Diamond and Related Materials 9 (2000) 358–363

www.elsevier.com/locate/diamond

Nitrogen-doped diamond films selected-area deposition by the

plasma-enhanced chemical vapor deposition process
Kuoguang Perng a, Kuo-Shung Liu a, I-Nan Lin b, *
a Department of Materials Science and Engineering, National Tsing-Hua University, Hsin-Chu, Taiwan 300, R.O.C.
b Materials Science Center, National Tsing-Hua University, Hsin-Chu, Taiwan 300, R.O.C.

Abstract

The nitrogen-doped diamond films have been successfully synthesized by using urea as the nitrogen source. Selected-area
deposition of diamond nuclei was formed by using a SiO layer as the masking material. Diamond pads, around 9 mm in diameter,
2
were obtained when the N-doped diamond films were deposited on these patterned diamond nuclei using the chemical vapor
deposition process. An emission current density as high as 200 mA/cm2, with a turn-on field of around 8 V/mm, was obtained.
However, the diamond emitters broke down easily, which is ascribed to the localized melting of the substrate materials surrounding
the diamond pads. © 2000 Elsevier Science S.A. All rights reserved.

Keywords: Chemical vapor deposition; Electron field emission; Nitrogen-doped diamonds; Selected-area deposition

1. Introduction [19–23]. Selective suppression on the formation of dia-

Field emission devices ( FED) with a high emission
current density have been obtained in metal tip- [1] and
silicon tip arrays [2]. They have a great potential for
applications as electron emitters in flat panel displays
and have attracted thorough investigations. Diamond
films have negative electron affinity (NEA) characteris-
tics [3]. They are considered to be highly promising for
applications in electron field emission devices, and the
related emission properties have been widely investigated
[4–12]. Moreover, the inclusion of aliovalent dopants
such as nitrogen, phosphor or boron to convert dia-
monds into semiconducting materials has been found to
enhance the field emission characteristics of these films
considerably [13–18].
Patterning of diamond films is a technique urgently
needed for devices such as electron emitters. However,
etching of diamond films is difficult due to their chemical
inertness. Therefore, selected-area deposition (SAD) of
diamond films, a self-aligned process, is an indispensable
alternative. SAD of diamond films is commonly achieved
by either enhancing the nucleation rate on selected
regions or suppressing the formation rate on the others
* Corresponding author. Fax: +886-3-5716977.
E-mail address: inlin@mx.nthu.edu.tw (I-Nan Lin)
mond nuclei has been obtained by precoating the
selected regions with low-nucleating materials such as
amorphous silicon oxide layers or nitride layers.
Selective enhancement on the rate of diamond nucle-
ation, however, has been successfully achieved by bom-
barding the selected area using hard materials, or by
ion implantation. The ability to grow the diamond films
selectively using silicon oxide as a masking material is
of practical importance in the development of novel
devices using diamond films since SiO layers are the
2
most commonly used masking materials in mechano-
electrical microsystem (MEMS).
Therefore, in this study, SiO materials were chosen
2
as masking materials for selective deposition of nitrogen-
doped diamond films on silicon substrates using the
microwave-enhanced CVD method. The electron field
emission properties of the SAD diamond films thus
obtained were examined, and the possible mechanism
was discussed.
2. Experimental
Diamond films were grown on silicon substrates by
a microwave plasma-enhanced chemical vapor depos-
ition (MPECVD) method, using an ASTeX 5400 system.
The substrates, (100) p-type silicon with the resistivity

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 K. Perng et al. / Diamond and Related Materials 9 (2000) 358–363 359

of 10 V-cm, were cleaned by acetone and deionized

water prior to deposition. The diamond grains were
directly nucleated on a mirror-smooth silicon surface
using a −170 V bias voltage for 12 min and then depos-
ited with a bias voltage applied in situ. In addition to
the CH and H (CH /H =18/300 sccm) gases used,
4 2 4 2
nitrogen species were incorporated into diamond films
by directly vaporizing urea maintained at 23°C (6 sccm).
The total pressure and microwave power were controlled
at 70 Torr and 2500 W, respectively, and the substrate
temperature was maintained at around 900°C. A SiO
2
layer, around 500 nm in thickness, was first deposited
on a silicon substrate using the atmospheric pressure
chemical vapor deposition (APCVD) process, followed
by the standard lithographic process to form 5 mm
patterns of exposed Si surface. The patterned Si sub-
strates were prenucleated under bias, followed by etching
of the SiO layer to yield patterns of nuclei. Finally,
2
diamonds were selectively grown on these prenucleated
patterns by the CVD process without bias.
The morphology and structure of the diamond films
were examined using a scanning electron microscope
(SEM, Hitachi S-4000) and Raman spectroscope (He–
Ne Laser, Renishaw), respectively. The electron field
emission behavior of diamond films was characterized
by a diode set-up, in which the as-deposited diamond
films, without any preconditioning process, were sepa-
rated from the anode (In Sn )O -coated glass, by
1−x x 2
using 50 mm glass fibers as spacers. The current–voltage
characteristics were measured by using an electrometer
( Keithley 237). The electron field emission properties
were analyzed using the Fowler–Nordheim model[24],
viz. I=aV2 exp(−bW3/2/V ), where a and b are constants.
e
The turn-on voltage was estimated as the voltage at
which the log(I/V2)−1/V curve deviates from the
Fowler–Nordheim plot, and the effective work functions
(W =W/b) of these films were calculated from the slope
e
of the Fowler–Nordheim plot, where b is the field Fig. 1. (a) SEM microscopy and (b) Raman spectra of nitrogen-doped
enhancement factor, and W is the true work function of diamond films grown with CH /H /urea=18/300/0 sccm (n ) or
4 2 0
these materials. 18/300/6 sccm (n ).
6

into diamond lattices. However, the SEM micrographs

3. Results and discussion
The incorporation of urea into CH /H mixture
4 2
substantially modifies the nucleation rate of diamonds
on the mirror surface of the silicon substrate. The bias
current induced with a bias voltage of −170 V in the
CVD chamber increases with nucleation time and
reaches the saturated value at 9 min, when 0 sccm urea
was introduced into the chamber (H /CH =
2 4
300/18 sccm). The saturated time interval (t ) increases
s
monotonously with the urea content in the gas mixture,
indicating that the nucleation of diamonds is signifi-
cantly retarded due to incorporation of nitrogen species
shown in Fig. 1a reveal that, when deposited for 1 h
under 0 V bias voltage after completion of the nucleation
period under a bias voltage of −170 V, these diamonds
grow to a size of around 0.6 mm, which does not vary
with the urea concentration in the gas mixture. The size
distribution of these diamonds is quite uniform. The
Raman spectra shown in Fig. 1b indicate that character-
istics of diamond films vary insignificantly with nitrogen
content. A sharp diamond characteristic peak, labeled
as the D-band, occurs at 1332 cm−1, whereas a diffused
graphite characteristic peak, labeled as the G-band,
occurs at 1593 cm−1. In addition, a diffused peak
(G∞-band) appears near the same location as the D-band
360 K. Perng et al. / Diamond and Related Materials 9 (2000) 358–363
Fig. 2. Electron field emission properties of nitrogen-doped diamond films grown with CH /H /urea=18/300/0 sccm (n ) or 18/300/6 sccm (n ); the
inset shows the corresponding Fowler–Nordheim plots.
resonance peak, and another diffused resonance peak
(D∞-band) is barely observed in the vicinity of
1160 cm−1. These diffused resonance peaks are presuma-
bly contributed from the amorphous carbon and nano-
sized diamond crystals.
The SEM microscopic and Raman spectroscopic
examination illustrates that the microstructure and crys-
tal structure of the diamond films is insignificantly
modified due to the incorporation of nitrogen. However,
the electrical resistivity and the electron field emission
properties of these diamond films vary markedly with
the concentration of urea in plasma. As shown in Fig. 2,
the undoped diamonds (n ) exhibit essentially no
0
electron field emission characteristics. The electron field
emission capacity of the films improves dramatically
due to the incorporation of nitrogen. The electron field
emission current density (J ) reaches J =1020 mA/cm2
e e
(at 21.6 V/cm) for nitrogen-doped samples (n ). The
6
resistivity of these diamond films, measured by the four-
point probe technique, decreases from 0.28 V-cm to
0.076 V-cm due to nitrogen doping.
The selected-area deposition of diamond nuclei on
patterned silicon substrate is much more difficult than
the formation of diamond nuclei directly on an unpat-
terned silicon substrate. An excessively high microwave
power induced overheating of the substrate due to the
insulating nature of the SiO coating, whereas insuffi-
2
cient microwave power would result in an insufficient
proportion of carbon species to form diamond nuclei.
A similar phenomenon occurred when the total pressure
of the deposition chamber was changed. The diamond
nuclei could be successfully formed only when the
4 2 0 6
plasma was induced in a very narrow range, i.e. 2500 W
microwave power and 70 Torr total pressure. Fig. 3a
and the corresponding inset illustrate the morphology
of the nuclei pattern after the SiO layer had been etched
2
away. Each of the nuclei pads, with an irregular shape
and with a size of around 10 mm, contains numerous
submicron-sized diamond grains (~0.5 mm). Fig. 3b
indicates that, after CVD growth for 1 h, a regular array
of these diamond pads, with a circular geometry and a
size of about 9 mm, was obtained. The enlarged micro-
graph shown in inset of this figure reveals that these
diamond pads consist of submicron-sized diamond
grains, which are not significantly different from the size
of the grains in the nuclei pads.
Field emission characteristics of the diamond pattern
thus obtained are shown in Fig. 4a, revealing that an
emission current as large as 4 mA was achieved for an
anode electrode area of about 0.1 cm2. It should be
noted that these diamond pads occupy only about 20%
of the substrate area. The electron field emission capacity
of the diamond pads is thus calculated to be around
200 mA/cm2, which is slightly smaller than the emission
capacity of planar N-doped diamond films shown in
Fig. 2. The probable cause is the uneven distribution of
the electron field emission current density, which will be
discussed shortly. The Fowler–Nordheim plot of the J–
E characteristics indicates that the field emission can be
turned on at 10 V/mm with an effective work function
around W =0.045 eV, which is comparable with that of
e
planar N-doped diamond films.
Although the emitters made of N-doped diamond
pads can provide a large electron density under a
 K. Perng et al. / Diamond and Related Materials 9 (2000) 358–363 361

Fig. 3. SEM micrographs of (a) as-nucleated diamond patterns and (b) CVD-grown diamond pads (CH /H /urea=18/300/6 sccm).
4 2

relatively low applied field, these emitters break down
easily during long-term tests. Fig. 5a indicates the mor-
phology of diamond pads after the occurrence of the
breakdown phenomenon. Fig. 5 reveals that the break-
down occurs only along the periphery of the emitter
diamond pads, whereas diamond grains inside the pads
remain intact. The implication of these results is that
the substrate material (Si) surrounding the emitting
pads was overheated during continuous flow of field
emission electrons.
There are two probable factors, which will lead to a
non-uniform distribution of field emission current den-
sity, viz. the geometric effect and surface conduction
process. A detailed examination of Fig. 5a reveals that
grains at the periphery of diamond pads are slightly
higher than those at the center, which results in a
localized increase on the field enhancement factor and
an uneven distribution in the electric field undergone by
the top surface of the diamonds in these two regions.
Electrons are thus extracted preferentially from the
periphery of the diamond pads. Moreover, the side walls
of the diamond pads, which are lying in parallel with
the applied field, are reported to conduct the electrons
more efficiently than bulk materials[25], as schematically
362 K. Perng et al. / Diamond and Related Materials 9 (2000) 358–363

Fig. 4. Electron field emission properties and Fowler–Nordheim plot of the nitrogen-doped diamond pads grown with
CH /H /urea=18/300/6 sccm.
4 2
illustrated in Fig. 5b. the emission current density (J ) is
e
mostly contributed by the surface current density (J )
s
rather than the bulk current density (J ). The substrate–
b
diamond interfaces surrounding the diamond pads thus
have a larger current density and are easily overheated.
Restated, the uneven distribution of emission current
density not only reduces the total emission current
available, but also induces localized melting of substrate
materials, resulting in a breakdown of emitters.

4. Conclusion

Nitrogen-doped diamond films, which possess a high

emission density, J =500 mA/cm2, with a turn-on field
e
E =5.0 V/mm, were synthesized using the CVD process
0
with CH /H /urea=18/300/6 sccm. The emission array
4 2
made up of N-doped diamond pads was successfully
obtained by forming the diamond nuclei pattern using
SiO as masking materials, followed by CVD deposition
2
of diamonds. The diamond pads thus obtained show an
emission current density of around 200 mA/cm2 with a
turn-on field, E =8.0 V/mm. Inferior emission properties
0
of diamond pads, as compared with those of planar
N-doped diamond films, are ascribed to the uneven
distribution of emission current density.

Acknowledgement
Fig. 5. (a) Typical SEM micrographs of the nitrogen-doped diamond
pads, after the occurrence of breakdown phenomenon and (b) sche- Financial support of National Science Council,
matics showing the flow of surface (J ) and bulk current (J ) density, R.O.C. through the project No. NSC89-2112-M-007-046
s b
which contribute to total field emission current density (J ).
e
is gratefully acknowledged by the authors.
 K. Perng et al. / Diamond and Related Materials 9 (2000) 358–363
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