IOP PUBLISHING

JOURNAL OF PHYSICS D: APPLIED PHYSICS

J. Phys. D: Appl. Phys. 42 (2009) 062002 (5pp)

doi:10.1088/0022-3727/42/6/062002

FAST TRACK COMMUNICATION

White light emission from chemically

synthesized ZnOporous silicon
nanocomposite
R G Singh1,4 , Fouran Singh2 , D Kanjilal2 , V Agarwal3 and R M Mehra1,4
1

Department of Electronic Science, University of Delhi, South Campus, New Delhi-110 021, India
Materials Science Group, Inter University Accelerator Centre, Aruna Asaf Ali Marg,
New Delhi-110067, India
3
Centro de Investigacion en Ingenieria y Ciencias Applicadas UAEM, Avenida Universidad 1001,
Colonia Chamilpa, CP 62210, Cuernavaca, Morelos, Mexico
2

E-mail: rgsnsc@gmail.com and rammehra2003@yahoo.com

Received 5 December 2008, in final form 31 January 2009

Published 26 February 2009
Online at stacks.iop.org/JPhysD/42/062002
Abstract
White light emission across the extended visible region of the electromagnetic spectrum from
the ZnOporous silicon (PS) nanocomposite is reported. Nanocrystallites of ZnO were grown
inside the spongy structures of PS by the chemical route of solgel spin coating. The property
of the material arises from versatile interactions among the host structures of PS and ZnO. The
origin of the observed extended white light emission from 1.4 to 3.3 eV is discussed by
developing a flat band energy diagram.
(Some figures in this article are in colour only in the electronic version)

of solid-state white light sources (SSWLSs). The potential

applications of SSWLS are immense because of their
distinctive properties such as low power consumption, high
efficiency, long lifetime, drastically reduced operating costs,
greenhouse gases and lack of toxic mercury [14]. These
nanocomposite materials have also received extensive attention
because of their other potential applications in various fields.
These composites will not only play a crucial role in improving
future optoelectronic devices [5, 6] but also have tremendous
applications in data storage [7, 8], field emission [9] and
biochemical and chemical sensors [10, 11].
In this work we have revived the use of ZnOPS
nanocomposites for extended white light emission. The direct
implications are still limited due to available packaging and
integration technology at present. The strong visible light
emission at room temperature (RT) [12] and the high surfaceto-volume ratio of PS make PS a suitable host for functional
materials [13] for development of white light from the ZnOPS
nanocomposites [14]. In addition ZnO has numerous other
attractive characteristics for electronics and optoelectronic

1. Introduction
There has been considerable interest in the development
of advanced luminescent materials for a variety of
applications such as indicators, control panel, signs decor
light, backlighting, panel indication, decorative illumination,
emergency lighting, animated signal and flat panel display
[1, 2]. The future is better focused on the exciting luminescent
characteristics of ZnO based nanocomposites and may lead to
futuristic bright light sources. The properties of the material
arise from complex interactions among the host structures of
porous silicon (PS) and ZnO. The various defects and surface
states on the interface of ZnOPS are strongly dependent on the
width of the interface. Consequently, combinatorial strategies,
in which large collections of materials are synthesized,
processed and screened, may accelerate the discovery and
optimization of phosphors with enhanced optical properties.
These nanocomposites generate special interest in the field
4

Author to whom any correspondence should be addressed.

0022-3727/09/062002+05$30.00

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J. Phys. D: Appl. Phys. 42 (2009) 062002

Fast Track Communication

devices. It has a direct band gap energy of 3.37 eV, which

makes it transparent in visible light and operates in the UV
to blue wavelength region. The exciton binding energy is
60 meV for ZnO, as compared with 25 meV for GaN.
The higher exciton binding energy enhances the luminescence
efficiency of light emission. ZnO exhibits better radiation
resistance than GaN for future devices for use in space and
nuclear applications [15]. The good luminescence efficiency,
functionality and stability of ZnO-based nanostructures are
desirable for SSWLS applications [16, 17].
SSWLS based on the existing Si-based technology is one
of the challenging goals in the field of display and light emitting
technology. Generally white light is obtained by combining
light emitting diode (LED) chips giving red, green and blue
colours [4]. But the present system does not need any colour
LEDs, due to the coupling of the UV (3.1 eV), yellowgreen
(2.342.48 eV) emission of ZnO and red (1.82 eV) emission
of PS. These couplings give a new range of luminescence
across the visible emission, which is very useful for the SSWLS
application.

PL intensity (arb. units)

2000

1.69 eV

1600

1200

2.34 eV
2.88 eV

800

400

0
1.2

1.5

1.8

2.1

2.4

2.7

3.0

3.3

Energy (eV)

Figure 1. PL spectra of ZnO/PS nanocomposites under 3.81 eV

excitation by a HeCd laser (circles). The observed spectrum is
deconvolved into three (red, green, blue) peaks and shown by solid
and dotted lines.

2. Experiments
6

PS was formed by electrochemical anodization of a boron

doped polished Si [1 0 0] wafer with a low 0.81.2
cm
resistivity. The anodization was carried out in HF (48%)
and ethanol (98%) based solution in the volumetric ratio of
1 : 1. Anodization is performed in a constant current density of
30 mA cm2 for 10 min. The ZnO crystallites were deposited
on PS using the wet chemical route of solgel spin coating.
In this process zinc acetate dehydrate [Zn(CH3 COO)2 2H2 O]
was first dissolved into the ethanol solution along with
monoethanolamine (MEA), which is highly water soluble,
non-ionic and a sol stabilizer. A homogeneous transparent
solution with a concentration of 0.2 M zinc acetate and a
1 : 1 molar ratio of MEA/zinc acetate dehydrate was prepared.
This solution was kept for hydrolysis for 48 h. The solution
was then spin coated on the PS substrate at 3500 rpm. The
precursor films were heated at 240 C for 20 min in air in
order to remove the volatile component. The synthesis was
conducted by the thermal decomposition of zinc acetate into
ZnO. The process of coating and preheating was repeated eight
times to fill the pores of PS. The annealing of the as-deposited
films was carried out at 700 C for 30 min in a controlled
argon environment using a tubular furnace. The PL studies
were carried out using a Mechelle 900 spectrograph under
3.8 eV excitation of the HeCd laser. Keithely source meters
were used for I V characterizations. Cross sectional scanning
electron microscopy (XSEM) were carried out using a JEOL
JSM5600 electron microscope at CSR, Indore.

Current (
A)

5
4
3
2
1

0
-6

-4

-2

0
-1

10

12

14

16

App. Voltage (Volt)

Figure 2. I V characteristics of a nanocomposite film:

experimental (symbol) and fitted with the trap-limited current model
(solid line) at RT.

best of our knowledge. The spectrum is deconvolved into

three bands peaking at the red (1.69 eV), green (2.34 eV) and
blue (2.88 eV) regions of the electromagnetic spectrum. The
origin of these various bands is explained later in this paper by
constructing a schematic band energy diagram.
Figure 2 shows the I V characteristics of the ZnO/PS/
p-Si/Al/ heterojunctions. A forward current of 6.0 A at
15 V, with an onset at 4 V, is obtained. It can also be seen
that up to 7 V the reverse voltage current is very small and
breakdown begins at 8 V in the reverse direction. In the
ZnO/PS heterojunction the electronhole pairs generated by
photo-excitations in the ZnO nanocrystals may get separated,
with electrons mainly transporting through ZnO channels and
holes in PS. Alternatively, one can view this as a large number
of ZnOPS heterojunctions connected in series and responsible

3. Results and discussions

Figure 1 shows the PL spectrum of the ZnOPS
nanocomposites under excitation by 3.81 eV photons. The
spectrum shows intense PL emission from 1.4 to 3.3 eV,
which seems to be the broadest spectral range from the single
inorganic solid state specimen reported in the literature to the
2

J. Phys. D: Appl. Phys. 42 (2009) 062002

Fast Track Communication

Figure 3. Cross sectional SEM micrograph of the ZnOPS interface and the inset shows the GIXRD pattern of the composite film.

in the yellowgreen part of the visible spectrum, with a

maximum between 2.35 and 2.50 eV. The origin of this
band has been attributed to deep level defects [19]. These
defects may be interstitial impurity atom and transition metal
ion vacancies in the crystal structure of ZnO produced by
deviations from stoichiometry [20]. The stable defect in
transition metal oxides generally gives too deep impurity
levels having an energy at least 1 eV away from the band
edges [21]. ZnO has a proportion of O vacancies present
in the structure and it has a great deal of complexity in the
defect chemistry [22]. Experimentally it is established from
many studies that true stoichiometry should really be written
as Zn1+ O with having a value ranging up to 103 depending
upon the conditions of preparation. This composition could
be consistent with the presence of either O vacancies or Zn
interstitials. n-type conductivity arises because of the extra
electron which is bound in the ground state but with a low
donor ionization energy. However, there is a disagreement
about the majority defect type and it may be both Zn interstitials
and O vacancies. There are also indications about the
presence of compensating defect forms of the O interstitials and
Zn vacancies [23].
For a better understanding of the carrier dynamics
associated with the light emission of ZnO/PS nanocomposites,
we propose a model to explain the PL spectra with the band
energy diagram as shown in figure 4. In this model, we have
shown the formation of the siloxene structure at the interface
of ZnO and PS. Lin et al [19] have reported that VO and
Zni are donors; VZn , Oi and OZn are acceptors in ZnO. It is
known that the band gap energies of Si, PS (considered as
a material consisting of Si nanocrystallites covered by a thin
film of a-Si : O : H layer [24]) and ZnO are 1.09 eV, 2.5 eV,

for a forward current as observed here. The observed forward

current can be attributed to the large interface of ZnO/PS
arising from the enhanced surface area of PS on account of its
proper integration with ZnO nanocrystallites and the built-in
potential across the heterojunction. Therefore, an attempt
has been made to investigate the behaviour of the observed
forward current. Three equations, I V 2 exp(a/V ), I
exp(eV /nkT ) and I V m , characteristic of the tunnelling,
thermionic and trap-limited current model [18], have been
fitted, respectively. The equation I V m fits reasonably
well and the value of m and the proportionality constants are
found to be 3 and 1.5, respectively. This analysis suggests that
transport in this case is controlled by the traps present in the
material.
Figure 3 shows the cross sectional scanning electron
micrograph of the ZnOPS nanocomposites. This micrograph
clearly reveals the filling of ZnO crystallites in the pores
of PS. The annealing at 700 C in the argon environment leads
to the formation of good quality polycrystalline crystallites
with wurtzite structure, as clearly indicated by the glancing
angle x-ray diffraction pattern, shown in the inset of figure 3.
The average size of the crystallites is also determined using
Scherrers formula and is found to be about 21 nm. Annealing
also gives rise to a strong interaction of ZnO with the PS
surface and the formation of siloxene structures at the ZnOPS
interface.
Generally, ZnO gives two emission bands; a relatively
weak and narrow UV emission band is observed around
3.25 eV due to the radiative annihilation of excitons. This
can be observed at a temperature far above RT due to
the relatively high exciton binding energy of 60 meV. The
other much stronger and broader emission band is situated
3

J. Phys. D: Appl. Phys. 42 (2009) 062002

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4. Conclusions
e -Si=4.04 eV

e-ZnO=4.35 eV

Synthesis of zinc oxide ZnOPS nanocomposites exhibiting

extended white light emission across the visible region of the
electromagnetic spectrum in the range from 1.4 to 3.3 eV is
reported. The outstanding white light emission from a single
specimen has considerable promise for the development of
advanced luminescent materials such as a solid-state white
light source (SSWLS). At a higher forward bias, the transport
of the carriers is attributed to field tunnelling. This kind of
transport is similar to the MTCE process. The energy band
gap diagram is proposed on the basis of electron tunnelling
between the interface of ZnO and PS through the siloxene
structure.

Tunneling
0. 05eV
Zn i 0 / Zn i X
0. 1 5eV

0. 0 5eV

Voo/ Vox

Zn i" / Zni '

VZn" / V Zn'
V Zn' / V Zn X

1. 69
eV

Excitation by 3.81eV
He-Cd laser

2.34 eV

2.88 eV
0.8eV

ZnO

Siloxene
structures

Porous silicon

Figure 4. Flat band energy diagram developed for the observed PL

transitions.

Acknowledgments
The authors are grateful to Dr D M Phase of UGC-DAE, CSR,
Indore, for extending their SEM facility and to Dr D K Avasthi
for his support. One of the authors (RGS) is grateful to UGC for
providing financial support under a senior research fellowship.
Another author (VA) acknowledges the financial support of
CONACyT (42939).

3.34 eV respectively. Therefore, it is clear that the band gap

energy of PS is adjusted in between the band gaps of Si and
ZnO. Therefore, the active PS layer plays a vital role in the
transport and optical properties due to the high interface state
density and the siloxene structure. The siloxene structure
works as a wavelength convertor at a higher wavelength.
This kind of transport is similar to the multistep tunnelling
captureemission (MTCE) process widely supported by
a number of studies in the field of hetero-structures
with disordered materials [25] and is consistent with the
I V studies.
The emission below 2.25 eV is explained by supposing
that luminescence is carried out at the luminescence centre
(LC) in the siloxene structure covering the nanoscale Si [26].
These are the possible siloxene structures existing according
to the temperature and formation conditions of our composite
samples. Thus, in figure 3 the band of the siloxene structure is
thus shown to depict the transitions through an arrow, which
covers the above wavelength range due to emission from
siloxene. Because of the larger surface-to-volume ratio of PS,
the direct tunnel transfer of photo-excited carriers across the
energy barrier from PS to the conduction of ZnO could be due
to the narrowing of the barrier. It seems that most photoexcited electronhole pairs tunnel outside the nanoscale Si
particles instead of recombining with them and tunnel through
the siloxene structure layer giving visible light with maxima
at 1.69 eV. There are some absorbent LCs on the surface of
PS. Some of the carriers may tunnel to the ZnO with the
narrowing of the barrier caused by increasing the conduction
band and then recombine with the V
o level deep into the
band gap, causing emission of a green light band at 2.34 eV.
The tunnelling of the conduction band electrons at the surface
decreases because it takes place between localized states while
the surface trapping of the conduction band electrons involves a
delocalized state [27]. Therefore, the emission around 2.88 eV
is attributed to the annihilation of bound excitons, i.e. electron
hole pairs from the excited state [Zn+ O ] to the initial state
[Zn2+ O2 ] [28].

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