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Ceramics International 41 (2015) 40424049

www.elsevier.com/locate/ceramint

Effect of Cu concentration on the structural and optoelectronic properties

of ZnO:Cu:Al prepared by the solgel deposition method
Ian Yi-Yu Bun
Department of Microelectronic Engineering, National Kaohsiung Marine University, Kaohsiung, 632 Taiwan, Republic of China
Received 19 August 2014; received in revised form 18 November 2014; accepted 18 November 2014
Available online 26 November 2014

Abstract
This study investigate the effects of Cu concentration on ZnO:Cu:Al lms by the solgel deposition method. It was found that the ZnO:Cu:Al
lms consist of wrinkled micro-bers, which become more prominent as the Cu concentration increases. Furthermore, the introduction of Cu
suppresses crystallite growth and creates structural defects in the ZnO lms. An increase in the Cu concentration also reduces the optical
transmittance of the deposited lms due to structural disorder. Electrical measurements suggest that a stable p-type ZnO can be obtained by
tuning the Cu to Al ratio.
& 2014 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Keywords: Zinc oxide; Solgel; Copper; Aluminium; Co-doping

1. Introduction
Zinc oxide (ZnO), with a large exciton binding energy
(60 meV) and a wide band gap (3.37 eV), is a semiconductor
material that has attracted increasing attentions due to its
potential application in a variety of elds [14]. In particular,
ZnO has been proposed as an active material in ultraviolet light
emitting diodes(LEDs) [5], transparent conductive lms [68],
piezoelectric nano-generators [9] and humidity gas sensors
[10]. It is well-known that the optoelectronic properties of ZnO
can be further tuned by adding the appropriate dopants into its
network. For example, the resistivity of ZnO can be adjusted
from 1011 to 10
3 -cm, depending on the impurity selection
and post-annealing conditions [11,12]. In the past, elements
such as In [13], Ga [14], Al [15] and Cu [16] have been added
into ZnO to increase its n-type conduction behavior. Among
the noteworthy dopants, Cu is of great interest due to the
production of diluted semiconductor [1719].
Previous studies have demonstrated that ZnO can be deposited
by sputtering [20], spray pyrosis [21], pulsed laser deposition [22],
n

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http://dx.doi.org/10.1016/j.ceramint.2014.11.095
0272-8842/& 2014 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

chemical vapor deposition [23] and solgel processing [24]. Due

to the ionization of excessive zinc atoms at interstitial positions
and the presence of oxygen vacancies [25], the as-deposited ZnO
tends to exhibit n-type conduction behavior. In contrast, it is
comparatively difcult in formation of stable p-type ZnO, which
means that n-type ZnO are often paired with other p-type
materials (e.g. NiO [26], Cu2O [27], GaN [28], etc.) to form
heterojunction device. The pn homojunction is one of the basic
building blocks of modern semiconductor devices and are proven
to be electrically superior than heterojunction devices due to
better lattice matching [29]. Past studies have also revealed that
Cu can act as an acceptor in ZnO, which lowers the electron
concentration, shifts the conduction towards the valence band
[30] and therefore create a p-type ZnO. However, the p-type
ZnO created by a single element is often unstable, and tends to
revert back to n-type conduction behavior over time [31]. One
proven strategy that has been used to create stable p-type
conduction behavior is the co-doping method. Traditionally,
co-doping in ZnO thin lms has been achieved by using the
combined addition of group III elements with VI elements, e.g.
a combination of N/Al [32,33], N/Li [34], and so on. However,
to the best of author's knowledge, the combination of Al/Cu has
not been explored. The effects of Cu concentration on the

I.Y.-Y. Bu / Ceramics International 41 (2015) 40424049

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Fig. 1. SEM images of the ZnO:Cu:Al thin lm sintered at Cu concentrations at (a) 1%, (b) 2%, (c) 3%, (d) 5% (scale bar 5 m) (e)EDX analysis of the sample,
(f) extracted chemical composition from EDX, and (g) cross section SEM image (scale bar 10 m).

optoelectronic properties of p-type ZnO:Cu:Al thin lms are

investigated in this study. The deposited thin lms are thoroughly characterized by scanning electron microscopy (SEM),
X-ray diffraction (XRD), UVvis spectroscopy, Hall effects and
photoluminescence measurements.

2. Experimental
All chemicals used during this study were of reagent grade and
used without further purication. Corning glass (Eagle 2000)
substrates were cleaned by sequential ultrasonic agitation in baths

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I.Y.-Y. Bu / Ceramics International 41 (2015) 40424049

Fig. 2. (a) XRD patterns of solgel derived ZnO:Cu:Al deposited at various

Cu concentrations and (b) extracted FWHM and grain size.

of acetone, isopropanol and deionised water for period of 30 min

in each solvent.
The precursor sol was prepared by mixing 0.7 M of zinc
acetate (Zn(CH3COO)2  H2O) in isopropanol with a drop of
monoethanolamine added as a chelating agent to prevent
precipitation. Al and Cu co-doping was achieved by adding
1 at% AlCl3 into the sols and copper acetate (varied from 1, 2,
3 and 5 at%). The solution was magnetically stirred at 70 1C
for 1 h and then the prepared sols were left to age for one day
in a sealed vessel. Film depositions were undertaken by using
a spin coater set at a rotation speed of 3000 rpm for 30 s.
The coated substrates were pre-annealed at 250 1C, in order to
ensure complete evaporation of the solvents, and subsequently
sintered at 550 1C using a hotplate to crystallize the lms.
Because the typical lm thickness derived per spin-dry cycle
was around 50 nm, ve coating courses were required in order
for each sample to accumulate a thickness of around 250 nm
(Fig. 1(g)). The structural and morphological properties of the
deposited thin lms were determined by using an FEI Quanta
400F Environmental Scanning Electron Microscope (SEM ),
equipped with an Energy Dispersive Spectroscopy (EDS). The
crystal orientations were investigated by using a Siemens
D5000 X-ray Diffractometer using Cu K radiation. Atomic
force microscopy (AFM) measurements were obtained using a
Digital instrument NanoMan NS4 D3100 in tapping mode.
Hall measurements were performed by a four-point probe in
Van der Pauw conguration to determine resistivity and carrier
concentration. Contacts were sputtered on the four corners of
the sample to ensure low contact resistances. The photoluminescence (PL) measurements were performed with a 325 nm
He/Cd laser (Jasco Model FP-6000). The optical transmittance

Fig. 3. Raman spectra of the ZnO:Cu:Al sintered at different doping Cu concentrations.

I.Y.-Y. Bu / Ceramics International 41 (2015) 40424049

and Tauc gap of the deposited thin lms were determined by

using a UVvis spectroscopy (JASCO V-600) sweep with
wavelengths from 200 to 1200 nm.
3. Results and discussion
Fig. 1 shows the SEM top-view images of the deposited ZnO:
Cux:Al, with x being the Cu concentration set at 1,2,3 and 5 at%.
Regardless of the deposition conditions, all of the investigated

4045

thin lms consist of wrinkled microbers. It can be observed

from the SEM images that the morphology of these microbers
is highly sensitive to the amount of Cu incorporation, and that a
higher Cu doping in ZnO:Cu:Al thin lm results in increased
diameters (50120 nm). Our group has previously reported that
the microbrous morphology is caused by the rapid heating
sintering process when using a hotplate [32]. Other studies
proposed that the lack of hydroxyl or alkoxy groups in the initial
sol precursor also contributes toward the formation of wrinkles

Fig. 4. (a) Photoluminescence of the ZnO:Cu:Al sintered at different Cu doping concentrations and (b) the same set of data stacked for comparison.

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I.Y.-Y. Bu / Ceramics International 41 (2015) 40424049

[32,35]. Since a hotplate was selected as the heating element in

this study, its contribution cannot be eliminated. It can also be
deduced from the SEM images that an increase in Cu addition
results in an increase in the length of the microbers length. This
feature is absent from the solgel deposited ZnO:Cu thin lms
that are deposited without the addition of Al [36]. This suggests
that the incorporation of Al can create additional stresses within
the lm, and contribute to the formation of wrinkles.
The chemical composition of the representative samples
(doped with 5 at% of Cu) were evaluated by EDS and plotted
in Fig. 1(e). Fig. 1(f) shows the extracted chemical composition of the lms at different concentration. It is reassuring that
Zn, O, Al and Cu elements are present within the lm with
concentration close to the initial precursor.
The structure and orientation of the deposited ZnO:Cu:Al thin
lms, doped with different Cu concentrations are evaluated using
XRD and presented in Fig. 2. Clearly, all of the deposited thin
lms are polycrystalline, with a hexagonal wurtzite structure.
The XRD patterns consist of a dominant diffraction peak indexed
to the (002) orientation, and two minor peaks at (100) and (101).
It is also evident from the XRD data that there are no diffraction
peaks indexed to Cu, CuO, Al or AlxOy. Since Cu and Al readily
oxidize upon heating in air, the absence of these peaks indicates
a high quality lm, and that the Cu and Al have been substituted
into the ZnO sites.
Fig. 2 shows that the (002) diffraction peak intensity increases
along with the Cu concentration in the initial sol. The increase in
the (002) intensity originates from the differences in the ionic
radius between the Zn and Cu. Similar effects on ZnO:Mn have

been previously reported [37].

The full width at half maximum (FWHM) and average grain
size can be estimated from the XRD data by using Scherrer's
formula:
d

0:9
B cos B

where is the X-ray wavelength of 1.54 ; B is the Bragg

diffraction angle and B is the FWHM of B. This extracted data
are plotted in Fig. 2(b). It is observed that an increase in Cu
incorporation leads to an increase in the FWHM. This indicates
the degradation of lm crystallinity, which can be attributed to
the differences in ionic radii between Zn and Cu. As the amount
of Cu incorporated into the ZnO increases, the crystallite size
decreases. This trend is consistent with the results obtained by a
previous reports on solgel deposited ZnO:CuO [38]. Furthermore, it would appear that Cu incorporation tends to suppress
crystallite growth, due to the stress arising from the difference
between ion radii of Zn and Cu.
Fig. 3 shows the Raman shift measurements of the investigated
ZnO:Al:Cu as a function of Cu doping concentration. Two
prominent peaks, centered at around 432 and 812 cm
1, can
observed in the gure. Whilst the ZnO signature peak at 432 cm
1
is assigned to that E2H peak, the peak centered at 812 cm
1 is
assigned to the second-order Raman modes with A1 symmetry. As
the amount of Cu incorporation increases, more pronounced
broadening and shifting of the E2H phonon peak appears in the
ZnO:Cu:Al due to the presence of structural defects.

Fig. 5. (a) Optical transmittance vs wavelength of the solgel derived ZnO:Cu:Al, (b) Plot from the AFM measurement, (c) extracted surface roughness from AFM
measurement, and (d) extracted Tauc gap from the UVvis.

I.Y.-Y. Bu / Ceramics International 41 (2015) 40424049

Photoluminescence (PL) emission measurements were performed in order to study the optical properties of the deposited
samples. Fig. 4(a) presents the room temperature PL emission
spectra for ZnO:Al:Cu doped with 1, 2, 3 and 5 at% Cu.
In general, undoped ZnO exhibits two PL emission peaks
centered at 380 nm and 550 nm, respectively [39]. The UV peak
centered at around 380 nm has been attributed to excitonic emission
and band-edge excitonic emission. On the other hand, the peak at
550 nm originates from the defect-related deep level emission in the
visible range (singly ionized oxygen or surface states). Fig. 4(b)
shows the same set of PL emission data stacked and plotted on a
narrower scale. It is interesting to note that all of the samples of our
study possess a single dominant peak centered at around 436 nm.
Furthermore, the PL emission peaks of the ZnO:Cu:Al thin lms
are rather broad, with the green band and band edge emission peak
appearing to have merged together and becoming indistinguishable.
To better understand the PL emission spectra of the deposited ZnO:
Cu:Al, the PL emission peak has been re-plotted in Fig. 5(b), using
a narrower wavelength scale (350 566 nm). It is interesting to
note from this gure that, as the Cu incorporation increases, the PL
peak at 434 nm decreases and a shift towards lower wavelengths.
The weakening and shifting effect of the PL emission peak is most
prominent in 5 at% doped ZnO thin lms, where the peak shifts to
506 nm. Therefore, the broadening of the PL emission peak at
434 nm can be tentatively assigned to the combined contribution of
the UV and green band, corresponding to oxygen vacancies, zinc
interstitials and copper ions. A previous PL study on ZnO:Cu
(without Al co-doping) has shown that the PL peak at 434 nm is
related to to the transfer from the Cu2 (2T2) state to the shallow
acceptor level (Cu , h) [40].
The optical transparence of the deposited ZnO:Cu:Al thin lms
are investigated by UVvis spectroscopy, with the results plotted in
Fig. 5(a). Clearly, all of the deposited lms exhibit a sharp
absorption edge, which shifts toward longer wavelengths when an
excessive (5 at%) amount of Cu is incorporated into the ZnO thin
lm. The UVvis spectroscopy measurements also show that the
optical transmittance (at 550 nm) is around 30 92%, depending
on the amount of Cu that is incorporated. An increasing amount of
Cu incorporation decreases the optical transmittance. Generally,
such a decreasing trend in the optical transmittance, as impurities
are introduced into the ZnO network, is due to scattering at grain
boundaries. The lack of this trend can be attributed to the effect of
surface wrinkles, which scatters the light and change the optical
transparency. Films deposited with a lower Cu content consist of
wrinkles, with smaller dimensions, that increasing the probability
of light scattering. The results suggest that the transparency of the
ZnO:Cu:Al thin lms is affected by the combination of surface
roughness and dopant incorporation. Fig. 5(b) shows the representative AFM measurement of the sample doped with 5% of Cu.
From the AFM measurements the root mean square (RMS) surface
roughness can be obtained and plotted in Fig. 5(c). For comparison, Fig. 5(c) also plot the effect of Cu concentration on optical
transmittance at 500 nm (extracted from 5(a)). The ZnO:Cu:Al the
shows the change of surface roughness and optical transmittance
(at 500 nm) as a function of Cu doping. As can be observed in
Fig. 5(c) there are some correlation between the surface roughness and optical transmittance, lms with higher surface roughness

4047

(e.g., 5% Cu doping) tend to exhibit lower transparency due to the

enhanced scattering effect.
The absorption edge of direct band gap semiconductors can
be evaluated by the following equation:

1=2
hv A hv
E g
Where is the absorption coefcient hv is the photon energy, A
is a constant and Eg is the band gap. The optical band gap of the
investigated ZnO:Cu:Al lms was determined by from Fig. 5(a)
using a previously described method [8] and summarized in

Fig. 6. (a) Carrier concentration, (b) mobility, and (c) resistivity of the
deposited ZnO:CuAl at different Cu concentrations.

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I.Y.-Y. Bu / Ceramics International 41 (2015) 40424049

Fig. 5(d). It is obvious from this gure that there is a lack of

trend in the band gap with increasing Cu incorporation, probably
due to the secondary Cu phase segregation.
As can be deduced from Fig. 5(d) the optical band gaps
obtained for the ZnO:Al:Cu thin lm are much narrower than
those of intrinsic ZnO thin lms (3.37 eV), and this is due to
the incorporation of Cu, which creates new recombination
centres [41].
In order to understand the inuences of Cu concentration on
the electronic properties of ZnO:Al:Cu, Hall effect measurements are obtained. The dopant concentration, resistivity and
mobility are measured and plotted in Fig. 6(a)(c).
Fig. 6(a) shows the effect of Cu concentration on the carrier
concentration of the ZnO:Cu:Al samples. All of the samples
exhibit hole conduction behavior and thus conrm the formation
of a p-type material. Initially, as the Cu concentration increases
(up to 2 at%), the hole concentration rises with no appreciable
variation in neither the resistivity nor mobility. However, a
further increase in the Cu concentration (42 at%) leads to raises
in both the resistivity and mobility, with a corresponding
decrease in the hole concentration. This increase in carrier
concentration is due to the fact that Cu behaves like an acceptor
in ZnO [42,43]. The reduction in the dopant concentration of the
lms doped with Cu42 at% can be ascribed to the signicant
change in their surface morphologies. The increased surface
roughness from the aforementioned wrinkling effect not only
reduces the carrier concentration, but also increases the resistivity. Other factors that could play a role in this are the formation
of Zn interstitials and O voids, which may have compensated the
p-type ZnO:Cu:Al. The increase in mobility can be related to the
increased in microbers, as observed in the SEM.

4. Conclusion
In summary, p-type ZnO:Cu:Al thin lms have been successfully synthesized on glass substrates. Regardless of the incorporated Cu:Al ratio, the lms exhibit wrinkled microstructures due
to the stress induced during the cooling of the samples. XRD
conrms that increasing the Cu concentration results in the
enhanced XRD peak intensity at the (002) phase. Both the PL
and Raman spectroscopy results suggest that the Cu is responsible for introducing structural defects within the investigated
lms. The UVvis spectroscopy measurements indicate that
increasing the amount of Cu incorporation decreased the optical
transmittance, due to scattering at grain boundaries created.
Electrical measurements conrm that all the deposited lms are
p-type ones, with the highest carrier concentration observed in
ZnO:Cu:Al lms doped with 2 at% Cu.

Acknowledgment
This work was supported by Ministry of Science and
Technology, Taiwan, Republic of China under Grant number
103-2221-E-022-022.

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