Polymer films as sensitive coatings for quartz crystal microbalance sensors array
This work reports on the results of investigation of quarts crystal microbalance sensors coated with polybutyl methacrylate and polyvinyl formal/ethylal to wide range of volatile organic compounds. Polymer film coated sensors showed a high sensitivity and an excellent selectivity towards these compo...
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| Опубліковано в: : | Semiconductor Physics Quantum Electronics & Optoelectronics |
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| Дата: | 2003 |
| Автори: | , , |
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| Мова: | Англійська |
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Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України
2003
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| Назва журналу: | Digital Library of Periodicals of National Academy of Sciences of Ukraine |
| Цитувати: | Polymer films as sensitive coatings for quartz crystal microbalance sensors array / I.A. Koshets, Z.I. Kazantseva, Yu.M. Shirshov // Semiconductor Physics Quantum Electronics & Optoelectronics. — 2003. — Т. 6, № 4. — С. 505-507. — Бібліогр.: 8 назв. — англ. |
Репозитарії
Digital Library of Periodicals of National Academy of Sciences of Ukraine| _version_ | 1859903867516354560 |
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| author | Koshets, I.A. Kazantseva, Z.I. Shirshov, Yu.M. |
| author_facet | Koshets, I.A. Kazantseva, Z.I. Shirshov, Yu.M. |
| citation_txt | Polymer films as sensitive coatings for quartz crystal microbalance sensors array / I.A. Koshets, Z.I. Kazantseva, Yu.M. Shirshov // Semiconductor Physics Quantum Electronics & Optoelectronics. — 2003. — Т. 6, № 4. — С. 505-507. — Бібліогр.: 8 назв. — англ. |
| collection | DSpace DC |
| container_title | Semiconductor Physics Quantum Electronics & Optoelectronics |
| description | This work reports on the results of investigation of quarts crystal microbalance sensors coated with polybutyl methacrylate and polyvinyl formal/ethylal to wide range of volatile organic compounds. Polymer film coated sensors showed a high sensitivity and an excellent selectivity towards these compounds. Good linearity of the concentration dependence has been obtained in almost all the concentration range of volatile compounds. The detection limit of several analytes was less than 100 ppm.
|
| first_indexed | 2025-12-07T15:59:02Z |
| format | Article |
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505© 2003, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
Semiconductor Physics, Quantum Electronics & Optoelectronics. 2003. V. 6, N 4. P. 505-507.
PACS: 07.07.Df
Polymer films as sensitive coatings for quartz crystal
microbalance sensors array
I.A. Koshets, Z.I. Kazantseva, Yu.M. Shirshov
V. Lashkaryov Institute of Semiconductor Physics, NAS of Ukraine, 41, prospect Nauky, 03028 Kyiv, Ukraine
E-mail: koshets@isp.kiev.ua
Abstract. This work reports on the results of investigation of quarts crystal microbalance
sensors coated with polybutyl methacrylate and polyvinyl formal/ethylal to wide range of
volatile organic compounds. Polymer film coated sensors showed a high sensitivity and an
excellent selectivity towards these compounds. Good linearity of the concentration depend-
ence has been obtained in almost all the concentration range of volatile compounds. The
detection limit of several analytes was less than 100 ppm.
Keywords: quartz crystal microbalance sensor, polymer coating, volatile organic compounds.
Paper received 06.11.03; accepted for publication 11.12.03.
1. Introduction
Nowadays a great attention is paid to creation and de-
velopment of miniaturized, low-cost, smart chemical sens-
ing systems based on various physical and chemical prin-
ciples, which provide accurate and reliable real-time con-
trol of ambient medium [1�2]. One of the most important
problems under creation of such systems (known as �Elec-
tronic noses�) for pattern recognition of smells is the
choice of appropriate sensitive materials used as coat-
ings of such a sensor. Requirements that should be met
with these layers are quite versatile and even con-
tradictious. On the one hand, the sensor should provide
good and quick response to the presence of analyzed
molecules in ambient air, on the other hand, the sensor
must have sensitivity to the interfering molecules as less
as possible. Besides, the sensor should be easily cleaned.
From this viewpoint, various types of polymers are very
promising materials, and many researchers focus their
attention on investigations of selective and sensitive prop-
erties of polymer films [3�5]. This work is aimed at the
study of polybutyl methacrylate (PBMA) and polyvinyl
formal ethylal (PVFE) as sensitive layers for (quarts crys-
tal microbalance) QCM sensor.
2. Experimental
The basis of QCM technique is the proportionality be-
tween mass loaded onto quartz surface and oscillations
frequency shifts in according to the Sauerbrey equation
[6]. So, measuring the frequency shift, one can easily
investigate adsorption-desorption processes occurring at
onto sensor surface. Sensitivity of this method is very high �
1�2 ng/Hz, which allows detecting the very low concen-
tration of organic vapors. 8-channel QCM sensor system
with all the necessary equipment (gas cell, gas-supplying
system and electronic circuits, etc.) designed in our labo-
ratory has been used in experiments. The experiment con-
trol and data acquisition were implemented with PC by
means of domestic software. Gas-supplying regime cho-
sen for our experiments was of non-flow type: after rap-
idly injected analyte gas, the cell was cut off from pipe-
line and no gas flow occured during the measuring pe-
riod. The detailed description of this device and gas sup-
plying regime can be found in [7].
Polymers were deposited onto quarts surface by means
of dipping and spin coating techniques. Information about
morphology and determination of the thickness of layers
deposited has been was obtained from ellipsometry and
AFM measurements. The average film thickness was
about 50-70 nm (on each side of quartz sensor), which
corresponds to 2000-3000 Hz frequency shift. After depo-
sition, sensors were dried with fresh dry air for 12-15
hours to draw out the remaining solvent from coatings.
Chemical structures of polymers are shown in Fig. 1.
Such volatile organic compounds as chlorbenzene
(C6H5Cl), benzene (C6H6), toluene (C7H8), dichloro-
methane (CH2Cl2), carbon tetrachloride (CCl4), chloro-
form (CHCl3) and ethanol (C2H6O) were involved in our
506
SQO, 6(4), 2003
I.A. Koshets et al.: Polymer films as sensitive coatings for quartz crystal ...
experiments. The required concentration was provided
with the home made vapor generating system based on
the diffusion tube principle [8].
3. Results and discussion
Typical kinetics of sensors response to injection of differ-
ent organic vapors (ethanol, dichloromethane and chlo-
robenzene) is presented in Fig. 2. Numbers in plots de-
note the concentration of analyte. Two types of the curve
shape are observed: the first one � gradual (�slow�)
changing of the frequency shift followed by the flat part
of the curve; the second � �fast� response with pronounced
maximum followed by a dip of the curve. Such distinct
behavior strongly depends on correlation of such factors
as gas cell capacity, initial number of volatile molecules
injected, numbers of sensors and cell sites, and their time
constants (�slow� or �fast� they are). The detailed de-
scription of this phenomenon can be found in [2].
It was found that PMBA film coated sensor exhibited
a high sensitivity and an excellent selectivity for
chlorbenzene, although the sensor also responded to chlo-
roform, chlormethelene and toluene, responses towards
alcohol were insignificant. The responses of PVFE film
coated show a high sensitivity towards alcohol but low
sensitivity towards chlorine organic vapors. In some cases,
e.g. chlormethelene, magnitude of response is similar for
two polymers, but the shape of kinetic curve strongly dif-
ferent. It provides us extra information for goals of pat-
tern recognition.
As known, selective features of organic sensitive layer
mainly coincide with solubility parameter towards or-
ganic solvents [1]. In other words, the closer solubility
parameters of given organic layer and given solvent, the
higher response of the sensor coated with this layer to the
vapor of that solvent. For example, solubility parameters
of PBMA are closer to those of benzene and chlorbenzene
but smaller than that of ethanol. Similar situation is ob-
served in QCM measurements � sensor coated with PBMA
shows maximal response to carbon tetrachloride vapor.
Although, situation is more complicated for copolymers
(PFE) consisting of different polarity monomers. In this
case, the dipole�dipole interaction plays a significant
role, which should be taken into account for analysis of
sensing features inherent to these coatings.
Concentration dependencies extracted from kinetic
curves are shown in Fig. 3. Good linearity is seen almost
over all the concentration range of analytes.
0 200 400 600 800 1000
�40
�30
�20
�10
0
10
PBMA
PVFE
10000
5000
3000
2000
1000
600
300
∆
f,
H
z
time, s
a
0 200 400 600 800 1000
�60
�40
�20
0
PBMA
PVFE
500
1000
2000 4000
8000
16000
∆
f,
H
z
time, s
b
0 200 400 600 800 1000
�60
�40
�20
0
PBMA
PVFE
100
200
300
500
1000
2000
∆
f,
H
z
time, s
c
Fig. 2. Kinetic response (frequency shift) of sensors coated with
polymers to injection of ethanol (a), dichloromethane (b) and
chlorbenzene (c) vapor.
a
[C � CH2 ] N
O = C � O � (CH2)3 � CH3
b
[CH � CH2 � CH � CH2 ]X [CH2 � CH ]Y
O � CH � O OH
CH3
[CH2 � CH ]Z
OCOCH3
Fig. 1. Chemical structure of polymers: a) � PBMA; b) � PVFE.
I.A. Koshets et al.: Polymer films as sensitive coatings for quartz crystal ...
507SQO, 6(4), 2003
Table.1. Sensitivity and detection threshold of sensors coated with PBMA and PVFE.
Volatile organic PBMA PVFE
molecules Sensitivity, Detection Sensitivity, Detection
10�4×Hz/ppm threshold, ppm 10�4×Hz/ppm threshold, ppm
Benzene 38.8 300 10.8 <300
Ethanol 9.34 2000 34 <300
Toluene 87.7 <250 10.5 <500
Carbon tetrachloride 86 <500 5.92 2000
Chloroform 93.4 <300 8.5 500
Dichloromethane 36 500 24 500
Chlorobenzene 34.5 <100 17.1 2000
0 3000 6000 9000 12000 15000
�60
�50
�40
�30
�20
�10
0
∆
f,
H
z
concentration, ppm
Benz
Eth
Tol
CCl4
Clor
ClMet
ClBen
a
0 3000 9000 15000
�30
�25
�20
�15
�10
�5
0
∆
f,
H
z
concentration, ppm
b
Benz
Eth
Tol
CCl4
Clor
ClMet
ClBen
Fig. 3. Sensitivity of sensors coated with PBMA (a) and PVFE (b) towards various volatile organic molecules.
Slightly sublinear shape of curves in the high concentra-
tion level (one or two last points) might be related to satura-
tion of sensitive sites in the film. Numerical values of the
sensitivity and detection limit are presented in Table1.
Sensors coated with PBMA and PVFE accompanied
with sensors coated with other polymers were combined
into array that was successfully tested for discrimination
of wide number of aromatic and chlororganic volatile
compounds and several items of brandy produced in
Ukraine.
4. Conclusions
Summarizing all mentioned above, we may conclude that
polymer and copolymer are promising materials for us-
ing them as a sensitive layer of sensors elements in a
chemical sensing system. Varying functional groups of
polymer, we can find appropriate set of sensors for reli-
able recognition of volatile organic compounds in ambi-
ent atmosphere and testing the quality of alcohol bever-
ages, perfumes, etc. Application of statistical apparatus
(PCA, Neural Network, etc.) to data obtained from the
sensor array allows increasing such recognition.
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|
| id | nasplib_isofts_kiev_ua-123456789-118076 |
| institution | Digital Library of Periodicals of National Academy of Sciences of Ukraine |
| issn | 1560-8034 |
| language | English |
| last_indexed | 2025-12-07T15:59:02Z |
| publishDate | 2003 |
| publisher | Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України |
| record_format | dspace |
| spelling | Koshets, I.A. Kazantseva, Z.I. Shirshov, Yu.M. 2017-05-28T16:34:48Z 2017-05-28T16:34:48Z 2003 Polymer films as sensitive coatings for quartz crystal microbalance sensors array / I.A. Koshets, Z.I. Kazantseva, Yu.M. Shirshov // Semiconductor Physics Quantum Electronics & Optoelectronics. — 2003. — Т. 6, № 4. — С. 505-507. — Бібліогр.: 8 назв. — англ. 1560-8034 PACS: 07.07.Df https://nasplib.isofts.kiev.ua/handle/123456789/118076 This work reports on the results of investigation of quarts crystal microbalance sensors coated with polybutyl methacrylate and polyvinyl formal/ethylal to wide range of volatile organic compounds. Polymer film coated sensors showed a high sensitivity and an excellent selectivity towards these compounds. Good linearity of the concentration dependence has been obtained in almost all the concentration range of volatile compounds. The detection limit of several analytes was less than 100 ppm. en Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України Semiconductor Physics Quantum Electronics & Optoelectronics Polymer films as sensitive coatings for quartz crystal microbalance sensors array Article published earlier |
| spellingShingle | Polymer films as sensitive coatings for quartz crystal microbalance sensors array Koshets, I.A. Kazantseva, Z.I. Shirshov, Yu.M. |
| title | Polymer films as sensitive coatings for quartz crystal microbalance sensors array |
| title_full | Polymer films as sensitive coatings for quartz crystal microbalance sensors array |
| title_fullStr | Polymer films as sensitive coatings for quartz crystal microbalance sensors array |
| title_full_unstemmed | Polymer films as sensitive coatings for quartz crystal microbalance sensors array |
| title_short | Polymer films as sensitive coatings for quartz crystal microbalance sensors array |
| title_sort | polymer films as sensitive coatings for quartz crystal microbalance sensors array |
| url | https://nasplib.isofts.kiev.ua/handle/123456789/118076 |
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