Application of ZnO nanopillars and nanoflowers to field-emission luminescent tubes

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Vol. 33, No. 4 Journal of Semiconductors April 2012
Application of ZnO nanopillars and nanoflowers to field-emission
luminescent tubes
+
Ye Yun()
1;
, Guo Tailiang()
1;
, and Jiang Yadong()
2
1
College of Physics and Information Engineering, Fuzhou University, Fuzhou 350002, China
2
State Key Laboratory of Electronic Thin Films and Integrated Devices, University of Electronic Science and
Technology of China, Chengdu 610054, China
Abstract: Zinc oxide (ZnO) nanopillars on a ZnO seed layer and ZnO nanoflowers were synthesized by elec-
trochemical deposition on linear wires. The morphologies and crystal orientation of the ZnO nanostructures were
investigated by a scanning electron microscopy and an X-ray diffraction pattern, respectively. Detailed study on
the field-emission properties of ZnO nanostructures indicates that nanopillars with a high aspect ratio show good
performance with a low turn-on field of 0.16 V/jm and a high field enhancement factor of 2.86 10
4
. A lumines-
cent tube with ZnO nanopillars on a linear wire cathode and a transparent anode could reach a luminance of about
1.5 10
4
cd/m
2
under an applied voltage of 4 kV.
Key words: ZnO nanopillars; electrochemical deposition; field emission; luminescent tube
DOI: 10.1088/1674-4926/33/4/043003 EEACC: 2520
1. Introduction
Developed over two decades ago, cold electron sources
based on field emission have such advantages over thermo-
electronic emission or semiconductor diodes as high bright-
ness, a larger color gamut, a long lifetime and are free of
hazardous substances
14
. A comprehensive overview of the
various applications in field-emission displays, lighting ele-
ments, electron microcolumns in lithography, mass spectrom-
etry for space exploration and radio frequency devices etc, is
presented by Xu and Huq
5
. So far, carbon nanotubes (CNTs)
are promising cold field-emitter candidates. Recently, a CNT-
based lighting source was successfully developed. The appli-
cation of CNTs to electron sources for lighting element tubes
is reported by Saito et al.
6
. Also, Bonard et al.
7
reported
the application of CNTs grown on metallic wire in luminescent
tubes, and more recently the lighting elements of the four pri-
mary colours were produced and a brightness >10 000 cd/m
2
was demonstrated
8
.
Meanwhile, one-dimensional nanoscale materials have
also appeared to be quite competitive. Zinc oxide (ZnO) is a
transparent semiconductor with a wide band gap of 3.37 eV
and a large excited binding energy of 60 meV at room tem-
perature
912
. Its band bending, which usually favors field
emission by lowering the surface barrier and bringing more
electrons to the bottom of conduction band, can be quite dra-
matic under high field. A striking advantage of ZnO lies in its
high field-emission stability, in comparison to the well-studied
CNTs, particularly in poor vacuum and low air pressure oper-
ating conditions
13
. Recently, it has been found that the syn-
thesis methods and field-emission performances of ZnO nano-
structures have been reported
1418
.
In the present work, we synthesize two different types
of ZnO nanostructures on a linear metallic wire, including
nanopillars and nanoflowers, using electrochemical deposi-
tion, and the field-emission properties of ZnO nanostructures
are studied. In particular, for future practical applications, we
try to assemble a field-emission luminescent lighting tube with
a linear cathode and a cylindrical anode, and the results are
quite encouraging.
2. Experimental methods
All the chemicals (Shanghai Chemicals Co. Ltd.) were
of analytical grade and used as received. Prior to the elec-
trochemical deposition, the nickel wires were ultrasonically
washed for 10 min in an acetone, absolute ethylalcohol, and
deionized water, respectively. After that, the ZnO seed-layer
films were deposited on nickel wires using the solgel method.
Zinc acetate dihydrate (Zn(CH
3
COO)
2
2H
2
O) was briefly dis-
solved in a mixed solution of ethanolamine (NH
2
CH
2
CH
2
OH)
and 2-methoxyethanol ((CH
3
)
2
CHOH) at a concentration of
0.75 mol/L. Then the resultant solution was stirred at 60

C
for 30 min to yield a homogeneous and clear colloid solu-
tion. The clean nickel wires were dipped into the colloid so-
lution for 5 min, and subsequently dried in a furnace at 350

C for 30 min. Details of the electrochemical deposition have

been given elsewhere
19
. As shown in Fig. 1, the ZnO nano-
structures were grown by amperometry potentiostatically at
1.20 V (with respect to an Ag/AgCl reference electrode) for
4 h on linear substrates in a three-electrode cell immersed in a
water bath held at 70

C. A nickel wire and a stainless steel cir-

cular cylinder served as the working electrode and counter elec-
trode, respectively. The electrolyte consisted of a zinc nitrate
* Project supported by the National High Technology Research and Development Program of China (No. 2008AA03A313), the National
Natural Science Foundation of China (No. 61106053), and the State Key Laboratory of Electronic Thin Films and Integrated Devices,
China (No. KFJJ200916).
f Corresponding author. Email: yeyun07@fzu.edu.cn, gtl@fzu.edu.cn
Received 16 September 2011, revised manuscript received 29 November 2011 c _2012 Chinese Institute of Electronics
043003-1
J. Semicond. 2012, 33(4) Ye Yun et al.
Fig. 1. Schematic of the ZnO nanostructures grown on metallic nickel
wire by electrochemical deposition.
(Zn(NO
3
)
2
6H
2
O) solution with a concentration of 0.01 mol/L
mixed with 0.02 mol/L sodium hydroxide (NaOH). Thus, the
general scheme of the electrochemical deposition of ZnO from
aqueous Zn(NO
3
)
2
solution is supposed as follows:
Zn
2C
NO

3
2e

ZnO NO

2
. (1)
5Zn
2C
NO

3
2H
2
O 8e

5ZnO NH
C
4
. (2)
The morphology of the as-grown samples was observed
with scanning electron microscopes (SEM, Hitachi 3000), and
the crystal structure of the products was characterized by X-
ray diffraction (XRD, Philips XPert, CuK line: 0.15419 nm).
The field-emission measurements were carried out in a vac-
uumsystemwith a base pressure of 10
5
Pa. Acylinder-shaped
quartz glass tube with ITO and phosphor film was used as the
anode. Two kinds of cathodes were used in the measurement.
One was a nickel wire coated with a ZnO seed layer and nano-
structure, and the other was a ZnO nanostructure on a nickel
wire. The cathode was fixed in the centre of cylinder-shaped
anode using two elasticity metal tongs. The spacing between
the phosphor screen anode and the cathode was 10 mm. The
J1 curve and the dependence of the luminance on the applied
voltage (1V curve) could be recorded automatically with a
self-developed signal acquisition system.
3. Results and discussion
Figure 2 shows the SEM images of the ZnO sam-
ples by electrochemical deposition. From the inserted high-
magnification SEM image (Fig. 2(a)), we can see that the ob-
tained ZnO nanopillars are all hexagonal, straight and rela-
tively vertical to the substrate, with average diameters of about
300 nm and lengths of about 5 jm. But the SEM image of
Fig. 2(b) shows that the ZnO nanoflowers are made up of one
centre about 400 nm in diameter and four leaves about 800 nm
in length. From the above observations, it is clear that the
morphologies of electrochemically deposited ZnO vary from
nanopillars to nanoflowers because of the existence of the seed
layer.
Figure 3 shows the XRD patterns of the electrochemi-
cally deposited ZnO nanopillars and nanoflowers. From these
XRD data, the characteristic diffraction peaks of the hexago-
nal wurtzite-structured ZnO are indexed as (100), (002), (101)
Fig. 2. SEM images of (a) ZnO nanopillars grown on a seed layer, and
(b) ZnO nanoflowers grown without a seed layer.
and (102). But, for the nanopillars electrochemically deposited
on a seed layer, the diffraction peak intensity ratio of (002)
is stronger than that of the ZnO nanoflowers, indicating their
highly c-axis orientation. This corresponds to the results of the
SEM image.
It is known that there are many factors (such as reduction
potential, substrate and capping agents) that affect the crystal
characteristics of ZnO nanostructures produced by the electro-
chemical deposition process. The presence of a ZnO seed layer
for the formation of c-axis oriented ZnO nanostructures has
been investigated in previous studies
2022
.
Field-emission measurements are carried out using a
cylinder-shaped configuration. The ZnO nanostructures on
metallic nickel wires and a cylinder-shaped quartz glass tube
coating with transparent ITOand phosphor films are used as the
cathodes and anodes, respectively. The distance between the
cylinder-shaped anode and the centric cathode wire is 10 mm.
When a high voltage is applied to the anode, electrons will be
emitted from the cathode wires and excite the phosphor screen.
The emission current is measured by applying a voltage,
which increases from 1 to 5.5 kV. The dependencies of the
field-emission current density on the applied electric field (J
1) are shown in Fig. 4. The turn-on fields (defined as the ap-
plied field to draw an emission current density of 10 jA/cm
2
)
are 0.16 V/jm for the ZnO nanopillars and 0.24 V/jm for the
ZnO nanoflowers, respectively, which are lower than those of
the ZnO nanostructures (~917 V/jm for 10 jA/cm
2
) grown
by electrochemical deposition
23
. And the threshold fields (de-
043003-2
J. Semicond. 2012, 33(4) Ye Yun et al.
Fig. 3. XRD patterns of (a) ZnO nanopillars grown on a seed layer,
and (b) ZnO nanoflowers grown without a seed layer.
Fig. 4. Dependencies of the field-emission current density on the ap-
plied electric field (J1) of ZnO nanopillars and nanoflowers.
fined as the applied field where an emission current density ar-
rives at 1 mA/cm
2
) of the ZnO nanopillars and nanoflowers
are 0.36 and 0.42 V/jm, respectively. The emission current
density is achieved about 8 mA/cm
2
at 0.4 V/jm of the ZnO
nanopillars, which is lower than that of the ZnO nanoflowers
at 0.54 V/jm. This means that the field-emission properties of
ZnO nanopillars are better than those of ZnO nanoflowers.
Generally, it is well agreed that field emission mainly de-
pends on the tip morphology and large aspect ratio of the nano-
structures. Since the ZnOnanopillars have a much larger aspect
Fig. 5. Corresponding FowlerNordheim plots of the ZnO nanopillars
and nanoflowers.
ratio compared to the ZnOnanoflowers, it is reasonable that the
electrons can be more easily emitted fromthe nanopillars based
on the seed layer in our case.
According to the FlowerNordheim(FN) theory, the rela-
tionship between current density (J) and applied electric field
(1) can be described as follows
24
:
J =

2
1
2

exp

T
3=2
1
!
. (3)
where = 1.54 10
10
(AeV/(V
2
jm)), T = 6.83
10
3
(V/(eV
3=2
jm)), and is the work function about 5.4 eV
for ZnO
25
. is the field-enhancement factor, which is asso-
ciated with the magnitude of the electric field at the emitting
surface by the relation 1
.local/
= 1, where 1
.local/
is the lo-
cal electric field at the emitting top surface. The FN plots for
the samples are shown in Fig. 5. These approximate straight
lines indicate that the emitting electrons mainly result from
field emission. From the averaged slope of the ln(J,1
2
) ver-
sus 1/1 plots, the values can be estimated, and are shown in
Fig. 5. It is interesting in our case that there is such a large
value of the ZnO nanostructures, which is caused by the cylin-
drical geometry. The total value can be expressed as
=
ZnO

cylinder
=
ZnO
V
1
1
ln
1
2
1
1
. (4)
where 1
2
=1 10
4
jm (the distance of the anode to the cath-
ode) and 1
1
= 150 jm (the radius of the cathode). The
ZnO
values are estimated to be about 1802 for the ZnO nanopillars
and about 397 for the ZnO nanoflowers, respectively. The ver-
tical growth of the ZnO nanopillars means they have a better
ability to enhance the local field at the emitting surface and
reduce the turn-on electric field. The above results indicate
that the cylindrical configuration produces better field emis-
sion than the parallel-plate configuration.
A luminescent tube is fabricated with a cylinder-shaped
quartz glass anode and ZnO nanopillars grown on the nickel
wire cathode, and the lighting photo of the sample tube is
shown in Fig. 6. The luminance of the tube achieves about
15000 cd/m
2
, measured by a photometer under the conditions
of a 4 kV applied voltage, and yields an emission current den-
043003-3
J. Semicond. 2012, 33(4) Ye Yun et al.
Fig. 6. (a) A luminescent tube fabricated with a metallic cathode wire
of ZnO nanopillars, and (b) a cylinder-shaped anode.
Fig. 7. Emission stability of a luminescent tube with a ZnO nanopillar
cathode.
sity of 8 mA/cm
2
. The luminance efficiency, j (lm/W), is de-
fined as
j =

1
1
V1
=

1
1

2
VJ
. (5)
where
1
and
2
are the anode and cathode areas, i.e. the
phosphor-coated and ZnOnanostructure-coated areas (m
2
), re-
spectively. 1is the measured luminance (cd/m
2
). We estimated
j =9.8 lm/Wat V =4 kV, J =8 mA/cm
2
,
1
=62.8 cm
2
,
2
=0.942 cm
2
and 1=15000 cd/m
2
in our device. The emission
stability of a luminescent tube with a ZnO nanopillar cathode
is given in Fig. 7. The stability measurement was performed
for 20 h with an initial current density of about 8 mA/cm
2
, and
it was clear that no obvious decrease can be seen after 20 h.
Therefore, the ZnO nanopillars grown on metallic wire should
be considered as a promising candidate in future device appli-
cations such as high-brightness electron sources.
4. Conclusion
In conclusion, we successfully synthesized ZnO nanopil-
lars on a seed-layer film and nanoflowers on metallic nickel
wires via simple electrochemical deposition. The seed layer
induces the highly c-axis orientation of the ZnO nanopillars,
which leads to a high aspect ratio. Efficient field emission
indicates that the cathode wires of the ZnO nanopillars and
nanoflowers possessed good performance with low turn-on
and threshold fields. The experimental results demonstrate that
ZnO nanopillars grown on metallic wires by electrochemical
deposition could be a significantly promising method for mak-
ing field-emission electroluminescent light sources.
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