Materials Chemistry and Physics xxx (2015) 1e5

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Materials Chemistry and Physics

journal homepage: www.elsevier.com/locate/matchemphys

Red light emission from ZnO:Eu3jCuSCN hetero-junction under

cathodic polarization
P.M. Sirimanne a, *, H. Minoura b
a
b

Department of Science and Technology, Uwa Wellassa University, Badulla, Sri Lanka
Environmental and Renewable Energy Systems Division, Graduate School of Engineering, Gifu University, 1-1 Yanagido, Gifu 501-1193, Japan

h i g h l i g h t s
 Europium doped ZnO ceramic exhibits photo-luminescence.
 Semiconductor hetro-junction was prepared.
 ZnO:Eu3jCuSCN hetero-junction emits red light under reverse bias.

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 8 February 2011
Received in revised form
9 September 2015
Accepted 3 October 2015
Available online xxx

Eu3 ions were bonded to ZnO ceramic via organic ligand. Surface bonded Eu3 ions were exhibited
specic luminescence bands due to electron transitions between fef intra-congurationally transitions.
Further enhancement of luminescence bands was observed by attaching selected oligomers to Eu3 ions.
A hetero-junction was prepared by depositing copper-thiocyanate on Eu3 ions bonded ZnO ceramic. Red
light emission was observed from surface bonded Eu3 ions in ZnO:Eu3jCuSCN hetero-junction under
reverse bias.
2015 Published by Elsevier B.V.

Keywords:
Zinc oxide
Propylsulde
2-Thenoyltriuoroacetone
2,2'-bipyridyl 4,4'-dicarboxylic acid
Copper thiocyanate

1. Introduction
In recent years, considerable interest has been focused on the
studies of luminescence of lanthanides doped oxide ceramics [1,2].
It is interesting rare-earth ions exhibit unique luminescence bands
at particulate wavelengths which are highly independent from host
matrix. However, width and intensity of luminescence bands
frequently change with host material. Eu3 ions are one of the best
candidates to study luminescence properties, rather than other
lanthanide elements due to its relatively simple energy scheme
[3e5]. Different techniques have been employed to dope, bond or
implant Eu3 ions to the host material [6,7]. In this study, Eu3 ions
were bonded to ZnO ceramic via organic molecules. Further
enhancement of luminescence bands was observed by coupling

* Corresponding author.
E-mail address: psirimane@hotmail.com (P.M. Sirimanne).

with selected oligomers to Eu3 ions. A hetero-junction was prepared by depositing copper-thiocyanate on surface modied zinc
oxide ceramic. Red light emission was observed from the surface
bounded Eu3 ions of ZnO:Eu3jCuSCN hetro-junction under
reverse bias.
2. Experimental
2.1. Deposition of zinc oxide and hybrid-zinc oxide lms on
conducting glass
Activation of uorine doped tin oxide (FTO) coated glass substrates (are not fully active for deposition of ZnO electrochemically)
was carried out by applying a constant potential of 1.0 V vs SCE, at
saturated O2 atmosphere (bubbling rate100 ml/min) in 0.1 M KCl
solution for 20 min. ZnO was deposited on activated FTO by adding
ZnCl2 to the electrolytic bath (until concentration reach 5 mM) and
continuing electrolysis for further 20 min by replacing Pt counter

http://dx.doi.org/10.1016/j.matchemphys.2015.10.001
0254-0584/ 2015 Published by Elsevier B.V.

Please cite this article in press as: P.M. Sirimanne, H. Minoura, Red light emission from ZnO:Eu3jCuSCN hetero-junction under cathodic
polarization, Materials Chemistry and Physics (2015), http://dx.doi.org/10.1016/j.matchemphys.2015.10.001

P.M. Sirimanne, H. Minoura / Materials Chemistry and Physics xxx (2015) 1e5

electrode used for pre-electrolysis from a pure Zn wire, under

similar potentiostatic conditions. Depositions were carried out in a
single compartment cylindrical cell, at a constant temperature of
70  C, in an aqueous medium by using three electrode conguration. The working electrode was kept at electrolytejair interface and
was rotated at a constant speed of 500 rpm throughout the
experiment. Hybrid organic-zinc oxide lms were prepared by
electrolyzing followed by adding eosin Y into the same electrolytic
bath (until concentration reach to 45 mM) for further 20 min, under
same conditions. Hybrid ZnO-eosin Y lms were then rinsed with
water dried under air stream and kept at atmospheric condition for
overnight. Eosin Y molecules were extracted from the hybrid lms
by immersing in a KOH solution (pH~10.5).
2.2. Chelation of Eu3 on ZnO lms
ZnO thin lms were kept immersed in 2,2'-bipyridyl 4,4'dicarboxylic acid (abbreviated as dcbpy and concentration was
maintained as 200 mM in ethanol), EuCl3 (1 mM in ethanol), and 2thenoyltriuoroacetone (abbreviated as TTA and concentration was
maintained as 200 mM in ethanol), for 1 h in each solution in order.
Temperature of solutions was maintained as 80  C. ZnOjdcbpyjEu3jTTA electrodes were lms dried at 60  C for 30 min.
2.3. Deposition and characterization CuSCNS on
ZnOjdcbpyjEu3jTTA electrodes
0.1 g of CuSCN was dissolved in propylsulde and centrifuging
the solution separated residue. Small amount of this solution was
spread on pre-heated surface modied ZnO electrodes. A thin layer
of graphite was nally coated on p-CuCNS layer by painting carbon
powder on the electrode as conductivity of the electrode increased
[8]. Characteristics of ZnOjdcbpyjEu3jTTA electrodes and
ZnOjdcbpyjEu3jTTAjCuSCN
hetro-junction
were
studied
(morphology-Jeol scanning electron micrograph luminescenceHitachi orescence spectrometer, and crystallinity-Rigaku X-ray
diffractometer).
3. Results and discussion
Chronoamperograms for a) pre-electrolysis of FTO and b)
deposition of ZnO lm are shown in Fig. 1. As is shown in curve a,
current ow across the electrodes due to reduction of molecular
oxygen initially increases with time and reaches of a saturation
level. Saturation of current indicates activation of FTO for oxygen
and seems to be due to limitation of diffusion of oxygen in the
electrolyte. Reduction of molecular oxygen takes place via four
electron reduction process in KCl [9]. ZnCl2 was added to the
electrolyte when the activation is completed. Addition of Zn2 into
the electrochemical bath changes kinetics in the system and forms
ZnO on FTO, via kinetically controlled process [9,10]. Peculiar
variation of current as soon as ZnCl2 is added to the electrolyte
(curve b) due to formation of ZnO nucleus on FTO. Resulted ZnO
lms exhibit thickness of 0.5 mm, highly compact structure (image
a, Fig. 2) and used as a template for deposition of hybrid lms.
Several organic molecules have been identied as competent for
fabrication of hybrid lms with ZnO by electrochemically [11,12].
Eosin Y was chosen as the organic competent since mechanism of
formation of ZnO-eosin Y hybrid lms is well understood. However,
in brief, E1/2 potential of eosin Y is located at 0.9 V vs SCE which is
close to externally opposed potential on ZnO electrode. At this
voltage eosin Y reduces and its reduced form couples with ZnO to
form hybrid lms [13]. Chronoamperogram for deposition of hybrid
ZnO-eosin Y lm is also shown in Fig. 1 (curve c). Thickness of
resulted hybrid ZnO-eosin Y lms is about 4 mm, exhibit almost

Fig. 1. Chronoamperograms for (a) pre-electrolysis, (b) deposition of ZnO lm and (c)
deposition of hybrid ZnO-eosin Y lm.

color less nature or slightly reddish color as deposition is completed

and become dark reddish color due to aerial oxidation being aged.
Morphologies of a ZnO-eosin Y hybrid lm is shown in Fig. 2 (image
b). As is shown, hybrid ZnO-eosin Y lms are composed of grains
with round headed tops. Desorption of dye from hybrid lms result
highly porous like nano-channels structured ZnO lms. However,
extraction of eosin Y is not possible when more positive potential
than E1/2 is opposed on the electrode, during electro-deposition.
Morphology of hybrid lm after desorption of dye is shown in
image c (Fig. 2). This nano-rod like ZnO structure occupies higher
surface area than its geometrical area and also exhibit high degree
of crystallinity with the predominant orientation of (100), (002)
and (101) crystal planes (Fig. 3). Growth of thin lms with a
preferred orientation is a specic feature of thin lms [14]. However peaks belonging to other lattice planes are also observed at
higher angles. In addition to these peaks some peaks related to
substrate were also observed.
Doping of Eu3 ions in metal oxide ceramics is known to increase the luminescence especially in visible region [15e17].
Generally, doping proceeds during fabrication of oxide lms or
pellets. However, a simple technique is chosen to link Eu3 ions to
ZnO lms by using organic molecules. Organic molecule dcbpy has
a capability of bonding with ZnO via carboxylic groups and also
with other cations by excess electrons at nitrogen sites in the same
molecule. Similar, techniques have been used to bind Ru3 ions
with TiO2 substrates in dye-sensitized solar cells [18]. Luminescence spectrum of (a) ZnO, (b) ZnOjdcbpyjEu3 in the visible region
is shown in Fig. 4. ZnO exhibits a feeble photoluminescence with
the maximum at 600 nm due to owing of defects in the host matrix
[19]. In addition to this luminescence band ZnO exhibits a narrow
band at 388 nm due to recombination of charge carriers at band gap
[20]. Eu3 doped ZnO electrodes exhibit several luminescence
bands at 578, 590, 612, 650 and 699 nm with different intensities.
These luminescence bands are due to electron transitions from fef
intracongarational transitions and can be assigned as 5D0/7Fj
(j 0,1,2,3,4) [15e17,21]. The band at 612 nm exhibited highest
intensity among those luminescence bands. Several attempts were
made to increase intensity of ZnOjdcbpyjEu3 electrodes. TTA was

Please cite this article in press as: P.M. Sirimanne, H. Minoura, Red light emission from ZnO:Eu3jCuSCN hetero-junction under cathodic
polarization, Materials Chemistry and Physics (2015), http://dx.doi.org/10.1016/j.matchemphys.2015.10.001

P.M. Sirimanne, H. Minoura / Materials Chemistry and Physics xxx (2015) 1e5

Fig. 3. X-ray diffractogram of ZnO lm.

established phenomenon [22]. Luminescence spectrum of

ZnOjdcbpyjEu3jTTA electrode is also shown as curve c in Fig. 4. The
enhancement of luminescence in the presence of TTA on the electrode is known as antenna effect [23]. It is known that water at the
coordination sphere of Eu3 ions act as a quencher of luminescence.
Once TTA molecules are attached to Eu3 ions less possibility is to
absorb water molecules on the electrode, thus resulting higher
luminescence on the electrode. We have studied absorption properties of (a) ZnOjdcbpyjEu3jTTA and (b) ZnO electrodes.

Fig. 2. (a) Morphology of compact ZnO lm and morphology of hybrid ZnO-eosin Y

lm (b) before and (c) after removing eosin Y.

found as a candidate to couple with Eu3 ligand that helps to

enhance luminescence of ZnOjdcbpyjEu3 electrodes. Coupling of
organic compounds belonging to oligomers with cations is a well-

Fig. 4. Emission spectra for (a) ZnO, (b) ZnOjdcbpyjEu3 and (c) ZnOjdcbpyjEu3jTTA
electrodes, excitation was carried out at 370, 315 and 374 nm, respectively.

Please cite this article in press as: P.M. Sirimanne, H. Minoura, Red light emission from ZnO:Eu3jCuSCN hetero-junction under cathodic
polarization, Materials Chemistry and Physics (2015), http://dx.doi.org/10.1016/j.matchemphys.2015.10.001

P.M. Sirimanne, H. Minoura / Materials Chemistry and Physics xxx (2015) 1e5

Fig. 5. Absorption of (a) ZnOjdcbpyjEu3jTTA and (b) ZnO electrodes.

ZnOjdcbpyjEu3jTTA electrodes absorb light with the maxima at

376 nm (curve a, Fig. 5). However, a broad hump with a weak intensity was observed at same wavelength for bare ZnO electrode
(curve b). As Dar et al. suggested this peak is due to nature of nanostructure of the lm [24]. An enhancement of intensity of the peak
at 376 nm was observed after attaching TTA with Eu3. Such an
enhancement did not observe in absence of Eu3 on the electrode,
indicating bonding of TTA with Eu3 ions. A semiconductor hetero-

Fig. 7. Light emission of ZnOjdcbpyjEu3jTTAjCuSCN device under reverse bias. Active

area of the device is 0.75 cm2. Inset shows formation of bonds between CuCNS and
surface modied ZnO.

junction was fabricated by depositing CuSCN on ZnOjdcbpyjEu3jTTA electrodes. Current-voltage characteristics of (a)
ZnOjCuSCN and (b) ZnOjdcbpyjEu3jTTAjCuSCN hetro-junctions are
shown in Fig. 6. Current ows through the junction, when CuSCN
layer is positively polarized (forward bias) from the equilibrium as
the result of resistance decreased. However, a feeble current is
observed when applied potential negatively increases from the
equilibrium, due migration of minority carries. This rectication
effect clearly indicates formation of semiconductor heto-junction
in electronically between CuCNS and ZnOjdcbpyjEu3jTTA. The
mechanism of formation of bonds between CuCNS and surface
modied ZnO is shown in the inset of Fig. 7. Formation of S/S
bonds among compounds has been observed previously [25,26]. A
negative shift of currentevoltage characteristics is observed in
absence of dcbpyjEu3jTTA complex on the ZnO electrode (curve a).
When the opposed potential was negatively increased (more
than 6.5 V) a weaker red light emission is observed probably due
to scattering of light in nano-porous ZnO electrode. The emission
spectrum of ZnOjdcbpyjEu3jTTAjCuSCN device is also shown in
Fig. 7. The mechanism of red light emission of ZnOjdcbpyjEu3jTTAjCuSCN device can be explained as follow, the minority
carries gathered large kinetic energy under reverse bias especially
at higher negative potentials. These hot electrons move toward the
junction with a higher velocity and get collapse with Eu3 ions and
get excited. Excited inner core electrons especially in the 5d orbital
reach to their ground status by emitting light. Thus results red light
emission from the device.

4. Conclusion

Fig. 6. Current-voltage characteristics of hetero-junction of a) CuSCNjZnO and (b)

ZnOjdcbpyjEu3jTTAjCuSCN, at dark. Electrodes were scanned with constant rate of
50 mV s-1. Active area of the device is 0.75 cm2.

An enhancement of luminescence was observed by doping Eu3

in ZnO matrix. Further enhancement in luminescence was observed
by coupling selected oligomers (TTA) to the Eu3 ions. A heterojunction was prepared by depositing CuSCN on Eu3 bonded ZnO
electrodes. Red light emission was observed under reverse bias
from the ZnOjdcbpyjEu3jTTAjCuSCN device.

Please cite this article in press as: P.M. Sirimanne, H. Minoura, Red light emission from ZnO:Eu3jCuSCN hetero-junction under cathodic
polarization, Materials Chemistry and Physics (2015), http://dx.doi.org/10.1016/j.matchemphys.2015.10.001

P.M. Sirimanne, H. Minoura / Materials Chemistry and Physics xxx (2015) 1e5

Acknowledgements
Mr. M.D. Nilantha is acknowledged for UVevis measurements.
References
[1] Li Yanhong, H. Guangyan, Synthesis and luminescence properties of nanocrystalline YVO4:Eu3, J. Solid State Chem. 178 (3) (2005) 645e649.
[2] F. Gu, S.F. Wang, M.K. Lu, Y.X. Qi, G.J. Zhou, D. Xu, D.R. Yuan, Luminescent
characteristics of Eu3 in SnO2 nanoparticles, Opt. Mater. 25 (1) (2004)
59e64.
[3] M. Nogami, Room temperature persistent spectral hole burning of Eu3 ions
doped in solegel derived glasses, J. Lumin. 98 (1e4) (2002) 289e294.
[4] H.P. You, M. Nogami, Persistent spectral hole burning of Eu3 ions in
TiO2eSiO2 glass prepared by solegel method, J. Alloys Compd. 408e412
(2006) 796e799.
[5] D. Ananias, L.D. Carlos, J. Rocha, Unusual full-color phosphors: Na3LnSi3O9,
Opt. Mater. 28 (6e7) (2006) 582e586.
[6] I.M. Nagpure, S. Saha, S.J. Dhoble, Photoluminescence and thermoluminescence characterization of Eu3 and Dy3 activated Ca3(PO4)2 phosphor,
J. Lumin. 129 (9) (2009) 898e905.
[7] J. Tronto, S.J.L. Ribeiro, J.B. Valim, R.R. Goncalves, Visible and near-infrared
luminescent Eu3 or Er3 doped laponite-derived xerogels and thick lms:
structural and spectroscopic properties, Mater. Chem Phy. 113 (1) (2009)
71e77.
[8] P.M. Sirimanne, E.V.A. Premalal, T. Soga, Utilization of poly[2-methoxy-5-(2ethyl-hexyloxy)-p- phenylene vinylene as a holeconductor in titania based
photovoltaic cells, Curr. Sci. 93 (2) (2007) 132e133, 2007.
[9] A. Goux, T. Pauporte, D. Lincot, Oxygen reduction reaction on electrodeposited
zinc oxide electrodes in KCl solution at 70  C, Electrochimia Acta 51 (15)
(2006) 3168e3172.
[10] A. Goux, T. Pauporte, T. Yoshida, D. Lincot, Mechanistic study of the electrodeposition of Nanoporous self-assembled ZnO/Eosin Y hybrid thin Films: effect of eosin concentration, Langmuir 22 (25) (2006) 10545e10553.
[11] T. Yoshida, T. Pauporte, D. Lincot, T. Oekermann, H. Minour, Cathodic electrodeposition of ZnO/Eosin Y hybrid thin lms from oxygen-saturated
aqueous solution of ZnCl2 and eosin Y, J. Electrochem. Soc. 150 (9) (2003)
C608eC615.
[12] T. Pauporte, F. Bedioui, D. Lincot, Nanostructured zinc oxideechromophore
hybrid lms with multicolored electrochromic properties, J. Mater. Chem. 15

(2005) 1552e1559.
[13] J.B. Zhang, T. Yoshida, D. Komatsu, H. Minoura, Electrocatalytic role of eosin Y
during electrodeposition of zinc oxide/eosin Y hybrid thin lms, in: Proceeding of 16th International Conference on Photochemical Conversion and
Storage of Solar Energy, 2006. W7-P-21.
[14] P.M. Sirimanne, T. Soga, M. Kunst, Observation of microwave conductivity in
copper iodide lms and relay effect in the dye molecules attached to CuI
photocathode, J. Solid State Chem. 178 (2005) 3010e3013.
[15] Q.G. Zeng, Z.L. Ding, Z.A. Zhan, structure and optical properties of Eu3/TiO2
nanocrystals at room temperature, J. Lumi. Synth. 118 (2) (2006) 301e307.
[16] S. Lu, J. Zhang, Study on UV excitation properties of Eu3doped rare-earth
phosphates, J. Lumin. 122e123 (2007) 500e502.
[17] P. Che, J. Meng, L. Guo, Growth and photoluminescence for undoped and Ndoped ZnO grown on 6H-SiC substrate, J. Lumin. 122e123 (2007) 165e167.
[18] M. Gratzel, K. Kalyanasundaram, Articial photosynthesis: efcient dyesensitized photoelectrochemical cells for direct conversion of light to electricity, Curr. Sci. 66 (10) (1994) 706e714.
[19] S.A.M. Lima, F.A. Sigoli, M. Jafelicci Jr., M.R. Davolos, Luminescent properties
and lattice defects correlation on zinc oxide, Int. J. Inorg. Mat. 3 (7) (2001)
749e754.
[20] A. Chrissanthopoulos, F.C. Kyriazis, V. Nikolakis, I.G. Giannakopouos,
V. Dracopoulos, S. baskoutas, N. Bouropoulos, S.N. Yannopoulos, ZnO/zeolite
hybrid nanostructures: synthesis, structure, optical properties, and simulation, Thin Solid Films 555 (2014) 21e27.
[21] Z. Zhao, Q.G. Zeng, Z.M. Zhang, Z.L. Ding, Optical properties of Eu3-doped
TiO2 nanocrystalline under high pressure, J. Lumin. 122e123 (2007) 862e865.
_ Kaya, S. Koyuncu, D. Senol, Conductivity and band gap of oligo-2-[(4[22] I.
uorophenyl) imino methylene] phenol and some of its oligomer-metal
complexes, Eur. Polym. J. 42 (11) (2006) 3140e3144.
[23] O.L. Malta, Organic Ligands and Rare Earth Ions: Energy Transfer, Encyclopedia of Materials: Science and Technology, 2001, ISBN 0-08-0431526, p.
6549.
[24] G.N. Dar, A. Umar, S.A. Zaidi, S. Baskoutas, Sw Hwang, M. Abaker, A. Al-Hajiry,
S.A. Al-Sayari, Ultra-high sensitive ammonia chemical sensor based on ZnO
nanopencils, Talanta 89 (2012) 155e161.
[25] P.M. Sirimanne, Yi-Bing Cheng, Inuence of some selected organic molecules
on intensity of photoluminescence of TiO2:Eu3 electrodes, J. Lumin 129
(2009) 563e565.
[26] P.M. Sirimanne, H. Tributsch, Thiocyanate ligands as crucial elements for
regeneration and photo-degradation in TiO2jdyejCuI solar cells, Mater. Chem.
Phy. 99 (2006) 5e9.

Please cite this article in press as: P.M. Sirimanne, H. Minoura, Red light emission from ZnO:Eu3jCuSCN hetero-junction under cathodic
polarization, Materials Chemistry and Physics (2015), http://dx.doi.org/10.1016/j.matchemphys.2015.10.001