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This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP: 133.1.48.67
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Graduate School of Engineering, Osaka University, 2-1, Yamada-Oka, Suita, Osaka 565-0871, Japan
Department of Materials Science and Engineering, National Tsing Hua University, Hsinchu 30013, Taiwan
3
Department of Physics, Tamkang University, Tamsui 251, Taiwan
2
(Received 29 August 2014; accepted 20 September 2014; published online 24 October 2014)
Enhanced electron field emission (EFE) properties for ultrananocrystalline diamond (UNCD)
films upon platinum (Pt) ion implantation and subsequent post-annealing processes is reported,
viz., low turn-on field of 4.17 V/lm with high EFE current density of 5.08 mA/cm2 at an applied
field of 7.0 V/lm. Current imaging tunneling spectroscopy (CITS) mode in scanning tunneling
spectroscopy directly revealed the increased electron emission sites density for Pt ion implanted/
post-annealed UNCD films than the pristine one. The high resolution CITS mapping and local
currentvoltage characteristic curves demonstrated that the electrons are dominantly emitted
C 2014 AIP Publishing LLC.
from the diamond grain boundaries and Pt nanoparticles. V
[http://dx.doi.org/10.1063/1.4898571]
Carbon and related materials have received great attention from research community due to their immense potential
to be employed as a cold cathode material in flat panel displays and electron field emitting devices.13 Among field
emitting materials, diamond is known as a fascinating electronic material due to its negative electron affinity (NEA) surface and low effective work function.4,5 Ultrananocrystalline
diamond (UNCD) film is a special form of diamond film that
has recently attracted broad interest because of its exclusive
granular structure and better electron field emission (EFE)
properties.6,7 The fact that diamond or UNCD films can be
used as a material for the fabrication of cold cathode or other
electron emitting devices require the film to be conductive.
The incorporation of N2 during the UNCD films growth
plasma can effectively improve the electrical conductivity and
the EFE properties of the films.810 This is due to the conversion of an amorphous carbon (a-C) phase to a graphitic phase
at the grain boundaries that increases the number of conductive grain boundary channels on the surface.8,9,11 It indicates
that the grain boundary conduction mechanism is responsible
for the observed increase in EFE properties of N2 doped
UNCD films,12,13 while nano-sized diamond grains play a little role. However, a very high temperature of about 800 C is
required for the synthesis of N2 doped UNCD films.12,13
On the other hand, ion implantation can modify the
properties of materials through controlled doping of variety
of dopants.14,15 Ion implantation can introduce defects and
break the CC and hydrocarbon bonds to form sp2 carbon
and can be used to tailor the sp2/sp3 ratio for the diamond or
related carbon materials by properly selecting the energy and
dose of implantation.16,17 The sp2-bonded carbon phase in
the diamond grain boundaries can be thought to be the prime
electrical conduction promoters, which form interconnected
networks of conducting sp2 path, where electrons can easily
move. However, the electrical conductivity of a-C phases
a)
b)
0003-6951/2014/105(16)/163109/5/$30.00
contained in the grain boundaries of UNCD films is not sufficiently high and therefore, limits the EFE properties achievable for UNCD films.12,13,18 Converting the a-C phase to
graphitic phase seems to be the right way for further improving the EFE properties of UNCD films.
Moreover, the direct detection of electron emission site
from the diamond grain or grain boundaries in such a microscopic scale is crucial. The grain boundary electron
emission was explained by May and co-workers19 who
intentionally used high input bias to burn out the emission
sites in polycrystalline diamond films. The damaged emission sites showed ring-like craters surrounding grains, suggesting that the grain boundaries were the electron
emission carriers that damaged due to passage of excessive
current. On the other hand, field electron emission microscopy (FEEM), is used to collect the field-emitted electrons
and image them enabling their origin to be determined.
Garguilo used FEEM20 to study the emitting sites from
NCD films and found that the emission originated from
localized regions smaller than 100 nm in size. Moreover, up
to date three experimental studies report the observation of
emission sites by using scanning tunneling microscopy
(STM) to map simultaneously the surface topography and
the emission site densities on diamond surfaces. Karabutov
et al.21 used STM to study the emission sites of microcrystalline diamond films and reported that the emission sites
were not due to the sharp morphology protrusions (grains)
but instead the morphology pits (grain boundaries).
However, it was not clear whether the diamond grain or
grain boundaries were the emission sites from the data for
one sample at 400 400 nm scale. Krauss and co-workers22
used STM to show that the emission sites from UNCD films
coated on sharp Si micro tip are related to minima or inflection points in the UNCD surface topography, and not to surface asperities. Their tight binding pseudo potential
calculations along with the STM results indicate that
the grain boundaries play a critical role in the electron
emission properties of UNCD films. Recently, Chatterjee
105, 163109-1
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Panda et al.
FIG. 1. Electron field emission properties (JE curves) of (I) P-UNCD, (II)
Pt&A-UNCD films. The inset shows the corresponding Fowler-Nordheim
(F-N) plot.
FIG. 2. STM image of (a) P-UNCD and (c) Pt&A-UNCD films with their
corresponding CITS mapping in (b) and (d), respectively.
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Panda et al.
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Panda et al.
implantation/post-annealing processes. Fig. 4(a) shows the typical bright field image for the Pt&A-UNCD films. Inset in Fig.
4(a) shows the selective area electron diffraction (SAED) pattern which illustrates that, besides the diffraction rings corresponding to the (111), (220), and (311) lattice planes of
diamond, there presents an extra diffraction ring corresponding
to Pt material (designated as (111)Pt), confirming the presence
of Pt nanoparticles on Pt&A-UNCD films. Dark-field images
were taken from a different part of SAED, i.e., from the diffraction spots corresponding to diamond, graphite, and Pt separately and the images were then superimposed to clearly
illustrate the distribution of these phase constituents. Figure
4(b) clearly shows that the Pt-clusters (blue color) were uniformly distributed among the UNCD grains (red color) in
Pt&A-UNCD films; so do the nano-graphitic clusters (green
color). More detailed microstructure of Pt&A-UNCD films
were illustrated by TEM. Fig. 4(c) shows the structure image
for a typical region in Pt&A-UNCD films (Fig. 4(a)). Fourier
transformed diffractogram (FT) image of the entire structure
image (FT0) in Fig. 4(c) shows a spotted diffraction pattern
arranged in ring, suggesting nano-sized nature of the diamond
(D) and platinum (Pt) phases. The donut-shaped diffused diffraction ring located at the center of FT0 image corresponds to
graphitic (G) phase. The existence of diamond (D) phase is
FIG. 4. The (a) bright field with corresponding SAED pattern in inset and
(b) dark field (DF) TEM micrographs of Pt&A-UNCD film. (c) Typical
High resolution TEM structure image of Pt&A-UNCD films. The FT image
corresponding to whole structure image is shown as FT0 and the FT images
of the selected regions as 14 are shown as insets FT1FT4, respectively.
Carbon edge (d) core-loss and (e) plasmon-loss EELS spectra of Pt&AUNCD films.
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Panda et al.
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