TNF the
mobility is several orders of magnitude smaller and is strongly
activated. The mobility in the amorphous solid is field dependent
however the field dependent part of the activation energy disappears
in going to the liquid state. Transport in the disordered TNF is by
intermolecular hopping of highly localized electrons.
REFERENCES
COMPOUNDS
W. A. Little
Stanford University
Stanford, California
Fig. 1
145
146 w. A. LITTLE
For economic and scientific reasons much work has been done to
attempt to raise the transition temperature of materials. The pro-
gress which has been made to date is illustrated in Fig. 3.
a:
UJ
III 50
~
o 5 10 20
T (Kl
Fig. 2
25r-----------------------------------~
Hg
Fig. 3
SUPERCONDUCTIVITY IN ORGANIC COMPOUNDS 147
This suggests that it is unlikely that one will find an alloy with
a transition temperature substantially above 2lK, at least in the
next decade. One may well ask, "How high a Tc can one obtain?"
To answer this we need to know something about the theory of super-
conductivity.
.
• • • •
t
.'• . . .•
1. •
• • • '
. . . '.
' '
.~ t:.
•:
'
2.
' '
Fig. 4
Fig. 5
T
1
b
Fig. 6
Tc
3D , ,-
~
R ,/ID
,
,
,,
..'
T
Fig. 7
REFERENCES
R. Aoki
153
154 R. AOKI
460
J;
}
220
,.·+.
•J
1'1
1· .
'80
I~
~
100
•,
j I
'0
1\
T (II:) (a) (b)
100
(TTF)(TCNQ)
()'
OR:r.
10
o
o
.1
10 100
( T - Te>
Fig. 3 Log-log plot of the conductivity
of (TTF)(TCNQ) single crystal vs. (T-Tc)
where Tc = 58K. The straight line has
slope of -1.5 [from Penn.group(2)]
156 R. AOKI
• Cu: Tc=40K
o Pb: Tc=10K
,I
REFERENCES
Aaron N. Bloch
159
160 A. N. BLOCH
N$X)
CH 3
~ ,I N
N· Methyl Phenazinium Quinolinium Acridinium
(NMP)
NC CN
o
.....C......
/ .......
NC CN
TCNQ
2eoo o
2600
2400
2200
2000
leoo
~1600
T
Eo
u E 1400
'----'
~ 1200
1000
600
400 •
!
200
o0 20 40 60 eo 100 120 140 160 leo 200 220 240 260 leo 300 320 340 360
T 'K
References
E E
$.. .. 0 k 0 :I(.
b J.. .L
•
(a) (I»
E E
D DA
o DA
k 0 1. k 0
J.
(e)
" .L
Cd)
F\
S""",S
II "
CH3
S~S
II
/'..
CH3
H
S"""S
II
/'..
CH3
6
NC
I I
N
S/"g s s
S~
II
\ I
H
(CH 31 (CH 3 1 C~ CH3 NC
/C,
CN
no sign of any such anomaly. Third, much of the case 2 for accept-
ing non-reproducible giant conductivities in TTF-TCNQ rested upon
reproducible results for the (cis, trans) -dimethyl derivative
ATTF-TCNQ (Figure 2). Here because of sample problems Colemanet al 2
were unable to measure the absolute magnitude of the conductivity,
but cited instead its strong temperature dependence for4~ silver-
paint compaction. We have since succeeded in measuring the ab-
solute microwave conductivity of single crystals of ATTF-TCNQ, and
found it to be comparatively small, with the reduced transition
temperature and partially "washed out" transition expected for a
weakly disordered material. Fourth, it is well known that inhomog-
eneous current distributions in highly anisotropic conductors can
lead to spuriously large apparent d.c. conductivities as measured
by the standard f0lla-probe techni~ue. Such an artifact has been
observed by Zeller in the ~uasi-one-dimen~ional mixed-valence
platinum salts. More recently Shafer et al 49 have shown experi-
ment~ly that spurious anomalies similar to the results of Coleman
et al can be induced in TTF-TCNQ by a simple misalignment of con-
tacts.
STUDIES IN JAPAN
HARUO KURODA
177
178 H. KURODA
J-
(( C 6HS ) 3 P CH 3 (TCNO) 2 is known to exhibit a phase
transition at about 315 K, where it shows a discontinuous change
of electrical conductivity as well as an appreciable change in the
magnetic properties. 4) The heat capacity of this radical salt in
11- 35 0 K region was measured by S. Seki and his collaborators
in Osaka University. 5) According to their results, the entropy of
transition is 1.7206 cal/deg. mol. When estimated from the
magnetic and electrical data, the contributions of spins and
charge carriers are expected only as 0.13 and 1.5 x 10- 3 cal/deg.
mol, respectively. Thus, Y. Iida attributed the main origin of
the observed entropy of transition to the structural changes in the
phase transition. 6)
the single crystal spectrum, and found that the intensity of the
charge-transfer band markedly increases as the temperature is
lowered below the transition point which has been found at 210 K
from the study on the magnetic property. As known for the
WUrster's blue perchlorate, there is a close correlation between
the intensity change of the charge-transfer band and the temperature
dependence of the paramagnetic susceptibility.
1497 (1969)
13) K. Kaneko and H. Kuroda; Molecular Structure Symposium of
Chem. E?oc. JAP.an (KYoto 1971)
14) N. Sakal, I. ~filrotanl and S. Minomura;
Bull. Chem. Soc. Japan, 44, 675(1971)
15) M. Konno, H. Kobayashi, F. Mar4mo apd Y. Saito;
Bull. Chem. Soc. Japan 46, 1987l1973}
16) S. Hiroma and H. Kuroda; Bull. Chem. Soc. Japan 46, (1973)
(to be published) -
17) S. Hiroma and H. Kuroda; Molecular Structure Symposium of
Chem. Soc. Japan (Sendai, 1972)
18) M. Ohmasa, M. Kinoshita and H. Akamatu;
Bull. Chem. Soc. Japan, 44,391(1971)
19) a) H. Kuroda, I. Ikemoto, K. Yakushi and K. Chikaishi;
Acta Cryst., S4, 5 (1972)
b) 1. Ikemoto, K. Chikaishi, K. Yakushi and H. Kuroda,
Acta Cryst. B28, 3502(1972)
c) K. Yakushi, I. Ikemoto and H. Kuroda; Acta Cryst. B29,
(1973) (to be published)
20) a) G. Saito and Y. Matsunaga; Bull. Chem. Soc. Japan, 44,
3328(1971)
b) Y. Matsunaga and G. Saito; ibid.,~, 963(1972)
c) N. Inoue andY. Matsunaga; ibid., 45,3478(1972)
d) G. Saito andY. Matsunaga; ibid., 46, 714(1973)
e) Y. Matsunaga; ibid., f§., 998(1973)
21) H .. Kobayashi and Y. Saito; Molecular Structure Symposium of
Chem. Soc. Japan (Kyoto, 1971)
22) a) T. Uchida, K. Kimura and K. Hoshino; Molecular
Structure Symposium of Chem. Soc. Ja pan (Kyoto, 1971)
b) T. Uchida, K. Kimura and T. Tokumoto;
26th Annual Meeting of Chem. Soc. Japan (1972)
MICROWAVE DIELECTRIC CONSTANTS OF SOLID MOLECULAR
COMPLEXES
where fl and fO are the resonance frequencies with and without the
specimen respectively, VI and V are the volume of the specimen and
that of the cavity, EO is the electric field vector in the absence of
the specimen, and A is a factor for the second order effect. Knowing
the volume fraction of the sample, 0, in the quartz tube, we calcu-
lated the dielectric constant of the crystal, €, from Es by using
B8ttcher's equation, 2)
35E s + 2 €s (€s - 1)
€ =
35Es - (Es - 1)
Although the value of € thus obtained is slightly dependent on 0, we
have found by examing the data of sample of known dielectric con-
stant that the €-value for 5 = 0.5 is best to be taken a s the dielectric
constant of the crystal. I)
Power
Supply Dual Beam
Oscilloscope
~"""'"'lI"-'"
Cavity
Wave Meter
* Unit; cm 3/mol.
2.9 •
•..00.··
0 .. ..... ~
v 0 {b0· • ....
2.8 o 0 ~ ..
00 00.
~. . 0
~
NO
2.7 '- 00...0....
.....
I O~
o
N
2.6
the sum of the observed polarization of the donor PD and that ofI I
Yoshio Matsunaga
Department of Chemistry, Faculty of Science, Hokkaido
CX:D
H
x =0
I
(I)
(II) XeS
(III) x= Se
189
190 Y. MATSUNAGA
+50
for the phenoxazine complex and 2.50 x 1021 per cm3 for the pheno-
selenazine complex, the electron mobility is estimated to be 0.04
and 2.6 em2/V sec respectively.
The 2:3 iodine complexes of N-alkyl- and benzo-phenothiazines
have been found to behave similarly (2,3). The results are SUllllla-
rized in Table 1. The Seebeck coefficients of the benzophenothi-
azine complexes are nearly parallel to that for the phenoselenazine
complex; however, the linear parts are too short to fit the equation
of Johnson and Lark-Horowitz.
Table 1 Electrical properties of the iodine complexes of N-alkyl-
and benzo-phenothiazines.
pat Qat
Organic component 20°0 E 20°0 b .lLe.
(ohm cm) (eV) ~V/deg) (cm2/V sec)
N-Methylphenothiazine 2.0 0.20 -+10 2.08 2.j
N-Ethylphenothiazine 74 0.15 -+57 0.20 10-
Benzo CaJ phenothiazine 34 0.16 -47 ~l
Benzo[cJphenothiazine 18 0.14 -57 -,1
The vibrational spectrum provides a good method for the char-
acterization of the electronic structure of the organic molecules
in these iodine complexes. For example, the spectrum of the pheno-
thia~ine complex is compared with the spectrum of the parent organic
PHENOTHIAZINE-IODINE AND RELATED COMPLEXES
191
, I
2000 1500 1000
Wave number
I I
2000 1500 1000
Wave number
0.1
o
3 0.2
o ~
..'"
>
E
I
a
I
I
I
I -0.2
I
1)--- ____ .A.-'"
-.~_
o
1
0.5 1.5 2
Mole Ratio
,X'\.
\
30
/0
/,6"';
3
/9/
/
/
/
/'0
/
/
, 0'
, I
d, I
, cf
'p /
, I
.5 1.5
Mole ratio
complex anion-radical salts well known for their low electrical re-
s:istivities, as Br.,I- is a well-known species. Drastic change. in
the vibrational ana electronic spectra b.r the iodine content have
been noted. The low-resistivity adduct shows a vibrational spectrum
consisting of very broad lines. Nevertheless, the whole pattern ia
rather close to the spectrum A of the bromide in Fig. 3. The elec-
tronic spectrum bears also some resemblance to that of the bromide,
especially the one showing the vibrational spectrum A. The maximum
of the low-energy absorption is located below 4 kK. At a mole ratio
of 0.40, an additional absorption appears at 5.5 kK. By further
addition of iodine, the absorption having a maximum below 4 kK is
completely replaced b.r the one at 5.5 kK. Then, around a mole ratio
of 1.00, the intensity of the absorption at 5.5 kK is markedly di-
minished. Moreover, the vibrational spectrum is characterized b.r a
superposition of a pattern consisting of lines as sharp as those in
the spectrum B of the bromide.
195
SUBJECT INDEX
197
198 SUBJECT INDEX
n~~M~D~f,lM~~
ZZ
200