~~ MATERIALS
SCIENCE &
ENGINEERING
ELSEVIER Materials Science and EngineeringC 5 (1998) 255-258
AC and DC measurements on Langmuir-Blodgett polypyrrole films for
selective NH3 gas detection
M. Penza *, E. Milella, F. Musio, M.B. Alba, G. Cassano, A. Quirini
PASTIS-CNRSM, SS. 7, Appia, K~ 7 + 300 per Mesagne, 72100 Brindisi, haly
Received 17 October 1996
Abstract
The Langmuir-Blodgett method has been used to deposit onto quartz substrate polypyn'ole film as gas sensitive coating. The AC and DC
electrical resistance and capacitance of the sensing device have been investigated under controlled ambient conditions, at room temperature,
during gas exposures of NH3, CH4, CO in dry air. The AC capacitance of the polypyrrole sensor was not affected by any test gases throughout
the examined frequency range (20 Hz 10 I MHz). The AC and DC electrical resistance showed a highly sensitive response towards NH~ and
negligibly small response towards interfering CH4 and CO: the sensitivity and selectivity of the NH3 detector increased with the decreasing
AC frequency obtaining the optimal working conditions in DC mode. The calibration curve of the sensor towards NH3 in the gas concentration
range 100-I0 000 ppm has been performed at different frequencies (DC to 1 MHz) indicating a linear relationship between AC and/or DC
resistance and NH~ concentration. Long-term stability tests have been cmTied out onto a polypyrrole detector exhibiting fairly reproducible
responses towards NH3 during a six-month period. An efficient recognition of NH.~ as one component of a gas mixture containing CO, CH4,
O_~in air has been successfully recorded. © 1998 Elsevier Science S.A.
Keywords: Polypyrrole film; Langmuir-Blodgett technique: Ammonia gas sensor
1. Introduction
In recent years, organic compounds have been investigated
as vapour and gas sensing interfaces of solid-state devices
[1-3]. The conducting polymers (polypyn'ole, polythio-
phene, polyacetylene, etc.) are the most studied due to their
reversible and highly sensitive response at room temperature
and low Iimit of detection. These systems are being used in
a number of application areas, including transportation,
robotics, industriaI manufacturing, consumer electronics,
health care, biomedicine, agro-industriaI sustainable
improvement. It is well known that ammonia sensing is a task
with a large demand for practicaI purposes.
The Langmuir-Blodgett (LB) method perlnits the depo-
sition of polypyrrole films with ultrathin thickness and well-
ordered structure in order to selectively detect ammonia using
a single sensing element [4].
While the DC electrical characteristics of the polypyrrole
detector have been well studied [5], the AC parameters of
resistance and capacitance of the sensing device are less well
known. Therefore, the measurements at AC frequency of
electrical parameters of the sensor may be useful to under-
* Corresponding author.
0928-4931/98/S19.00 © 1998 Elsevier Science S.A. All rights reserved
PILS0928-4931 (97) 00057-X
stand the chemical interaction mechanisms between the
adsorbed gas molecules and the sensitive coating and to dis-
criminate a specific analyte from its interfering species [6].
This paper focuses on comparison between AC and DC
electrical responses of the LB polypyrrole film sensor for
selective detection of ammonia gas.
2. Experimental details
2.1. Synthesis of Langmuir-Blodgett polypyrrole jSIm
The LB method was used for film deposition. A solution
( I mg mI- t) of stearic acid in chloroform was spread out
onto a subphase of deionized water containing 4× 10 -s M
ferric chloride. The subphase pH and temperature were kept
constant at 5.6 and 15 °C (+0.02 °C), respectively. The
pressure-area ('a-A) isotherms of the film deposition were
performed by a KSV LB5000 apparatus ensuring high accu-
racy of the surface pressure ( _+4 p~N m- ~ ) and the area per
molecule ( > 99%). The film was compressed with a barrier
rate of 5 mm min-~ up to a pressure of 35 mN m- 1, the
dipping rate was 1 mm min- t and the drying time was about
60 min. A determined number of monolayers of feITiC stearate