Fabrication and Characterization of Thin Film Nanocrystalline Graphite for Resistive Sensing Applications

T. Y. Ling a,b, M. S. Shamsudin a, S. M. Sultan c, J. W. McBride a, H. M. H. Chong b, S. H. Pu a,b

a
Mechatronics Research Group, University of Southampton Malaysia Campus, Iskandar Puteri, Johor, Malaysia
b
Nanoelectronics and Nanotechnology Research Group, Faculty of Physical Sciences and Engineering, University of Southampton, Southampton, UK
c
Department of Electronic and Computer Engineering, Universiti Teknologi Malaysia, Skudai, Johor, Malaysia

e-mail: ivan.ling@soton.ac.uk

Keywords: Nanocrystalline graphite (NCG), resistive sensor, thin film

Introduction
Current thin-film resistive sensors are based on semiconducting metal
oxides [1], conducting polymers (CPs) [2] and carbon materials [3]. Metal
oxide sensors are used for sensing oxidising or reducing gases through
redox reactions with oxygen ions on the surface of the metal oxide. These
sensors often require higher temperature (>300oC) to work due to the
reaction temperature of oxygen ions [4]. Thus, controlled heating is often
required to maintain constant temperature for metal oxide sensors to work.
Both CPs and carbon based films are capable of sensing at room
temperature. However, long term exposure to the environment can
destabilize the CPs [5]. Carbon based sensors, such as carbon nanotubes, Figure 1: Raman spectra of the film showing distinctive NCG peak
graphene, nano-diamond and NCG are challenging to synthesize because signatures at 1334.52 cm-1 (D-peak) and 1605.27 cm-1 (G-peak).
they require high temperature processes or metal catalysts [6, 7]. We Inset: Edge-enhanced height and phase image of the NCG film
propose using plasma enhanced chemical vapour deposition (PECVD) to deposited on SiO2 obtained via AFM
deposit NCG directly onto SiO2 substrates at a much lower deposition
temperature (750 - 850 oC) [8] for resistive sensing. As a proof of concept,
ionic sensing and humidity sensing experiments are carried out on 9 nm
thick PECVD NCG strips to investigate the effect of conductive ions and
moisture on the grain boundaries of NCG and its resistivity. At a later
stage, we aim to investigate using NCG as a potential NOx gas sensor for
environmental monitoring.

Process Description
In this work, nanocrystalline graphite films are deposited by PECVD onto
150mm, p-type, <100> silicon wafers with 450 nm of thermal oxide
grown by wet oxidation. Various PECVD deposition temperatures,
ranging from 750 oC to 850 oC were used to obtain films with varying Figure 2: Resistance versus Figure 3: Time-response graph of
thickness and grain size. Deposition was carried out with methane and (NH4)2SO4 concentration resistance change due to humidity
hydrogen at a ratio of 5:4. The chamber pressure is kept constant at 1500 change in the environment
mTorr with RF power of 100 W. The NCG film is then patterned into
strips with various dimensions using optical lithography, and etched with
oxygen plasma. The resulting film was characterized using Raman
spectroscopy and AFM. The Raman spectrum of the film (Fig. 1) shows
D-G intensity ratio of 2.3, which is attributed to the presence of grain
boundaries. The AFM image (Fig. 1 inset), edge enhanced to highlight the
grain boundaries, shows grain sizes between 20 to 60 nm.

Results
Ionic sensing test was done on a piece of 1.3 mm 15.4 mm bare NCG
strip with thickness of 9 nm. Ammonium sulphate solution, (NH4)2SO4,
of various concentration was prepared and dispensed onto the NCG strip
with a micropipette at constant droplet volume of 0.5 L. The electrical
resistance of the strip was measured using a standard 2-point probe
measurement, with probe spacing of 5 mm, using a Keithley 2100 high
precision multimeter. The resistance result (Fig. 2) shows a linear
characteristic, with a gradient of -0.40 M/(mol L-1), and reversible
decrease in resistance at room temperature, which is attributed to the
increase in possible current conduction pathways in the grain boundaries
introduced by the ionic solution. Humidity test was set up using the same
measurement set-up inside a sealed chamber with inert nitrogen
atmosphere. A commercial humidity sensor (DHT22) was used to
measure chamber relative humidity, while a commercial humidifier was
used to introduce water vapor. The time-response graph (Fig. 3) shows
increased resistance due to interaction with water vapor, possibly
demonstrating the p-type conduction of NCG films.
Future Work
Resistive strips with length measuring 1000 microns and width measuring
50 to 500 microns have been fabricated, with thickness ranging from 50
nm to 200 nm as gas sensors (see Fig. 4). Tests will be carried out using
NO2 as the analyte gas. The fabricated devices have 4-terminal aluminum
contact pads deposited with e-beam metal evaporation and patterned using
standard metal lift-off process to allow low-noise resistance
measurement.
Figure 4: Optical microscope image of some fabricated NCG resistive
sensor with four-terminal resistance readout.
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Acknowledgement
T.Y. Ling acknowledges his PhD support from the Malaysian Ministry of
Higher Education (MOHE) MyPhD Scholarship, and the Faculty of
Engineering and the Environment, and University of Southampton,
Malaysia Campus. H.M.H. Chong acknowledges Innovate UK grant for
the NEMICA project (102575). The authors acknowledge the
Southampton Nanofabrication Centre for the fabrication support. Funding
from MOHE under grant FRGS/2/2014/TK03/USMC/02/1 is also
gratefully acknowledged.