Synthetic Metals, 60 (1993) 111-114 111
Conducting Langmuir-Blodgett films of hexadecyl-BEDT-TTF
charge-transfer salts with inorganic compounds
Tatiana S. Berzina and Vladimir I. Troitsky
Zelenograd Research Institute of Physical Problems, 103460 Moscow (Russian Federation)
Elisa Stussi, Marcello Mul6 and Danilo De Rossi
Centro 'E. Piaggio; University o f Pisa, via Diotisalvi 2, 1-56122 Pisa (Italy)
(Received December 11, 1992; in revised form March 18, 1993; accepted March 19, 1993)
Abstract
A method for forming conducting Langmuir-Blodgett films of charge-transfer salts based on the interaction
between surfactant donor molecules spread at the air/water interface and inorganic compounds dissolved in water
is proposed. Films of hexadecylbis(ethylenedithio)tetrathiafulvalene with small additions of surfactant acceptor
molecules were deposited from water subphases containing FeCI3 or CuSO4. High quality films with conductivity
of 2 ~-~ cm -1 were deposited at pH of 3.8 when Fe 3÷ ions at a concentration of 10 -4 M were used. In order
to study the interaction of donor molecules with the compounds dissolved in water, electron probe analysis of
the films was carried out. Variants of charge-transfer salt formation are discussed.
Introduction
Conducting Langmuir-Blodgett (LB) films [1] are
promising components for the development of molecular
electronic devices. Conducting layers can be introduced
into assemblies of alternating LB monolayers [2] to
provide electron transfer in horizontal planes. In ad-
dition, discovery of field effect in conducting LB layers
[3] makes conductivity modulation possible by means
of an external electric field. Film conductance was
proved to be destroyed by electron beam effect [4].
Therefore, high resolution patterns can be created using
the electron beam lithography technique. Patterning of
conducting paths can be obtained in principle with
much higher spatial resolution by the effect of the
current of the STM tip. In order to realize such
possibilities, highly conductive, uniform and stable LB
films with good sensitivity to the electron beam are
necessary. In the pioneering work on conducting LB
films of docosylpyridinium charge-transfer salt with
TCNQ [1], precursor nonconducting films with a high
degree of charge transfer between pyridinium and
TCNQ groups were deposited. Then, stacks of TCNQ-
anions were partially oxidized by iodine to obtain con-
ductivity. The same procedure of iodine doping was
used for preparing conducting films of one-component
donor molecules [5]. In many cases some uncontrolled
doping took place in the process of deposition and
conductance without any treatment was observed. Two-
component LB films consisting of alternating surfactant
donor and acceptor monolayers [6] were used in another
attempt. LB films consisting of mixed monolayers of
such compounds [7] were also formed to provide charge
transfer between donor and acceptor molecules.
Electrically conducting polypyrrole LB films were
deposited from the surface of a subphase containing
ferric chloride [8, 9]. This inorganic compound was
used to polymerize and oxidize the mixture of pyrrole
monomer and surface active pyrrole derivative at the
air/water interface, giving rise to electrical conductance.
The best value of conductivity obtained was equal to
0.1 l'1-1 cIr1-1.
In the present work we used a procedure for forming
LB films of charge-transfer salts based on the interaction
between surfactant donor molecules spread at the air/
water interface and inorganic compounds dissolved in
water. Conducting films of hexadecylbis(ethylenedi-
thio)tetrathiafulvalene (C16-BEDT-TrF) with small ad-
ditions of surfactant acceptor molecules were deposited
from water subphases containing FeC13, or CuSO4 at
different concentrations and pH values. Quality of the
deposited films was verified by optical microscopy and
conductivity was measured. Electron probe analysis of
the films deposited onto ultrathin collodion substrates
was carried out in order to study the interaction of
donor molecules with the compounds dissolved in water.
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