Self-organized ZnO nanodot arrays: Effective control using SiN x interlayers and low-

temperature plasmas
S. Y. Huang, Q. J. Cheng, S. Xu, D. Y. Wei, H. P. Zhou, J. D. Long, I. Levchenko, and K. Ostrikov

Citation: Journal of Applied Physics 111, 036101 (2012); doi: 10.1063/1.3673593

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 JOURNAL OF APPLIED PHYSICS 111, 036101 (2012)

Self-organized ZnO nanodot arrays: Effective control using SiNx interlayers

and low-temperature plasmas
S. Y. Huang,1 Q. J. Cheng,2,3 S. Xu,1,a) D. Y. Wei,1 H. P. Zhou,1 J. D. Long,4 I. Levchenko,2,3
and K. Ostrikov2,3
1
Plasma Sources and Applications Center, NIE and Institute of Advanced Studies,
Nanyang Technological University, 1 Nanyang Walk, Singapore 637616
2
CSIRO Materials Science and Engineering, Lindfield, New South Wales 2070, Australia
3
Plasma Nanoscience @ Complex Systems, School of Physics, The University of Sydney, Sydney, New South
Wales 2006, Australia
4
Solar Energy Research Institute of Singapore (SERIS), National University of Singapore, Singapore 117574
(Received 8 November 2011; accepted 29 November 2011; published online 7 February 2012)
An advanced inductively coupled plasma (ICP)-assisted rf magnetron sputtering deposition method
is developed to synthesize regular arrays of pear-shaped ZnO nanodots on a thin SiNx buffer layer
pre-deposited onto a silicon substrate. It is shown that the growth of ZnO nanodots obey the cubic
root-law behavior. It is also shown that the synthesized ZnO nanodots are highly-uniform,
controllable by the experimental parameters, and also feature good structural and photoluminescent
properties. These results suggest that this custom-designed ICP-based technique is very effective and
highly-promising for the synthesis of property- and size-controllable highly-uniform ZnO nanodots
suitable for next-generation light emitting diodes, energy storage, UV nanolasers, and other
C 2012 American Institute of Physics. [doi:10.1063/1.3673593]
applications. V

ZnO is an advanced metal oxide material with a wide the base pressure in the chamber of approximately
direct band-gap of about 3.37 eV at room temperature and a 1.0  103 Pa was achieved. After pre-evacuation, high-
large exciton binding energy of 60 meV. The exciton binding purity (99.99%) argon and hydrogen gases were let into the
energy of ZnO (60 meV) is significantly higher than that of chamber at a rate of 9.6 and 3.2 sccm, respectively. The mag-
GaN (25 meV), which enables ZnO to emit short-wavelength netron target used in this work is a high-purity (99.995%)
light more efficiently even at room temperature.1–4 Recently, stoichiometric ZnO ([Zn]/[O] ¼ 1.0). In addition, a thin SiNx
a broad range of deposition methods have been developed to buffer layer was deposited from a mixture of reactive argon,
prepare various ZnO nanostructures, such as nanowires, hydrogen, silane, and nitrogen precursor gases using the ICP-
nanorods, nanobelts, nanopins, nanorings.5–9 assisted chemical vapor deposition. The thickness of the SiNx
However, only a few research works have been focused buffer layer was approximately 30 nm.
on the preparation of zero-dimensional ZnO nanodots.10–12 A series of samples with different deposition times rang-
Compared with one-dimensional nanostructures, zero- ing from 10 to 40 min was prepared under a ZnO target
dimensional ZnO nanodots show a stronger exciton effect power of 300 W, an inductive rf power of 1000 W, a sub-
due to the three-dimensional quantum confinement. This strate temperature of 450  C, a ratio of the flow rates of the
leads to numerous applications of ZnO nanodots in short- argon and hydrogen gases of 3: 1, and a working pressure of
wavelength optoelectronic devices such as UV light emitting 2.0 Pa. Figures 1(a)–1(d) show the top-view scanning elec-
diodes, UV nanolasers, as well as gas sensors, dye sensitized tron microscopy (SEM) images of the samples with deposi-
solar cells, and some other devices and systems.10–12 tion times of 10, 15, 30, and 40 min, respectively. At a
In this work, a custom-designed, low-frequency glimpse, one can notice the following features from the SEM
(460 kHz), low-pressure, high-density inductively coupled images with the increase of the deposition time: (1) ZnO
plasma (ICP)-based deposition technique is used to synthesize nanodots are uniformly distributed throughout the substrate;
regular patterns of highly-uniform pear-shaped ZnO nanodots. (2) the average size of the nanodots increases; (3) the density
Moreover, we have systematically studied the growth dynam- of the nanodots decreases; (4) the spacing between the nano-
ics of the synthesized ZnO nanodots and investigated the dots increases. In order to further demonstrate that the ZnO
effect of the experimental parameters on the growth behavior nanodots are uniformly distributed throughout the substrate,
of the ZnO nanodots through the use of a broad range of the inset of Fig. 1 shows a typical size distribution of the
advanced analytical tools. ZnO nanodots with a deposition time of 30 min. One can
ZnO nanodots are grown on a thin SiNx buffer layer pre- notice that about 41% of the synthesized ZnO nanodots fall
deposited onto the (100) silicon substrate using an ICP- within the narrow range of 60-65 nm and the mean size is
assisted rf magnetron sputtering deposition system.13,14 In 63 nm. Furthermore, our experiments reveal that at earlier
this system, it is possible to control the plasma production growth stages the average size d of ZnO nanodots follows
and the sputtering independently.13,14 Prior to the deposition, the cubic root-law dependence on deposition time tD (d 
tD1/3), which is consistent with the established theories of
a)
Electronic mail: [email protected]. nanodot growth.15,16

0021-8979/2012/111(3)/036101/3/$30.00 111, 036101-1 C 2012 American Institute of Physics

V

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 036101-2 Huang et al. J. Appl. Phys. 111, 036101 (2012)

ation centers can be formed, which in turn leads to the high

nanodot density.1,17 However, at a higher substrate tempera-
ture of 450  C, the diffusion and desorption rates of the
adsorbed Zn and O atoms increase. The increase of diffusion
rates leads to a large diffusion length, which in turn results in
a large size and low density of ZnO nanodots at a higher sub-
strate temperature of 450  C.
We have also investigated the influence of the inductive
rf power on the growth of ZnO nanodots. Figures 3(c) and
3(d) show two typical SEM images of the ZnO nanodots de-
posited at inductive rf powers of 0 (without turning on the in-
ductive rf power) and 500 W, respectively, while the other
experimental parameters remained the same as before. With-
out turning on the inductive rf power, ZnO continuous films
with quite small spacing between ZnO grains are formed
FIG. 1. (Color online) (a)–(c): Top-view SEM images of the samples with
deposition times of 10 (a), 15 (b), 30 (c), and 40 (d) min, respectively. The (Fig. 3(c)). However, at an inductive rf power of 500 W, the
inset shows a typical size distribution of the ZnO nanodots with a deposition uniform nanodots with a larger spacing can be obtained. This
time of 30 min. result can be interpreted based on the effect of the plasmas
on the growth behavior of the ZnO nanodots. It is well
Another distinctive feature of the synthesized ZnO known that the ICP source features high-density and highly-
nanodots on the SiNx buffer layer is revealed in the side- uniform plasmas.18,19 The electron number density obtained
view SEM image. Figure 2 shows the tilt-view SEM image in the ICP plasmas can be approximately two orders of mag-
of the synthesized ZnO nanodots with a deposition time of nitude higher than that produced by the capactively coupled
30 min. One can clearly observe that the densely packed plasmas under quite similar discharge conditions.20,21 With
spherical and pear-shaped structures with a large surface the addition of the ICPs, the density of reactive species can
area to volume ratio are formed on the solid. These structures be significantly increased due to the strong interactions
are arranged as if they do not wet the Si surface, which, to between the electrons and atoms. This increases the atom
the best of our knowledge, has never been reported before fluxes (Zn or O atoms) to the substrate due to the strong sput-
for ZnO nanostructures.6,7 tering of the target and also the surface temperature due to
Figures 3(a) and 3(b) show two typical SEM images of the strong ion bombardment of the substrate surface. As a
the ZnO nanodots deposited at substrate temperatures of 350 result, the surface diffusion length of Zn atoms increases,
and 450  C with a deposition time of 40 min, respectively, leading to larger nanodot sizes and inter-nanodot
while the other parameters remained the same. When the spacing.14,22,23
substrate temperature is increased from 350 to 450  C, the Figures 4(a) and 4(b) show the typical narrow scan XPS
average size of the nanodot increases from 56 to 79 nm while spectra of the O 1 s and Zn 2p3/2 for the sample with a deposi-
the dot density significantly decreases from 3.33  1010 to tion time of 30 min. The peak fitting performed on the O 1 s
1.76  1010 cm2. This result can be interpreted in terms of spectrum yields two peaks, located at binding energies of
the classical nucleation theory. When the substrate tempera- 530.01 and 531.62 eV, respectively. These two peaks are
ture is low (350  C), the conditions for the high-density
nucleation are favorable. Therefore, a large number of nucle-

FIG. 2. A typical tilt-view SEM image of the ZnO nanodots with a deposi- FIG. 3. (a) and (b): Two typical SEM images of the ZnO nanodots deposited
tion time of 30 min (the left and right insets show zoom-in cross-sectional at substrate temperatures of 350  C (a) and 450  C (b), respectively; (c) and
and tilted views of the pear-shaped structures, respectively). A shape close (d): Two typical SEM images of the ZnO nanodots deposited at inductive rf
to spherical is clearly seen on the left inset. powers of 0 W (c) and 500 W (d), respectively.

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 036101-3 Huang et al. J. Appl. Phys. 111, 036101 (2012)

attributed to O2 ions in the normal wurtzite structure of ZnO In summary, highly-uniform and size-controllable pear-
single crystal and O2 ions in the oxygen deficient regions shaped ZnO nanodots have been synthesized using ICP-
within the matrix of ZnO.1,24 Meanwhile, the Zn 2p3/2 peak can assisted rf magnetron sputtering deposition system. Experi-
only be fitted with one single peak, located at a binding energy mental results show that the growth of ZnO nanodots can be
of 1022.18 eV. This peak is attributed to Zn2þ ions in the effectively controlled by the process parameters. X-ray photo-
oxygen-deficient ZnO matrix, which suggests that Zn exists electron spectroscopy measurements show that the ZnO nano-
only in the oxidized state.6,24 The relative atomic concentra- dots are oxygen deficient with 42.3 at % of O and 57.7 at % of
tions of Zn and O elements calculated by using the Zn. Room temperature photoluminescence measurements
corresponding integrated peak areas and sensitivity factors demonstrate a dominant near-band-edge UV peak at 387 nm
(Zn: 2.768, O: 0.733) are 42.3 at % of O and 57.7 at % of Zn.1,6 in the ZnO nanodots. These results are highly-relevant to the
Fig. 4(c) shows the room temperature PL spectrum of development of the next-generation light emitting diodes, UV
the sample with a deposition time of 30 min. Two distinct nanolasers, solar cells, and other devices.
peaks can be observed: one is sharp ultraviolet emission This work is partially supported by the National
located at 387 nm, and the other one is broad green emis- Research Foundation (Singapore), CSIRO’s OCE Science
sion located at 550 nm. These two peaks are related with Leadership Scheme, the Australian Research Council (Aus-
near-band-edge emission generated by free-excition recom- tralia), and the National Natural Science Foundation of
bination and deep-level defect emission mostly generated by China (Grant No. 90 923 005), Collaborations and fruitful
the single ionized oxygen vacancies.1,25 As can be seen in discussions with X. X. Zhong are gratefully acknowledged.
Fig. 4(c), the ratio of the intensity of the UV peak to that of
the green peak is very high, suggesting that the ZnO nano-
1
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