Materials Letters 76 (2012) 131134

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Materials Letters
journal homepage: www.elsevier.com/locate/matlet

Ion-induced secondary electrons emission measurement from MgO lms deposited

on multiwalled carbon nanotubes
Chandra Bhal Singh a, c,, Surajit Sarkar a, b, Vandana Singh a, Sanjay K. Ram b, d, Satyendra Kumar a, b
a

Samtel Centre for display Technologies, IIT Kanpur, Kanpur-208016, India

Department of Physics, IIT Kanpur, Kanpur-208016, India
SSN Research Centre, SSN Nagar, Kalavakkam-603110, India
d
CEMOP, New University of Lisbon, Caparica-2829516, Portugal
b
c

a r t i c l e

i n f o

Article history:
Received 12 January 2012
Accepted 21 February 2012
Available online 3 March 2012
Keywords:
Carbon nanotubes
Nano-pores
Microstructure
Firing voltage
MgO
Thin lms
Secondary electron emission

a b s t r a c t
This study reports on the ion-induced secondary electrons emission (SEE) from MgO lms deposited on multiwalled carbon nanotubes (MWCNTs). MWCNTs are grown on quartz substrates using plasma enhanced
chemical vapor deposition system and MgO lms are deposited on that MWCNTs using electron-beam evaporation technique. The SEE coefcients are obtained from experimentally measured ring voltage. We observed stabilized and lower ring voltage of MgO lms deposited on MWCNTs than that for MgO. The
experimental results suggest that the density, uniformity and alignment of nanotubes inuence the local
electric eld in nano-pores of MgO lms which in turn affects the emission of secondary electrons from
MgO surface.
2012 Elsevier B.V. All rights reserved.

1. Introduction
The study of secondary electron emission mechanism from MgO
materials has been a matter of great importance as it plays signicant
role in decreasing the operating voltage and increasing the life-time
and luminescence of plasma display panels (PDPs). The high secondary electron emission of MgO is important in lowering the ring voltage while low sputtering yield provides long life time [1]. Wide range
of interesting applications of MgO thin lms has led to the emphasis
on increasing the SEE () coefcient as high as possible. Ultra high
coefcient (~ 123) from single walled nanotubes has been reported
by Luo et al. [2]. And, more recently M. K. Alam et al. (2011) measured
the coefcient around 1 for single MWCNTs and concluded that
depends on the number of walls, internal structure of CNT forest and
nanotube density in forest [3,4]. Very high coefcient of CNTs has
paved the way to make MgO/CNT combination to increase the of
MgO. Indeed, an enormously high electron-induced yield (~1500)
for MgO/CNTs has been reported in literature [5]. MgO is an insulating
material and its high resistivity slows down the electron emission
through its lm. Inclusion of CNTs in MgO changes its geometrical
structure. High aspect ratios and small tip radius of CNTs may cause

Corresponding author at. SSN Research Centre, SSN College of Engineering,

Kalavakkam-603110, India. Tel.: +91 8939402621; fax: +91 44 27469772.
E-mail address: cbs.sbc@gmail.com (C.B. Singh).
0167-577X/$ see front matter 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2012.02.083

a high eld across the MgO lm and an increase in yield [6]. In the
present work, idea of using two different densities of CNTs has been
developed to study the discharge characteristics of MgO lms. For
our experiment, MWCNTs are grown on quartz substrates by plasma
enhanced chemical vapor deposition (PECVD), followed by deposition
of MgO lm using electron-beam evaporation technique. Ion-induced
of MgO and MgO/MWCNT lms are measured.
2. Experimental details
MWCNTs were grown on quartz substrates using PECVD process. A
thin layer of Ti (~500 A) followed by Ni (~40 A), which acts as the catalyst layer was deposited by e-beam evaporation. Ti and Ni coated
quartz substrates were annealed to 800 C in a vacuum so that nickel
layer breaks into very small islands. These small islands of nickel act
as catalysts for the growth of the MWCNTs. A hydrogen plasma treatment was performed on Ni lms for 10 min to remove oxides and dangling bond. This H2-plasma treatment further breaks Ni islands into
nano-clusters. A mixture of C2H2 and H2 with ratio 20:80 is used to
grow MWCNTs. Oxygen treatment for 30 min was done to remove
amorphous carbon from the walls of MWCNTs. Thin MgO lms of
1 m in thickness were deposited by e-beam evaporation on MWCNT
coated quartz substrates. Three different samples of MgO, MgO/
MWCNTs (1) and MgO/MWCNTs (2) were prepared to study the effect
of MWCNTs on SEE from MgO lms. In MgO/MWCNTs (1) sample, CNTs
were less dense as compared to sample MgO/MWCNTs (2).

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C.B. Singh et al. / Materials Letters 76 (2012) 131134

Scanning Electron Microscopy (SEM) is used to generate images of

MgO/CNT structure. For the secondary electron yield () measurement
of these lms, we have designed a set up with conditions similar to
those in plasma display panels. The methodology of calculation of is
based on Paschen curves in which plasma ring voltages vs. the product
of p d are measured. The MgO coating to be tested is deposited onto
1 in. 1 in. quartz plates. Two such coated plates form an open glass
cell with the coated inner surfaces kept at a well-dened distance of
0.5 mm by spacer. Copper electrodes of 10 mm diameter are used to
connect the mounted cell to an AC high voltage source. The cell is put
in series with a reference capacitor Cref known value. Firing of the plasma results in charge transfer between the cell and Cref. Plotting the voltage measured across Cref against the total voltage applied to the system
results in a Lissajous-like gure as soon as plasma ignites. The details of
setup and measurement procedure are described in another paper [7,8].
Measurement of was done at 5 kHz frequency, 0.2 mm electrode distance and 1 nano-farad reference capacitance and neon gas is used to
create plasma between two cells. Breakdown voltage measurements
based on the Lissajous method was used to calculate . Plasma ring
voltages vs. the product of pressure and distance are measured using
the set up depicted in Fig. 1 and using equations
Vf

0:5  Cdiel
C
V ref V
Cgap 0:5  Cdiel s Cdiel R

is the chamber pressure, d is the distance between electrodes,

C (=8.2 cm 1 Torr 1) and D (=17 (V cm 1 Torr 1)1/2) are constants for neon gas. Experimentally measured ring voltage is compared with theoretically calculated ring voltage, using Eq. (2), to get
ion-induced yield. Effective yield is measured using the Paschen
curve and equation E/p=V/(p.d) and eff = 1/(exp(.d)-1); where
is a Townsend coefcient and E is electric eld which corresponds to ring voltage.
3. Results and discussion
Fig. 2 shows a typical Scanning Electron Image (SEM) of MgO thin
lm deposited on MWCNTs. It is apparent from Fig. 2 that MgO is deposited on the tips of MWCNTs. For sample MgO/MWCNTs (1), it is
clearly seen in Fig. 2(a) that CNTs are uneven in length, less dense


2

  
1
2
Vf D :p:d = ln C:p:d=ln
1

where Cdiel is capacitance of MgO lm, Cgap is capacitance of gap between the cell and Cref is capacitance of reference capacitor. Where p

HV

Electrode

Glass
Spacer
Surface
Discharge

MgO

Cdiel
Cgap
Cdiel

Cref
Reference
Capacitor

Fig. 1. The schematic of the ion-induced SEE measurement setup. The equivalent electrical circuit of cross section of discharge cell present the various capacitors (where
Cdiel = capacitance of MgO, Cgap = capacitance of gap between cell formed with two
MgO lms Cref = reference capacitor).

Fig. 2. (a) SEM image of sample MgO/MWCNT (1) (b) SEM image of sample MgO/
MWCNT (2).

C.B. Singh et al. / Materials Letters 76 (2012) 131134

and are not well aligned. SEM image of sample MgO/MWCNTs (2)
shows uniform, highly dense and well aligned CNTs as depicted in
Fig. 2(b). A comparison between the experimentally measured ring
voltage of MgO and MgO/MWCNTs lms at different neon gas pressure is shown in Fig. 3(a). A marked reduction in ring voltage for
MgO/MWCNTs can be observed in Fig. 3(a). Firing voltage for MgO/
MWCNTs lms decreases with the increase in discharge pressure
and becomes constant in range 510 Torr.cm. While for MgO lms, ring voltage rst decreases with the increase in discharge pressure and
then again starts increasing at high discharge pressure as illustrated in
Fig. 3(a). This observed change in the trend of the curve may be because of the structural change in MgO/MWCNT lms, which affect
the SEE process. Experimentally obtained Paschen curves of MgO
and MgO/MWCNTs lms are compared with the theoretically calculated ring voltage using Eq. (2) to deduce the ion-induced SEE coefcient as presented in Fig. 3(a). MgO lm shows lower coefcient
(~0.07) which becomes constant (~0.10) at p.d equals 10 Torr.cm.
Both MgO/MWCNT lms show higher coefcient than pure MgO
lm. However, higher coefcient is measured for sample MgOs/
MWCNTs (2) as compared to MgO/MWCNTs (1). For sample MgO/
MWCNTs (1), there was not much improvement in coefcient
(~0.08) at lower gas discharge pressure but with increasing pressure
it showed enhancement in coefcient and reached at ~ 0.23 for
p.d = 10 Torr.cm. Whereas, for sample MgO/MWCNTs (2), we found
coefcient 0.40 at p.d = 10 Torr.cm, which may be because of well
aligned and dense CNTs. We obtained ion-induced yield between
0.20 and 0.40 for MgO/MWCNTs, which is higher than previously
reported value (~0.1) by Won Tae Lee et al. [9]. Effective SEE (eff) of
these lms has been calculated, and results are shown in Fig. 3(b).
eff is higher than coefcient because it also includes the emitted
SEs due to the interaction with photons and other charged particles.
The value of eff for MgO/MWCNTs (2) varies from 0.40 to 0.60
while it ranges in 0.250.43 for MgO/MWCNTs (1). At E/

133

p = 30 Vcm 1 Torr 1, eff is found to be around 0.40, 0.30 and 0.20

for sample MgO/MWCNTs (2), MgO/MWCNTs (1) and MgO, respectively. The increased SEE from MgO/MWCNT combination is because
of reduced work function and high local eld near the tip of MWCNTs
[10]. There is no direct interaction of ions with MWCNTs and SEs are
emitted only from MgO surface, but MgO surface modied because of
CNTs. This surface modication reduces the work function of MgO.
The surface modication of MgO depends on geometry, diameter
and alignment of CNTs. Hollow structure of CNTs makes MgO/
MWCNTs structure porous in nature. Small diameter and nano-scale
tip of nanotubes create nano-porous close to the surface of MgO.
Strong electric eld is generated inside the vacuum of these nanopores after the accumulation of positive surface charge on MgO [11].
This accumulated positive surface charge is being formed on MgO
during interaction of charged particles and emission of secondary
electrons. The increased local electric eld strength near the tip of
Nanotubes promotes more emission of electrons.
It can be noted from Fig. 3(b) that higher discharge pressure results
in enhancement of effective SEE. At E/p = 20 V cm 1 Torr 1, eff is
nearly 0.55 for MgO/MWCNTs (2), 0.4 for MgO/MWCNTs (1) and a
lower value around 0.28 for pure MgO lm. These enhanced values of
eff for MgO/MWCNT sample are because of enhanced local eld near
the tip of nanotubes which acts as porous medium. Sample MgO/
MWCNTs (1) shows lower eff than sample MgO/MWCNTs (2). The observed difference between the values of eff for these samples of MgO/
MWCNTs can be attributed to the density, diameter and alignment of
nanotubes. In sample (1) of MgO/MWCNTs (1), lower density of nanotubes means lower number of nano-pores which also reduces total local
eld for MgO. If nanotubes are uneven in length and are not well aligned
then they create traps for emitted secondary electrons and thus lower
the eff. For higher eff, nanotubes should be highly dense, uniform
and well aligned which is found in sample (2) of MgO/MWCNTs (2).
Changes in surface properties of MgO lm due to CNTs highly affect the SEE process. It is known that grain boundaries in oxides
strongly inuence their properties [12]. Grain boundaries are extrinsic defects in MgO lms that act as source and sink of vacancies and
thus affect the emission of secondary electrons. Multiple grain boundaries between segments deposited onto different neighboring CNTs
create traps for electrons and holes. Excess Mg 2+ cations which act
as electron trap site are segregated to the grain boundaries. At grain
boundaries F-centers (O 2 vacancies) show positive nature with respect to the lattice. So, trapping of conduction-band electrons at
grain boundaries build up the charge and H-atoms, molecules
[13,14]. Work function and band gap of MgO lms decreased due to
presence of F-centers and charge-induced defects at grain boundaries
[15]. According to the relations Ei > 2w and Ei > 2( Eg + ), decreased
value of work function and band gap increases the emission of secondary electron from MgO coating on aligned CNTs .
4. Conclusions
We have experimentally demonstrated that the enhancement in
SEE of MgO coated MWCNTs is mainly because of the structural change
of MgO due to MWCNTs. It is concluded that the creation of nano-pores
due to MWCNTs in MgO lms can signicantly contribute to the enhancement of the local electric eld and subsequently emission of secondary electrons. The change in SEE yield of MgO/MWCNT lms has
been explained in terms of density, uniformity and alignment of nanotubes. This study can be utilized to increase the SEE yield of MgO by controlling the density and structural properties of nanotubes.

Fig. 3. (a) Experimental Paschen curves, ring voltage (Vf) versus (p d) measured for
MgO (open circle + line), MgO/MWCNTs (1) (open square + dash line) and MgO/
MWCNTs (2) lms (lled triangle + line). The dot and dashed lines represent the theoretically calculated Paschen curves using xed value of . (b) Effective secondary electron emission (eff ) as a function of E/p, where E corresponds to ring voltage and p is
pressure. Figure shows MgO (lled circle + line), MgO/MWCNTs (1) (open square +
dot line) and MgO/MWCNTs (2) lms (lled triangle + dash line).

Acknowledgments
The authors would like to thank SCDT, IIT Kanpur and Council for
Scientic and Industrial Research, India, Ministry of Information
Technology, New Delhi, India for funding this research.

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