NANO

LETTERS

Ultraviolet Electroluminescence from 2005

Vol. 5, No. 10
ZnO/Polymer Heterojunction 2005-2008
Light-Emitting Diodes
R. Ko1 nenkamp,* R. C. Word, and M. Godinez

Physics Department, Portland State UniVersity, 1719 Southwest 10th AVenue,

Portland, Oregon 97201

Received August 1, 2005; Revised Manuscript Received September 1, 2005

ABSTRACT
We report ultraviolet electroluminescence at 390 nm from diode structures consisting of electrodeposited ZnO nanorods sandwiched between
a transparent SnO2 film and a p-type conducting polymer. The nanorods are embedded in an insulating polystyrene layer. ZnO deposition
occurs at 90 °C and produces vertically oriented nanorods with very high uniformity over areas of ∼20 cm2. Electron diffraction shows the
nanorods to be single crystalline wurtzite ZnO. As-grown films show a broad electroluminescence band over the visible spectrum. Annealing
at moderate temperatures (T ) 300 °C) increases the emission and strongly raises the excitonic contribution. Optimally processed films show
a narrow ultraviolet electroluminescence line at ∼390 nm.

With its large exciton binding energy of ∼60 meV, ZnO is
a promising candidate for high-stability, room-temperature
luminescent and lasing devices. Recent research has dem-
onstrated strong ultraviolet and visible photoluminescence1-4
as well as optically pumped lasing4 in ZnO nanocrystals. So
far, however, p-type doping of ZnO has remained a chal-
lenge, and as a consequence, only a few LED structures could
be fabrictated successfully.5 Until now, only electrolumi-
nescence in the visible region has been observed from homo-5
and heterojunction6 nanorod structures, but ultraviolet (UV)
electroluminescence from nanostructures has remained out
of reach. In most of the ongoing work, ZnO nanostructures
are prepared in a variety of gas-phase methods. Typical
deposition temperatures are 300-500 °C for CVD- and
MOCVD-based techniques,7 600-900 °C for vapor-transport
techniques,8 and 900 °C for thermal evaporation techniques.9
Vapor-liquid-solid2 techniques at 900 °C have also been
applied. A much lower deposition temperature regime is
accessible from solutions. Lincot et al.10,11 have reported
epitaxial thin film and nanorod growth on sapphire and GaN
grown in electrodeposition at temperatures as low as 80 °C.
Nonepitaxial nanorod growth has been demonstrated by us
in the same technique on a variety of polycrystalline metal
and metal-oxide films.12
Here we report ultraviolet electroluminescence from ZnO
nanowire heterojunctions prepared in this low-temperature
regime. We show that high-quality single-crystalline nano-
wire crystals with surface roughnesses of ∼3 nm can be
obtained at temperatures of 70-90 °C. In an LED config-
* Corresponding author. E-mail: rkoe@pdx.edu.
10.1021/nl051501r CCC: $30.25 © 2005 American Chemical Society
Published on Web 09/17/2005
uration, the as-grown material exhibits broad-band electro-
luminescence across the spectral region from 350 to 850 nm.6
Processing and annealing at temperatures of 300 °C in air
improves the sample quality, reduces the surface roughness,
increases the electroluminescence intensity, and shifts the
emission maximum to the ultraviolet region. A narrow UV-
electroluminescence line is observed at 393 nm in the
annealed material.
The ZnO nanorods were grown at 90 °C on 5 × 5 cm2
fluorine-doped SnO2 films on glass substrates using a
standard three-electrode electrochemical cell with a Pt
counter electrode and a Ag/AgCl reference electrode. Before
deposition, the substrates were cleaned in an ultrasonic bath
of acetone and methanol with subsequent rinsing in HNO3
and distilled H2O. The deposition used aqueous solutions of
0.1 M KCl and 0.1 mM ZnCl2 saturated with O2 gas. The
uniformity of the deposition over the complete substrate area
was excellent. More details on the electrodeposition are given
in refs 6 and 12.
Figure 1 a and b shows an electron-diffraction micrograph
and a high-resolution STEM obtained from a single as-grown
nanorod. The images demonstrate clearly that the as-grown
material is single-crystalline. From the orientation of the
nanorod in the microscope, it is concluded that the growth
direction and the nanorod axis coincide with the c axis of
the wurtzite unit cell. Previous studies12 showed that the
carrier mobilities in the as-grown material are as high as 20
cm2/Vs.
Annealing took place in dry air at a temperature of 300
°C for 1 h at atmospheric pressure and was followed by
Figure 1. (a) Electron diffractogram of a single as-grown ZnO
nanorod electrodeposited at T ) 90 °C from an aqueous solution;
(b) high-resolution transmission electron micrograph of an as-grown
nanorod; (c) high-resolution transmission electron micrograph
obtained after annealing at 300 °C.
Figure 2. Scanning electron micrograph of a ZnO nanorod
embedded in a polystyrene layer that was subsequently plasma-
etched to reduce the coverage of the nanorod tip.
cooling in ambient air. Figure 1c shows markedly improved
crystallinity at the nanorod surface. This observation has been
confirmed in a large number of micrographs. It is difficult
to assert that the higher surface crystallinity is the cause for
the electronic improvement of the material. But the finding
is at least consistent with the notion that the processing
temperature in the low-temperature regime has considerable
influence on the O-vacancy density and that the prevalent
defect configuration is a deficiency in O at the surface.
Because the electrodeposition process involves the transfer
of electrons from the substrate to ZnO, the electronic contact
between the substrate and the nanorods is necessarily
conductive; we also find it to be mostly ohmic at room
temperature. Diode-like structures can be created by bringing
the electrodeposited nanorods into contact with a p-type
material, such as thin-film inorganic or organic semiconduc-
tors. To fabricate light-emitting diodes, we have grown the
ZnO nanorods on fluorine-doped SnO2/glass substrates and
then applied an insulating polystyrene film in order to
2006
Figure 3. (a) Room-temperature photoluminescence obtained on
ZnO nanorods showing excitonic and defect-related transitions; (b)
electroluminescence obtained from as-grown nanorods showing a
broad emission band from defect-related transitions and a small
ultraviolet shoulder; (c) electroluminescence of nanorods annealed
at T ) 300 °C for 2 h in air. Current values refer to the driving
current for a device area of 0.3 cm2.
insulate the uncovered SnO2 areas. The polystyrene deposi-
tion typically involves a multilayer process using high
molecular weight solutions (MW ≈ 1 800 000) of poly-
styrene in toluene. The deposition is carried out in such a
way that the space between nanorods is homogeneously filled
with the insulator, while there is only very thin coverage of
insulator material on the tip of the nanorods. Subsequently,
a strongly p-doped layer of PEDOT/PSS (poly(3,4-ethylene-
dioxythiophene)/poly(styrenesulfonate)) is deposited on top
of the polystyrene layer serving as a hole-injecting contact.
The layer thickness of the PEDOT/PSS is typically 0.5 µm.
The top contact is made by vacuum-evaporation of a ∼200-
nm Au layer. This contact configuration to ZnO is strongly
rectifying. With a tip coverage of less than 50 nm, carrier
Nano Lett., Vol. 5, No. 10, 2005
Figure 4. (a) Current-voltage characteristics of the nanorod-LED structure. The arrow indicates the emission threshold. (b) Energy diagram
for the nanorod LED with work function values for the contact and transport layers, and conduction and valence band edges for ZnO.
injection is found to be sufficient to produce visible electro-
luminescence at room temperature.6 To further reduce the
insulator coverage, we can thin the polystyrene at the ZnO
tips by mild plasma-etching in oxygen. Typically we used 3
min, 100 W O2 rf-plasma exposure at a pressure of 30 Pa to
obtain nearly bare ZnO tips as shown in Figure 2.
Figure 3 shows the electroluminescence results for as-
grown and annealed ZnO. Although visible broad-band
luminescence over the 360-850 nm region is observed in
the as-grown ZnO nanorods, improved intensities and an
additional narrow UV emission line is observed in LEDs
made of material annealed at 300 °C. The UV-emission is
centered on a wavelength of 393 nm and has a full width of
24 nm at half-maximum. The band gap energy of ZnO is
3.37 eV, corresponding to 360 nm. In polycrystalline films
and nanostructures, room-temperature photoluminescence
and lasing has been observed in the region around 390 nm13
and has been ascribed to bound-exciton and vacancy-related
transitions.14,15 A comparison between the photoluminescence
and the electroluminescence spectra of the annealed ZnO
shows nearly identical features in the two spectra, indicating
that the injection and transport processes in the annealed ZnO
are very efficient. For the UV transitions to have intensities
similar to those of the defect transitions, the electronic
transport for electrons and holes must occur with only a very
small reduction in carrier energy over the transport path
length, which corresponds to the nanorod height, that is, ∼2
µm. The unannealed material shows a weak shoulder in the
UV region, indicative of less efficient transport and the
presence of other nonradiative recombination channels,
bypassing the excitonic transitions. Figure 4 shows the
current-voltage characteristics of the SnO2/ZnO/PEDOT/
Au heterostructure and an energy level diagram based on
published data for the involved materials. The I-V charac-
teristics show excellent rectification; the luminescence onset-
voltage is typically about 5-7 V.
A comparison to the energy level diagram indicates that
a horizontal band alignment, which is necessary for carrier
injection, requires a forward potential of at least 3.1 V: there
is a 2.4 eV barrier for hole injection from the PEDOT
Nano Lett., Vol. 5, No. 10, 2005
transport level to the ZnO valence band edge and an
additional 0.7 eV barrier between the SnO2 Fermi energy
and the ZnO conduction band edge. It can be expected that
a more elaborate choice of contact materials will bring about
substantial reduction of these barriers or that a sequence of
small energy barriers can be constructed in multilayer
contacts. These refinements may eventually lead to further
improvement of the luminescence onset voltage and the
current densities in this type of heterojunction device.
Overall, this device presents an interesting alternative to
organic LEDs. Because the optically active material in this
hybrid structure is inorganic, stability issues may be less
critical than in all-organic LEDs. The device also satisfies
all of the requirements for flexible-substrate and large-area
applications. Processing temperatures and procedures prin-
cipally allow the use of polymeric substrates such as Kapton,
and the nanorod/polystyrene composite appears sufficiently
robust to absorb large mechanical strain.
To conclude, we have reported narrow-line ultraviolet
electroluminescence in ZnO nanorods, grown at 90 °C in
electrodeposition and annealed at 300 °C. The LED con-
sisted of SnO2/ZnO/PEDOT structures with an internal
polystyrene insulator layer. The complete processing pro-
cedure is compatible with large-area fabrication on flexible
substrates.
Acknowledgment. We gratefully acknowledge Dr.
Chunfei Li for help with the microscopy work.
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NL051501R
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