Room Temperature CO2 Detection using

Interdigitated Capacitors with

Heteropolysiloxane Sensing Films

Choongsoon Kim, Spyridon Pavlidis,

Min-gu Kim, Oliver Brand Hang Chen
School of Electrical and Computer Engineering Institute for Electronics and Nanotechnology
Georgia Institute of Technology Georgia Institute of Technology
Atlanta, GA, USA Atlanta, GA, USA
E-Mail: ckim96@gatech.edu

Abstract—This paper investigates the detection of carbon
dioxide at room temperature using microfabricated, interdigitated
capacitive (IDC) sensors coated with an amino-functionalized
sensing film. Sensing experiments performed at temperatures
ranging from room temperature to 100ÛC indicate two different
temperature-dependent sensing mechanisms. Around room
temperature, physisorption dominates the sensor response,
resulting in fast signal transients and negative capacitance
changes. Above 80ÛC, chemisorption appears to dominate,
resulting in larger, positive capacitance changes with longer signal
transients.
Keywords—capacitive sensor, CO2, amino group
I. INTRODUCTION
As one of the greenhouse gases, which critically affect
climate change, carbon dioxide (CO2) has drawn much attention
in recent years. Over 80% of the atmospheric CO2 is emitted
from human activities, such as transportation, and power plants
[1]. To monitor CO2 concentrations, a variety of CO2 sensors
have been investigated, with NDIR (non-dispersive infrared)
sensors based on infrared absorption being the most widely used
approach. To lower sensor cost, non-optical sensing techniques
relying on different sensing materials, including solid
electrolytes [2], metal oxides [3], mesoporous materials [4],
silicon-based polymers [5], as well as polymeric amino groups
[6], have been investigated. However, because of the strong C-
O double bonds [6], most of the aforementioned sensing
materials require elevated temperatures (>60ÛC) in order to drive
chemical reactions with CO2 and create a detectable signal.
Recently, CO2 sensors operating at room temperature have
also been proposed using new materials, such as graphene oxide
[7], carbon nanotubes [8], and poly-ionic liquids [9]. Despite
offering the possibility of low-temperature operation, these
materials can be hard to work with compared to polymer-based
sensing films. Organically modified siloxanes, in particular 3-
aminopropyltrimethoxysilane (AMO) and propyltrimethoxy-
silane (PTMS), are two examples of such materials. Mass-
sensitive and capacitive sensors have been demonstrated with
AMO and PTMS, however with an operating temperature of
70ÛC [5,10]. Stegmeier et al., on the other hand, showed room-
temperature CO2 detection by measuring the change in work
This work was performed in part at the Georgia Tech Institute for
Electronics and Nanotechnology, a member of the National Nanotechnology
Coordinated Infrastructure, which is supported by the National Science
Foundation (Grant ECCS-1542174).
978-1-4799-8287-5/16/$31.00 ©2016 IEEE
function of a floating gate field effect transistor (FET) device
using Kelvin probe measurements, while also providing an
explanation for the different CO2 sensing mechanisms at room
temperature versus elevated temperature [11].
In this paper, room-temperature CO2 detection is
demonstrated using a capacitive sensor coated with an amino-
functionalized sensing film. The key advantages of capacitive
sensors are easy fabrication, low cost, and straight-forward
integration with CMOS technology for miniaturization of the
sensing system. Furthermore, the polarity and sensitivity of the
sensor’s response as a function of the operating temperature is
investigated.
II. IDC SENSOR AND SENSING FILM
A. Interdigitated Capacitor Layout and Fabrication
Interdigitated capacitors (IDC) have been widely used for
chemical sensing because of their simplicity, low cost and ease
of integration with readout electronics [2]. Figure 1 shows the
layout and cross-section of the IDC used in this work.
Figure 1. (left) Layout and (right) cross-sectional view of the interdigitated
capacitor (IDC). Changes in the dielectric permittivity of the sensing film as a
function of the adsorbed gas-phase chemical analyte are detected by the IDC and
converted into an electrical output signal.
The capacitors, shown in Figure 2, were batch manufactured
using microfabrication techniques. First, a 1 μm thick thermal
oxide (SiO2) layer is grown on the Si wafer to isolate the
capacitive sensors from the silicon substrate. Then a 200 nm
thick film of aluminum (Al) was deposited using electron-beam
evaporation, and subsequently patterned via dry etching. This
layer defines the interdigitated electrodes of the capacitor.
 Figure 3. Diagram of the gas measurement setup: Three mass flow controllers
control the flow rate from N2 and CO2 (10,000ppm)/ N2 gas cylinders. A four-
way valve instantly switches between the purge and analyte-loaded gas streams.
Figure 2. Photograph of part of the fabricated interdigitated capacitor structure. The system is controlled by a circuit board and LabView program.
The electrode width and spacing is 6 μm.
At room temperature, the response time is short (<10s), with
Plasma-enhanced atomic layer deposition (PE-ALD) was near instantaneous changes in capacitance observed after
then used to deposit a 100 nm thick film of SiO2 at 250ÛC. Dry switching gases, and the capacitance change upon CO2 exposure
etching was once again employed to selectively create via is negative. In contrast, a similar measurement performed at
openings through the ALD SiO2 down to the bottom Al layers. 95ÛC (Figure 4b) shows a distinctly slower sensor response and
A second metal layer of chrome/gold (Cr/Au) with 25/200 nm a positive capacitance change upon CO2 exposure. Moreover,
thickness was defined using lift-off. This layer fills the vias and the signal baseline is more stable at elevated temperature and,
defines bond/probe pads. Following wafer dicing, individual though the response time constant has increased, the steady-state
dies were wire-bonded in dual-in-line (DIL) packages that are sensitivity is larger than for the room temperature measurement.
compatible with our gas measurement system (Figure 3). IDCs It should be noted that for higher CO2 concentrations at 95ÛC
were fabricated with an overall square shape whose side length longer measurement times would be needed to reach
was 1 mm. The electrode width and spacing are both 6 μm. equilibrium.
B. Amino-Functionalized Polysiloxane
AMO and PTMS were mixed together with a ratio of 70:30
(volume:volume). PTMS was added for hydrophobization in
order to reduce the interference of water vapor [6]. This sensing
material was deposited on the sensor by spin coating at 2000
RPM for 30 s, which resulted in a film thickness of approx. 2.3
μm. Afterwards, the devices were annealed for 10 hours at
120°C in an oven. This curing process serves to build stable Si-
O-Si-O linkages within the polymer matrix.
III. EXPERIMENTAL SETUP
Figure 3 shows the in-house gas measurement setup that was
used for the CO2 sensing measurements. Three mass flow
controllers (MFCs) control gas flows from nitrogen (N2) and
CO2(10,000ppm)/N2 gas cylinders. MFC1 is used to control the
reference/purge gas line, always flowing nitrogen gas at
80ml/min total flow rate. MFC2 controls the flow rate of N2 that
is mixed with the analyte gas stream (10,000 ppm CO2 in N2)
from the MFC3-controlled gas line. The total gas flow was
maintained at 80 ml/min. By mixing analyte gas stream with
reference gas at controlled ratios, CO2 concentrations were Figure 4. Measured sensor capacitance vs. time while subsequently exposing the
adjusted from 1250 to 3750 ppm. Using a 4-way valve, it is sensor to 1250, 2500, 3750, 2500 and 1250 ppm CO2 at (a) 22°C and (b) 95°C.
possible to rapidly switch between analyte-loaded gas and In-between each 10-minute analyte exposure, the measurement chamber is
reference gas, while keeping the total gas flow constant. Real- flushed with carrier gas for 10 minutes. The humidity level was measured to be
approx. 5% at 22°C and 2% at 95°C using a commercial humidity sensor
time measurements of the capacitance were captured using an mounted inside the test chamber. The limit of detection for the room temperature
Agilent 4284A Precision LCR meter at a frequency of 10 kHz. measurement is approx. 500ppm.

IV. RESULTS AND DISCUSSION Figure 5 summarizes the observed temperature dependence
of the capacitive sensor response to CO2. Figure 5a shows the
Figure 4a shows a typical capacitance measurement upon
measured relative capacitance change upon exposure to 1250,
subsequent exposures to CO2 concentrations of 1250, 2500,
2500, and 3750 ppm of CO2 as a function of the sensor
3750, 2500, and 1250 ppm at room temperature (22°C). In-
temperature. Near room temperature, the sensor response is
between each 10-minute analyte exposure, the measurement
negative and a near-zero response is observed around 60-70°C.
chamber is flushed with carrier/reference gas for 10 minutes.
As the temperature is increased further, two changes are seen:
(a) the signal polarity changes from negative to positive, and (b)
the sensitivity reaches a maximum around 80-90ÛC and rapidly
decreases afterwards. It should be noted that the relative
capacitance change was always recorded after 10-minute CO2
exposure and the signal may not have reached steady-state due
to the long time constants for temperatures >80ÛC. Figure 5b
directly compares the signal transients recorded at room
temperature and at 95ÛC.
Figure 5. (a) Measured relative capacitance change as a function of the sensor
temperature for CO2 concentrations of 1250, 2500, and 3750ppm. The relative
capacitance change is measured at the end of the 10-minute analyte exposure.
(b) Comparison of the sensor responses, i.e. signal transients, upon exposure to
1250ppm CO2 at 22ÛC (red data) and 95ÛC (blue data).
The interaction mechanisms between the amino-
functionalized polysiloxane and the CO2 gas have been reported
previously [11]. Thus, the observed CO2 sensing signals can be
explained by two interaction mechanisms, physical and
chemical interaction. Physical interactions are the dominant
factor for CO2 detection at lower temperatures. The CO2
molecules can be easily sorbed and desorbed in the sensing film
during CO2 exposure and N2 purging, respectively, leading to
the sensor’s short time constant at low temperatures. However,
as the CO2 concentrations become higher, the desorption process
takes longer, which may explain the base-line signal drift
observed in Figure 4a. The polarity of the sensor response
depends on the dielectric constant of the analyte with respect to
the sensing film. The dielectric constant (İr) of CO2 has been
reported in the literature as ~1.6 [12]. The exact dielectric
constant of the polymerized AMO/PTMS films has not been
measured. However, this amino group has been investigated and
used to produce low-İr materials [13], with a dielectric constant
in the range of İr~2-3. Thus, it can be assumed that the sensing
film has a larger İr than CO2. As a result, the negative response
at room temperature can likely be explained by the lower
dielectric constant of CO2 compared to the amino-functionalized
sensing film. As the temperature increases, chemisorption
becomes the dominant factor affecting the sensing signal.
Chemisorption processes take longer time to occur than
physisorption processes, so the sensor response time is slower
than at lower temperature. The process produces carbamate and
bicarbonate by chemical reaction of CO2 and the amino-
functionalized sensing film [11], and it results in a positive
sensor response as shown in Figure 4b. The total sensor response
is the summation of responses from both physisorption and
chemisorption. These two competing mechanisms cancel out
each other around ~70°C and the total response becomes zero.
When the temperature further increases sensitivity reaches a
maximum value at ~80°C and starts decreasing after that. The
decrease is caused by shortening of the CO2 retention time at
high temperature. Over 80°C, the CO2 retention time becomes
shorter than the time needed for the chemisorption process of
CO2 within the amino sensing film. Therefore, amino-
functionalized sensing film can no longer detect the presence of
CO2 at temperatures around 100°C.
V. CONCLUSION
Room temperature CO2 detection has been demonstrated
using an interdigitated capacitor structure coated with an amino-
functionalized polysiloxane sensing film. While the observed
room-temperature CO2 sensing is promising, showing fast
response times, the observed baseline drift must be studied in
more detail.
ACKNOWLEDGMENT
The authors would like to thank the cleanroom staff at the
Georgia Tech Institute for Electronics and Nanotechnology
(IEN) for their help with fabrication and characterization.
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