We investigated transport properties of organic heterointerfaces formed by single-crystals of two organic donor-acceptor molecules, tetramethyltetraselenafulvalene and 7,7,8,8-tetracyanoquinodimethane (TCNQ). Whereas the individual crystals have unmeasurably high resistance, the interface exhibits a resistivity of few tens of megohm with a temperature dependence characteristic of a small gap semiconductor. We analyze the transport properties based on a simple band diagram that naturally accounts for our observations in terms of charge transfer between two crystals. Together with the recently discovered tetrathiafulvalene–TCNQ interfaces, these results indicate that single-crystal organic heterostructures create functional electronic systems with properties relevant to both fundamental and applied fields.

1.
C. W.
Tang
and
S. A.
VanSlyke
,
Appl. Phys. Lett.
51
,
913
(
1987
).
2.
G.
Yu
,
J.
Gao
,
J. C.
Hummelen
,
F.
Wudl
, and
A. J.
Heeger
,
Science
270
,
1789
(
1995
).
3.
T.
Ando
,
A. B.
Fowler
, and
F.
Stern
,
Rev. Mod. Phys.
54
,
437
(
1982
).
4.
A.
Tsukazaki
,
A.
Ohtomo
,
T.
Kita
,
Y.
Ohno
,
H.
Ohno
, and
M.
Kawasaki
,
Science
315
,
1388
(
2007
).
5.
K. v.
Klitzing
,
G.
Dorda
, and
M.
Pepper
,
Phys. Rev. Lett.
45
,
494
(
1980
).
6.
T.
Mimura
,
S.
Hiyamizu
,
T.
Fujii
, and
K.
Nanbu
,
Jpn. J. Appl. Phys.
19
,
L225
(
1980
).
7.
M.
Nakano
,
A.
Tsukazaki
,
A.
Ohtomo
,
K.
Ueno
,
S.
Akasaka
,
H.
Yuji
,
K.
Nakahara
,
T.
Fukumura
, and
M.
Kawasaki
,
Adv. Mater. (Weinheim, Ger.)
22
,
876
(
2010
).
8.
H.
Alves
,
A. S.
Molinari
,
H.
Xie
, and
A. F.
Morpurgo
,
Nature Mater.
7
,
574
(
2008
).
9.
T.
Ishiguro
,
K.
Yamaji
, and
G.
Saito
,
Organic Superconductors
, 2nd ed. (
Springer
,
Berlin
,
1998
).
10.
D.
Jérome
and
H. J.
Schulz
,
Adv. Phys.
31
,
299
(
1982
).
11.
TMTSF in combination with TCNQ has been reported to form two bulk charge-transfer complexes with different crystal structures. One material exhibits metallic conduction reaching values in excess of 104Ω1cm1 and undergoes a Peierls transition into an insulating state at around 57 K (Refs. 12 and 13). The other, which has received much less attention in the literature, is a semiconductor (Refs. 14 and 15). In both cases, a considerable charge transfer takes place from TMTSF to TCNQ; in the metal approximately 0.57 electrons/molecule are transferred, whereas in the semiconductor the charge transfer is reported to be 0.21 electrons/molecule (Ref. 16).
12.
C. S.
Jacobsen
,
K.
Mortensen
,
J. R.
Andersen
, and
K.
Bechgaard
,
Phys. Rev. B
18
,
905
(
1978
).
13.
S.
Bouffard
,
M.
Ribault
,
R.
Brusetti
,
D.
Jérome
, and
K.
Bechgaard
,
J. Phys. C
15
,
2951
(
1982
).
14.
K.
Bechgaard
,
T. J.
Kistenmacher
,
A. N.
Bloch
, and
D. O.
Cowan
,
Acta Crystallogr., Sect. B: Struct. Crystallogr. Cryst. Chem.
B33
,
417
(
1977
).
15.
T. J.
Kistenmacher
,
T. J.
Emge
,
A. N.
Bloch
, and
D. O.
Cowan
,
Acta Crystallogr. Sect. B: Struct. Crystallogr. Cryst. Chem.
B38
,
1193
(
1982
).
16.
J. S.
Chappell
,
A. N.
Bloch
,
W. A.
Bryden
,
M.
Maxfield
,
T. O.
Poehler
, and
D. O.
Cowan
,
J. Am. Chem. Soc.
103
,
2442
(
1981
).
17.
H.
Xie
,
H.
Alves
, and
A. F.
Morpurgo
,
Phys. Rev. B
80
,
245305
(
2009
).
18.
We performed cyclic-voltammetry measurements to evaluate the relative energy difference between the HOMO of TMTSF and the LUMO of TCNQ. By regarding the electrochemical half-wave potentials as the corresponding donor or acceptor levels, we obtained the relative energy difference of 230 meV in acetonitrile and 270 meV in dichloromethane, respectively (Pt working electrode, Ag/AgCl reference electrode). These values are in good agreement with those extracted from transport measurements (2Ea140240meV).
19.
E. A.
Silinsh
and
V.
Capek
,
Organic Molecular Crystals
(
AIP
,
New York
,
1994
).
20.
G.
Brocks
,
J.
van den Brink
, and
A. F.
Morpurgo
,
Phys. Rev. Lett.
93
,
146405
(
2004
).
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